KR102451298B1 - Photosensitive composition and method for forming cured film - Google Patents

Abstract

[PROBLEMS] An object is to provide a photosensitive composition in which the generation of foreign substances in the photosensitive composition is suppressed and capable of resolving a fine pattern favorably, and a method for forming a cured film using the photosensitive composition.
[Solution Means] An amine (E) is blended in a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (S), and an oxime as a photoinitiator (C) An ester compound (C1) and compounds (C2) other than an oxime ester compound are used in combination, and the amount of chloride ions in the photosensitive composition shall be 1000 weight ppm or less.

Description

The photosensitive composition and the formation method of a cured film TECHNICAL FIELD

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 needs to efficiently transmit light emitted from a light source such as a backlight. For this reason, in order to form an insulating film, the material which can form the film|membrane excellent in transparency is calculated|required.

Such a transparent insulating film is usually patterned on a substrate. As a method of forming a patterned transparent insulating film, for example, a method using a negative photosensitive composition comprising an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and an α-aminoalkylphenone-based photopolymerization initiator (patent) Reference 1) is known.

By the way, in recent years, the production amount of a color filter is also increasing along with the increase in the number of production units of a liquid crystal display, and the highly sensitive photosensitive composition which can form a pattern with the low exposure amount from a viewpoint of further productivity improvement is desired.

However, various functional films included in the color filter contain a colorant. When a coloring agent is contained in the photosensitive composition, when the alpha-amino alkylphenone type photoinitiator of patent document 1 is used, there exists a problem that it is difficult to obtain a sufficiently high sensitivity.

In such a situation, the present applicant is proposing a photosensitive composition containing an oxime ester compound of a specific structure as a photoinitiator as a photosensitive composition with high sensitivity (refer to Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 2012-173678 Japanese Patent Laid-Open No. 2012-189996 Japanese Patent Laid-Open No. 2012-189997

However, while the sensitivity is good in the photosensitive composition containing an oxime ester compound as a photoinitiator, there exists a problem that a foreign material is easy to generate|occur|produce in the photosensitive composition, or it is difficult to resolve a fine pattern at the time of development.

This invention was made in view of the above situation, and it aims at providing the photosensitive composition which generation|occurrence|production of the foreign material in a photosensitive composition is suppressed and can resolve a fine pattern favorably, and the formation method of the cured film using the said photosensitive composition.

The present inventors mix|blend an amine (E) with the photosensitive composition containing alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (S), and an oxime ester as a photoinitiator (C) By using a combination of a compound (C1) and a compound (C2) other than an oxime ester compound to make the amount of chloride ions in the photosensitive composition 1000 ppm by weight or less, it was found that the above problems could be solved, and the present invention was completed. 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 photoinitiator (C), a solvent (S), and an amine (E),

A photoinitiator (C) contains an oxime ester compound (C1) and a compound (C2) other than an oxime ester compound,

It is a photosensitive composition whose amount of chloride ions in the photosensitive composition is 1000 weight ppm or less.

A 2nd aspect of this invention apply|coats the photosensitive composition which concerns on 1st aspect on a board|substrate to form a coating film,

It is a formation method of a cured film including exposing a coating film.

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

«Photosensitive composition»

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

A photoinitiator (C) contains an oxime ester compound (C1) and compounds (C2) other than an oxime ester compound.

Moreover, the amount of chloride ions in the photosensitive composition is 1000 weight 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 (made by Thermo Scientific Dionex)

Eluent: Mixed solution of water and acetonitrile

Injection volume: 1 μL

The conventionally known photosensitive composition containing an oxime ester compound (C1) contained the chloride ion mainly derived from an oxime ester compound (C1). For this reason, content of the chloride ion in the conventional photosensitive composition had many things exceeding 1000 weight ppm.

Here, when this inventor investigated, it became clear that the high amount of chloride ions of the photosensitive composition is concerned with generation|occurrence|production of the foreign material in the photosensitive composition.

Moreover, while the sensitivity was favorable, the photosensitive composition containing only the oxime ester compound (C1) as a photoinitiator (C) was difficult to resolve a fine pattern at the time of image development after exposure.

Although this inventor also examined this point, it became clear that a fine pattern can be resolved using the photosensitive composition by using together an oxime ester compound (C1) with compounds other than an oxime ester compound (C1) with respect to a photoinitiator (C) lost.

As mentioned above, generation|occurrence|production of the foreign material in the photosensitive composition is suppressed, and said photosensitive composition can resolve a fine pattern favorably.

Hereinafter, the essential or arbitrary components contained in the photosensitive composition are demonstrated.

<Alkali-soluble resin (A)>

The alkali-soluble resin refers to a resin film having a thickness of 1 µm formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 wt%, and immersed in a KOH aqueous solution having a concentration of 0.05 wt% for 1 minute. , refers to a resin that melts with a film thickness of 0.01 µm or more.

As a suitable example of alkali-soluble resin (A), resin (A1) which has a cardo structure is mentioned. By using the photosensitive composition containing resin (A1) which has cardo structure as alkali-soluble resin (A), it is easy to form the cured film excellent in heat resistance, mechanical properties, solvent resistance, chemical resistance, etc. in a well-balanced way.

It does not specifically limit as resin (A1) which has a cardo structure, Conventionally well-known resin can be used.

Especially, resin represented by a following formula (a-1) is preferable.

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

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

Moreover, in said Formula ( ^a -1), Y<a> represents the residue which removed the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, anhydride glutaric acid etc. are mentioned.

Moreover, in said Formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

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

The weight average molecular weight of the resin (A1) having a cardo structure (Mw: a value measured in terms of polystyrene by gel permeation chromatography (GPC). The same is the same herein) is preferably 1000 or more and 40,000 or less, and 2000 or more and 30000 or less. more preferably. By setting it as said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

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 easy formation of a film excellent in mechanical strength or adhesion to a substrate.

Examples of the unsaturated carboxylic acid (a1) include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and the like. Among these, (meth)acrylic acid and maleic anhydride are preferable from points, such as copolymerization reactivity, alkali solubility of resin obtained, and availability. These unsaturated carboxylic acids (a1) can be used individually or in combination of 2 or more types.

The copolymer (A2) may be a copolymer of an unsaturated carboxylic acid (a1) and an alicyclic epoxy group-containing unsaturated compound (a2). It will not specifically limit, if it is an unsaturated compound which has an alicyclic epoxy group as an alicyclic epoxy group containing unsaturated compound (a2). The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, tetracyclododecyl group, etc. are mentioned. These alicyclic epoxy group containing unsaturated compounds (a2) can be used individually or in combination of 2 or more types.

Specifically, examples of the alicyclic epoxy group-containing unsaturated compound (a2) include compounds represented by the following formulas (a2-1) to (a2-15). Among these, in order to make developability suitable, the compound represented by following formula (a2-1) - (a2-5) is preferable, and the compound represented by following formula (a2-1) - (a2-3) is more desirable.

In the formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, t represents an integer of 0 or more and 10 or less. R ^a21 is preferably a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, -CH ₂ -Ph-CH ₂ -(Ph represents a phenylene group) is preferable.

The copolymer (A2) may be a copolymer obtained by copolymerizing an alicyclic group-containing unsaturated compound (a3) having no epoxy group with the unsaturated carboxylic acid (a1) and the alicyclic epoxy group-containing unsaturated compound (a2).

The alicyclic group-containing unsaturated compound (a3) is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These alicyclic group containing unsaturated compounds (a3) can be used individually or in combination of 2 or more types.

Specifically, examples of the alicyclic group-containing unsaturated compound (a3) include compounds represented by the following formulas (a3-1) to (a3-7). Among these, in order to make developability suitable, the compound represented by the following formulas (a3-3) - (a3-8) is preferable, and the compound represented by the following formula (a3-3) and (a3-4) is more desirable.

In the 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 is a hydrogen atom or 1 to 5 carbon atoms represents an alkyl group. R ^a24 is preferably a single bond, linear or branched alkylene group, for example, a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, or hexamethylene group. As R ^a25 , for example, a methyl group or an ethyl group is preferable.

In addition, the copolymer (A2) is an epoxy group-containing unsaturated compound having no alicyclic group together with the unsaturated carboxylic acid (a1) and the alicyclic epoxy group-containing unsaturated compound (a2), and additionally the alicyclic group-containing unsaturated compound (a3) ( A copolymer obtained by polymerizing a4) may be used.

Examples of the epoxy group-containing unsaturated compound (a4) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth). (meth)acrylic acid epoxy alkyl esters such as acrylate; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylic acid 6,7-epoxy α-alkyl acrylic acid epoxy alkyl esters such as heptyl; and the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate are preferable from the viewpoint of copolymerization reactivity and strength of the resin after curing. do. These epoxy-group containing unsaturated compounds (a4) can be used individually or in combination of 2 or more types.

Further, the copolymer (A2) may be a copolymer obtained by further polymerizing a compound other than the above. Examples of such other compounds include (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds can be used individually or in combination of 2 or more types.

Examples of (meth)acrylic acid esters include linear or branched methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Chain alkyl (meth) acrylate; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylic a rate, benzyl (meth)acrylate, and puffril (meth)acrylate; etc. are mentioned.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl ( Meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate; allyloxyethanol; etc. can be heard

Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl Ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurpril vinyl ether alkyl vinyl ethers such as; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; .

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl acetate. , vinylacetoacetate, vinyllactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrene include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene Alkoxy styrene such as , acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene; chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromostyrene, halostyrenes such as dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; can

It is preferable that they are 1 weight% or more and 50 weight% or less, and, as for the ratio of the structural unit derived from the said unsaturated carboxylic acid (a1) to a copolymer (A2), it is more preferable that they are 5 weight% or more and 45 weight% or less.

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

In addition, when the copolymer (A2) contains a structural unit derived from the alicyclic group-containing unsaturated compound (a3), the proportion of the structural unit derived from the alicyclic group-containing unsaturated compound (a3) in the copolymer (A2) is It is preferable that it is 1 weight% or more and 30 weight% or less, and it is more preferable that it is 5 weight% or more and 20 weight% or less.

It is preferable that they are 2000 or more and 200000 or less, and, as for the weight average molecular weight of a copolymer (A2), it is more preferable that they are 3000 or more and 30000 or less. By setting it as said range, there exists a tendency for it easy to balance the film-forming ability of a photosensitive composition, and developability after exposure.

Moreover, as alkali-soluble resin (A), the copolymer (A3) which has at least the structural unit which has the structural unit derived from the said unsaturated carboxylic acid (a1), and the structural unit which has the polymerizable site|part of the photopolymerizable compound (B) mentioned later, or the said unsaturated carboxylic acid A structural unit derived from (a1), a structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) and/or an epoxy group-containing unsaturated compound (a4), and a photopolymerizable compound (B) described later. Resin containing the copolymer (A4) which has at least a unit can also be used suitably. When alkali-soluble resin (A) contains a copolymer (A3) or a copolymer (A4), the adhesiveness to the board|substrate of the film|membrane formed using the photosensitive composition, and the mechanical strength of the cured film obtained using the photosensitive composition can be raised.

Copolymer (A3) and copolymer (A4) are (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes described as other compounds for copolymer (A2). A copolymer obtained by further copolymerizing the same may be used.

It is preferable that the structural unit which has a polymerization site|part with a photopolymerizable compound (B) has an ethylenically unsaturated group as a site|part which can superpose|polymerize with a photopolymerizable compound (B). Copolymerization having such a structural unit, for the copolymer (A3), at least a part of the carboxyl groups contained in the polymer containing the structural unit derived from the unsaturated carboxylic acid (a1) and the alicyclic epoxy group-containing unsaturated compound (a2) and / Or it can prepare by making an epoxy-group containing unsaturated compound (a4) react. Further, the copolymer (A4) is a copolymer having a structural unit derived from the unsaturated carboxylic acid (a1) and a structural unit derived from an alicyclic epoxy group-containing unsaturated compound (a2) and/or an epoxy group-containing unsaturated compound (a4). It can prepare by making at least one part of epoxy groups of , and an unsaturated carboxylic acid (a1) react.

1 weight% or more and 50 weight% or less are preferable, and, as for the ratio which the structural unit derived from the unsaturated carboxylic acid (a1) in a copolymer (A3) occupies, 5 weight% or more and 45 weight% or less are more preferable. In the copolymer (A3), the proportion of the structural unit having a polymerization site with the photopolymerizable compound (B) is preferably 1% by weight or more and 45% by weight or less, and more preferably 5% by weight or more and 40% by weight or less. desirable. When a copolymer (A3) contains each structural unit in such a ratio, it is easy to obtain the photosensitive composition which can form the film|membrane excellent in adhesiveness with a board|substrate.

1 weight% or more and 50 weight% or less are preferable, and, as for the ratio which the structural unit derived from the unsaturated carboxylic acid (a1) occupies in a copolymer (A4), 5 weight% or more and 45 weight% or less are more preferable. The proportion of structural units derived from the alicyclic epoxy group-containing unsaturated compound (a2) and/or the epoxy group-containing unsaturated compound (a4) in the copolymer (A4) is preferably 20 wt% or more, and 50 wt% or more 95 It is more preferable that it is weight % or less, and it is still more preferable that it is 60 weight% or more and 80 weight% or less.

In the copolymer (A4), the proportion of the structural unit having a polymerization site with the photopolymerizable compound (B) is preferably 1% by weight or more and 45% by weight or less, and more preferably 5% by weight or more and 40% by weight or less. desirable. When a copolymer (A4) contains each structural unit in such a ratio, it is easy to obtain the photosensitive composition which can form the film|membrane excellent in adhesiveness with a board|substrate.

It is preferable that they are 2000 or more and 50000 or less, and, as for the weight average molecular weights of a copolymer (A3) and a copolymer (A4), it is more preferable that they are 5000 or more and 30000 or less. By setting it as said range, there exists a tendency for it easy to balance the film-forming ability of a photosensitive composition, and developability after exposure.

The content of the alkali-soluble resin (A) is preferably 40 wt% or more and 85 wt% or less, and more preferably 45 wt% or more and 75 wt% or less, based on the weight of the photosensitive composition excluding the weight of the solvent (S) to be described later. Moreover, when alkali-soluble resin (A) makes the total amount of content of alkali-soluble resin (A), content of photopolymerizable compound (B), and content of photoinitiator (C) 100 weight part, the photopolymerizable compound in a photosensitive composition It is preferable to mix|blend with the photosensitive composition so that content of (B) may become 5 weight part or more and 50 weight part or less.

As described above, the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. For this reason, the amount of chloride ions in alkali-soluble resin (A) also needs to 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 after preparing a solution of the alkali-soluble resin (A), the obtained solution is brought into contact with an anion exchange resin method and the like.

<Photopolymerizable compound (B)>

As the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group can be preferably used. Monofunctional monomers and polyfunctional monomers exist in the monomer which has this ethylenically unsaturated group.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citracone Acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Rate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydropuffril (meth) Acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl ( and meth)acrylate and half (meth)acrylate of a phthalic acid derivative. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ( meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryl) Roxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene Glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycy dilether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate), methylenebis Polyfunctional monomers, such as condensate of (meth)acrylamide, (meth)acrylamide methylene ether, polyhydric alcohol, and N-methylol (meth)acrylamide, triacryl formal, etc. are mentioned. These polyfunctional monomers can be used individually or in combination of 2 or more types.

Among the monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer is preferable, and a tetrafunctional or higher polyfunctional monomer is more preferable from the viewpoint of increasing the adhesiveness of the photosensitive composition to the substrate and the strength after curing of the photosensitive composition. and a polyfunctional monomer having 5 or more functions is more preferable.

The content of the photopolymerizable compound (B) in the composition is preferably 1 wt% or more and 50 wt% or less, more preferably 5 wt% or more and 40 wt% or less, based on the weight of the photosensitive composition excluding the weight of the solvent (S) to be described later. do. By setting it as said range, there exists a tendency for a sensitivity, developability, and the balance of resolution to be easy to achieve.

As described above, the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. For this reason, the amount of chloride ions in the photopolymerizable compound (B) also needs to be reduced to some extent.

As a method of reducing the amount of chloride ions in the photopolymerizable compound (B), washing with water, an organic solvent, an aqueous solution of an organic solvent, etc., distillation, recrystallization, preparing a solution of alkali-soluble resin (A), and then anion exchange the obtained solution The method of making it contact with resin, etc. are mentioned.

<Photoinitiator (C)>

The photosensitive composition contains a photoinitiator (C). A photoinitiator (C) contains an oxime ester compound (C1) combining compounds (C2) other than an oxime ester compound. Hereinafter, an oxime ester compound (C1) and a compound (C2) are demonstrated.

(Oxime ester compound (C1))

The photosensitive composition essentially contains the oxime ester compound (C1) as a photoinitiator. As an oxime ester compound (C1), it is a compound which acts as a photoinitiator, If it is a compound which contains an esterified oxime group and acts as a photoinitiator, it will not specifically limit.

Typically, as an oxime ester compound (C1), the compound represented by following formula (1) is used suitably.

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

and a compound represented by For this reason, the photosensitive composition is excellent in sensitivity.

However, when only the oxime ester compound (C1) is used as a photoinitiator (C), it is difficult to resolve a fine pattern. In contrast to this, when an oxime ester compound (C1) and a compound (C2) other than an oxime ester compound are used together as a photoinitiator (C), it is easy to remodel a fine pattern by image development, having favorable sensitivity.

The photoinitiator (C) may contain the oxime ester compound (C1) in combination of 2 or more types.

In the formula (1), examples of the organic group suitable as R ¹ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, and a substituent The phenoxy group which may have, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, a substituent The naphthoxy group which may have, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the hetero which may have a substituent and a cyclyl group, an optionally substituted heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

Moreover, as R< ¹ >, the phenylthioalkyl group which may have a substituent on the cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the aromatic ring is preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R< ¹ > may have.

When R< ¹ > is an alkyl group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkyl group, 1 or more and 6 or less are more preferable. Moreover, when R< ¹ > is an alkyl group, linear or branched may be sufficient as it. Specific examples of the case in which R ¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopene. tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n - A decyl group, an isodecyl group, etc. are mentioned. Moreover, when R< ¹ > is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R< ¹ > is an alkoxy group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxy group, 1 or more and 6 or less are more preferable. Moreover, when R< ¹ > is an alkoxy group, linear or branched may be sufficient as it. Specific examples when R ¹ is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. Moreover, when R< ¹ > is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R< ¹ > is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3 or more and 6 or less are more preferable. Specific examples when R ¹ 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 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 acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples of the case in which R ¹ is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, and an n-hexanoyl group. , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples in the case where R ¹ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropano group. yloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R< ¹ > is an alkoxycarbonyl group, 2 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxycarbonyl group, 2 or more and 7 or less are more preferable. Specific examples when R ¹ is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Moreover, when R< ¹ > is a naphthylalkyl group, 11 or more and 20 or less are preferable and, as for the number of carbon atoms of a naphthylalkyl group, 11 or more and 14 or less are more preferable. 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 a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or the naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of condensed rings is limited to three. A heterocyclyl group may be an aromatic group (heteroaryl group), or a non-aromatic contribution may be sufficient as it. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine. Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ¹ is a heterocyclyl group.

When R ¹ is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and 2 or more and 21 or less carbon atoms. A saturated aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 or more and 20 or less carbon atoms which may have a substituent, a naphthyl group which may have a substituent, naph which may have a substituent A toyl group, a C11 or more and 20 or less naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as for R ¹ . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ have a further substituent, the substituent includes an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group. , phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent , phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naph which may have a substituent Toyloxy group, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, heterocyclylcarbonyl group which may have a substituent, amino group, amino group substituted with 1 or 2 organic groups, morpholin-1-yl group , a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group included 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, 1 or more and 20 or less carbon atoms are preferable, and 1 or more and 6 or less carbon atoms are more preferable. When a substituent is an alkyl group, linear or branched chain may be sufficient as it. Specific examples when the substituent is an alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group , sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- A decyl group, an isodecyl group, etc. are mentioned. Moreover, when a substituent is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When the substituent is an alkoxy group, 1 or more and 20 or less carbon atoms are preferable, and 1 or more and 6 or less carbon atoms are more preferable. Moreover, when a substituent is an alkoxy group, linear or branched may be sufficient as it. Specific examples when the substituent is an alkoxy group include a methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. Moreover, when a substituent is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When a substituent is a cycloalkyl group or a cycloalkoxy group, C3 or more and 10 or less are preferable, and C3 or more and 6 or less are more preferable. Specific examples when the substituent 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 in the case where 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 a substituent is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, C2 or more and 20 or less are preferable, and C2 or more and 7 or less are more preferable. Specific examples when the substituent is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when the substituent is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoyloxy group Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When a substituent is an alkoxycarbonyl group, C2 or more and 20 or less are preferable, and C2 or more and 7 or less are more preferable. Specific examples when the substituent is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyl group Oxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec -octyloxyrcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When the substituent is a phenylalkyl group which may have a substituent, 7 or more and 20 or less carbon atoms are preferable, and 7 or more and 10 or less are more preferable. Moreover, when a substituent is a naphthylalkyl group which may have a substituent, C11 or more and 20 or less are preferable, and C11 or more and 14 or less are more preferable. Specific examples in the case where the substituent is a phenylalkyl group which may have a substituent include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where the substituent is an optionally substituted naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. can be heard

When the substituent is a heterocyclyl group which may have a substituent, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclic ring obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring is a cyclyl group. When the heterocyclyl group is a condensed ring, the number of condensed rings is set to three. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine. Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, and quinoxaline; and the like.

When the substituent is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and a saturated group having 2 or more and 20 or less carbon atoms. An aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphtho which may have a substituent A diyl, a C11 or more and 20 or less naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as those exemplified for the substituents above. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

In the above substituent, examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic acyl group having 2 or more and 7 or less; Alkoxycarbonyl group having 2 or more and 7 or less carbon atoms; Saturated aliphatic acyloxy group having 2 or more and 7 or less carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; Carbon atom A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 or more and 6 or less, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkyl having an alkyl group having 1 or more and 6 or less carbon atoms Amino group; Dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen atom; nitro group; cyano group. When the phenyl group, naphthyl group, heterocyclyl group, etc. included in the above substituent have additional substituents, the number of the substituents is not limited within the scope not impairing the object of the present invention, but preferably 1 or more and 4 or less. When a phenyl group, a naphthyl group, a heterocyclyl group, etc. have several substituents, the some substituent may be same or different.

Among the organic groups, R ¹ is preferably an alkyl group, a cycloalkyl group, a phenyl group or cycloalkylalkyl group which may have a substituent, or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and the 2-methylphenyl group is more preferable. 5 or more and 10 or less are preferable, as for the number of carbon atoms of the cycloalkyl group contained in a cycloalkylalkyl group, 5 or more and 8 or less are more preferable, 5 or 6 are especially preferable. 1 or more and 8 or less are preferable, as for the number of carbon atoms of the alkylene group contained in a cycloalkylalkyl group, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. 1 or more and 8 or less are preferable, as for the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferable.

Moreover, as R< ¹ >, the group represented by -A ^c1 -CO-OA ^c2 is preferable. A ^c1 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ^c2 is a monovalent organic group, and it is preferable that it is a monovalent|monohydric hydrocarbon group.

When A ^c1 is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When A ^c1 is an alkylene group, 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkylene group, 1 or more and 6 or less are more preferable, and 1 or more and 4 or less are especially preferable.

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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, and a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

Suitable specific examples of the group represented by -A ^c1 -CO-OA ^c2 include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxy group Carbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n- Propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycar A bornyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned. have.

As mentioned above, although R< ¹ > was demonstrated, the group represented by a following formula (c1a) or (c1b) as R< ¹ > is preferable.

(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 may be bonded to each other to form a ring, q 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 (r+3) or less, and R ⁹ is organic)

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

When R ⁷ and R ⁸ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As the group represented by the formula (c1a), suitable examples of the group in which R ⁷ and R ⁸ form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In said formula (c1a), p is an integer of 0 or more and 4 or less, It is preferable that it is 0 or 1, and it is more preferable that it is 0.

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

Among the organic groups as R ⁹ , an alkyl group is preferable. The alkyl group may be linear or branched. 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkyl group, 1 or more and 5 or less are more preferable, 1 or more and 3 or less are especially preferable. As R< ⁹ >, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are illustrated preferably, Among these, it is more preferable that it is a methyl group.

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

In Formula (1), R< ² > is an organic group. As such an organic group, the aryl group which may have a substituent, or the 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 the heteroaryl group which may have a substituent, the carbazolyl group which may have a substituent is mentioned, for example.

In ^R2 , the substituent which an aryl group, a heteroaryl group, a phenyl group, or a carbazolyl group may have is not specifically limited in the range which does not impair the objective of this invention. Examples of suitable substituents which the aryl group, heteroaryl group, phenyl group or carbazolyl group may have on a carbon atom include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group. , phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent , phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naph which may have a substituent Toyloxy group, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, heterocyclylcarbonyl group which may have a substituent, amino group, amino group substituted with 1 or 2 organic groups, morpholin-1-yl group , a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ² is a heteroaryl group or a carbazolyl group, examples of suitable substituents that the heteroaryl group may have on a heteroatom such as a nitrogen atom, and suitable substituents that the carbazolyl group may have on a nitrogen atom include an alkyl group, cyclo An alkyl group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. have. Among these substituents, an alkyl group is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is still more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the aryl group, heteroaryl group, phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. The phenylalkyl group which may have, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with 1 or 2 organic groups are the same as those described for R ¹ .

In the above substituents, the substituents in the case where the phenyl group, the naphthyl group, and the heterocyclyl group further have a substituent are the same as those described for R ¹ .

In R ² , the group represented by the following formula (1-1) or (1-2) is preferable, and the group represented by the following formula (1-1) is more preferable from the viewpoint that the photosensitive composition has excellent sensitivity, and the following As the group represented by the formula (1-1), a group in which A is S is particularly preferable.

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

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

When a pattern is formed using a photosensitive composition, it is easy to produce coloring in a pattern by the heating in the post-baking process at the time of pattern formation. However, in the photosensitive composition, when using the oxime ester compound represented by the formula (1) as a photoinitiator, R ² is a group represented by the formula (1-1), and A is a group of S, the pattern by heating It is easy to suppress coloration.

When R< ⁴ > in Formula (1-1) is an organic group, it can select from various organic groups within the range which does not impair the objective of this invention. Suitable examples of when R ⁴ in the formula (1-1) is an organic group include an alkyl group having 1 or more and 6 carbon atoms; an alkoxy group having 1 or more and 6 carbon atoms; a saturated aliphatic group having 2 or more and 7 or less carbon atoms. Actual group; Alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; An alkyl group having 1 to 6 carbon atoms, Mor A benzoyl group substituted by a group selected from the group consisting of a polyin-1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group of; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; and cyano group.

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

Moreover, in Formula (1-1), the integer of 0 or more and 3 or less is preferable, as for n, the integer of 0 or more and 2 or less is more preferable, It is especially preferable that it is 0 or 1. When n is 1, it is preferable that the bonding position of R ⁴ is para to the hand to which the phenyl group to which R ⁴ is bonded is bonded to the atom A.

R< ⁵ > in Formula (1-2) can be selected from various organic groups in the range which does not impair the objective of this 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, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms. , an alkoxycarbonyl group having 2 or more and 20 or less carbon atoms, an optionally substituted phenyl group, an optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally having 7 or more carbon atoms and 20 or less phenyl An alkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, which may have a substituent A heterocyclyl group, the heterocyclylcarbonyl group which may have a substituent, etc. are mentioned.

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

R< ⁶ > in Formula (1-2) is not specifically limited in the range which does not impair the objective of this invention, It can select from various organic groups. Specific examples of the group suitable as 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 heterocyclyl group. Among these groups as R ⁶ , a phenyl group which may have a substituent and a thienyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a thienyl group are particularly preferable.

When the phenyl group, the naphthyl group, and the heterocyclyl group included in R ⁴ , R ⁵ or R ⁶ further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. group, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms a monoalkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in R ⁴ , R ⁵ or R ⁶ further have a substituent, the number of the substituent is not limited within a range that does not impair the object of the present invention, but 1 or more 4 The following are preferable. When the phenyl group, naphthyl group, and heterocyclyl 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, An alkyl group and an aryl group are preferable. 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 substituent in the phenyl group which may have a substituent is the same as the substituent demonstrated for R< ¹ >.

As R ³ , an alkyl group and phenyl group having 1 or more and 6 or less carbon atoms 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.

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

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

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino 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,

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 or more and 6 or less carbon atoms)

In formula (c1), R ^c1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Suitable examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. , benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy which may have a substituent A group, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, and an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. In addition, the carbon atom number of the substituent which a substituent further has is not included in the carbon atom number of a substituent.

When R ^c1 is an alkyl group, 1 or more and 20 or less carbon atoms are preferable, and 1 or more and 6 or less carbon atoms are more preferable. Moreover, when R ^c1 is an alkyl group, linear or branched may be sufficient as it. Specific examples when R ^c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopene tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n - A decyl group, an isodecyl group, etc. are mentioned. Moreover, 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, 1 or more and 20 or less carbon atoms are preferable, and 1 or more and 6 or less carbon atoms are more preferable. Moreover, when R ^c1 is an alkoxy group, linear or branched may be sufficient as it. Specific examples when R ^c1 is an alkoxy group include a methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. Moreover, when R ^c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less carbon atoms are preferable, and 3 or more and 6 or less are more preferable. 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 acyl group or a saturated aliphatic acyloxy group, 2 or more and 20 or less carbon atoms are preferable, and 2 or more and 7 or less carbon atoms are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropano group yloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c1 is an alkoxycarbonyl group, 2 or more and 20 or less carbon atoms are preferable, and 2 or more and 7 or less carbon atoms are more preferable. Specific examples when R ^c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxyrcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, 7 or more and 20 or less carbon atoms are preferable, and 7 or more and 10 or less carbon atoms are more preferable. Moreover, when R ^c1 is a naphthylalkyl group, 11 or more and 20 or less carbon atoms are preferable, and 11 or more and 14 or less carbon atoms are more preferable. 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 a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. 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.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings to be condensed is set to up to three. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine. Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, and quinoxaline; and the like. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and 2 or more and 20 or less carbon atoms. A saturated aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 or more and 20 or less carbon atoms which may have a substituent, a naphthyl group which may have a substituent, naph which may have a substituent A toyl group, a C11 or more and 20 or less naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

When the phenyl group, naphthyl group and heterocyclyl group included in R ^c1 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 or more carbon atoms. A saturated aliphatic acyl group of 7 or less, an alkoxycarbonyl group of 2 or more and 7 or less, a saturated aliphatic acyloxy group of 2 or more and 7 or less of carbon atoms, a monoalkylamino group having an alkyl group of 1 or more and 6 or less of carbon atoms, a carbon atom and a dialkylamino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group having 1 or more and 6 or less alkyl groups. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

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

The position at which R ^c1 is bonded to the phenyl group is 4th when the position of the bond between the phenyl group and the main backbone of the oxime ester compound is the 1st position and the methyl group is 2nd position with respect to the phenyl group to which R ^c1 is bonded. Or 5th place is preferable and 5th place is more preferable. Moreover, the integer of 0 or more and 3 or less is preferable, as for n1, the integer of 0 or more and 2 or less is more preferable, 0 or 1 is especially preferable.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. Moreover, when R<^c2> is the carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted by the C1-C6 alkyl group.

In R ^c2 , the substituent included in the phenyl group or the carbazolyl group is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on a carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, The phenyl group which may have a substituent, the phenoxy group which may have a substituent, the phenylthio group which may have a substituent, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, A phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent , naphthoyloxy group which may have a substituent, naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, heterocyclyl group which may have a substituent, heterocyclylcarbonyl group which may have a substituent, amino group, 1 or an amino group substituted with an organic group of 2, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

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, a cycloalkyl group having 3 to 10 carbon atoms, and 2 carbon atoms. Saturated aliphatic acyl group with 20 or more, alkoxycarbonyl group with 2 or more and 20 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, carbon which may have a substituent A phenylalkyl group having 7 to 20 atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphtha having 11 to 20 carbon atoms which may have a substituent A tylalkyl group, the heterocyclyl group which may have a substituent, the heterocyclylcarbonyl group which may have a substituent, etc. are mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

For specific examples of the substituent which the phenyl group or carbazolyl group may have, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may have a substituent; The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with 1 or 2 organic groups are the same as that of R ^c1 .

In R ^c2 , examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the phenyl group or the carbazolyl group have a further substituent include an alkyl group having 1 or more and 6 or less carbon atoms; 1 to 6 alkoxy group; Saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group ; Benzoyl group; Naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 or more and 6 or less; a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; a cyano group. can When the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group have additional substituents, the number of the substituents is not limited in the range that does not impair the object of the present invention, but 1 or more and 4 or less is preferable When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c2 , the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable from the viewpoint of easy to obtain a photopolymerization initiator having excellent sensitivity, and the group represented by the following formula (c2) is more preferable, the following formula (c2) As the group represented by , a group in which A is S is particularly preferred.

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino 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)

When R ^c4 in Formula (c2) is an organic group, it can select from various organic groups within the range which does not impair the objective of this invention. Suitable examples when R ^c4 is an organic group in formula (c2) include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; alkyl group having 1 to 6 carbon atoms, morpholine- A benzoyl group substituted by a group selected from the group consisting of a 1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; An alkyl group having 1 to 6 carbon atoms a dialkylamino group having; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; and cyano group.

Among R ^c4 , a benzoyl group; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, and a benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group is more preferable.

Moreover, in Formula (c2), the integer of 0 or more and 3 or less is preferable, as for n3, the integer of 0 or more and 2 or less is more preferable, It is especially preferable that it is 0 or 1. When n3 is 1, it is preferable that the bonding position of R ^c4 is para to the hand at which the phenyl group to which R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom.

R ^c5 in formula (c3) can be selected from various organic groups in the range which does not impair the objective of this 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, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and an alkoxyalkyl group having 2 to 20 carbon atoms. , an alkoxycarbonyl group having 2 or more and 20 or less carbon atoms, an optionally substituted phenyl group, an optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally having 7 or more carbon atoms and 20 or less phenyl An alkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, which may have a substituent A heterocyclyl group, the heterocyclylcarbonyl group which may have a substituent, etc. are mentioned.

In R ^c5 , an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms is more preferred, and particularly preferred is 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 impaired, and can be selected from various organic groups. Specific examples of the group suitable as 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 heterocyclyl group. Among these groups as R ^c6 , an optionally substituted phenyl group or optionally substituted thienyl group is more preferable, and a 2-methylphenyl group or a thienyl group is particularly preferable.

When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 have a further substituent, the substituent includes an alkyl group having 1 or more and 6 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms. , a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atoms monoalkylamino group, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 further have a substituent, the number of the substituent is not limited within a range that does not impair the object of the present invention, but 1 or more 4 The following are preferable. When the phenyl group, naphthyl group and heterocyclyl 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 the 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 synthesize|combined according to the following Scheme 1, for example. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (c1-2) to obtain the following formula (c1-3) The ketone compound represented is obtained, and the obtained ketone compound (c1-3) is oximeated with hydroxyl amine to obtain an oxime compound represented by the following formula (c1-4), and then the oxime compound of the formula (c1-4) By acylating the hydroxyl group in it, the oxime ester compound represented by following formula (c1-7) can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c1-5) or an acid halide (R ^c3 COHal, Hal is a halogen) represented by the following formula (c1-6) is used. desirable. In addition, in the following formula (c1-2), Hal is halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4) and (c1-7) , R ^c1 , R ^c2 , R ^c3 and n1 are the same as in formula (c1).

<Scheme 1>

When n2 is 1, the oxime ester compound represented by Formula (c1) can be synthesize|combined according to the following Scheme 2, for example. Specifically, a nitrite ester represented by the following formula (c2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) is reacted with a ketone compound represented by the following formula (c2-1) in the presence of hydrochloric acid to obtain a keto oxime compound represented by the following formula (c2-3), followed by acylation of a hydroxyl group in the keto oxime compound represented by the following formula (c2-3) to an oxime represented by the following formula (c2-6) An ester compound can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c2-4) or an acid halide (R ^c3 COHal, Hal is a halogen) represented by the following formula (c2-5) is used. desirable. In addition, in the following formulas (c2-1), (c2-3), (c2-4), (c2-5) and (c2-6), R ^c1 , R ^c2 , R ^c3 and n1 represent the formula (c1 ) is the same as

<Scheme 2>

Further, in the oxime ester compound represented by formula (c1), when n2 is 1, R ^c1 is a methyl group, and R ^c1 is para to the methyl group bonded to the benzene ring to which R ^c1 is bonded, for example, For example, the compound represented by the following formula (c2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1. In addition, in the following formula (c2-7), R ^c2 is the same as that of the formula (c1).

The following PI-1 to PI-42 are mentioned as a compound especially suitable among the oxime ester compounds represented by Formula (c1).

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 each a chain alkyl group optionally having a substituent, a cyclic organic group optionally having a substituent, or a hydrogen atom, R ^c8 and R ^c9 are may combine with each other to form a ring, R ^c10 is a monovalent organic group, R ^c11 is an alkyl group having 1 to 11 carbon atoms which may have a substituent or an aryl group which may have a substituent, and n4 is 0 to 4 Integer below, n5 is 0 or 1)

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

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as in 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 fluorene ring in the formula (c4). In formula (c4), the bonding position of R ^c7 to the fluorene ring is not particularly limited. When 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 to the second position in the fluorene ring from the viewpoint of easy synthesis of the compound represented by the formula (c4). do. When plural R ^c7 is plural, plural R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as the object of the present invention is not impaired, and is 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 acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. , benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy which may have a substituent Group, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, a substituent The heterocyclylcarbonyl group which you may have, the amino group substituted by 1 or 2 organic groups, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned.

When R ^c7 is an alkyl group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkyl group, 1 or more and 6 or less are more preferable. Moreover, when R ^c7 is an alkyl group, linear or branched may be sufficient as it. Specific examples when R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isophene tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n - A decyl group, an isodecyl group, etc. are mentioned. 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c7 is an alkoxy group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxy group, 1 or more and 6 or less are more preferable. Moreover, when R ^c7 is an alkoxy group, linear or branched may be sufficient as it. Specific examples when R ^c7 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. Moreover, when R ^c7 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a meth Toxypropyloxy group, etc. are mentioned.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3 or more and 6 or less are more preferable. 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 acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropano group yloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c7 is an alkoxycarbonyl group, 2 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxycarbonyl group, 2 or more and 7 or less are more preferable. Specific examples when R ^c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^c7 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Moreover, when R ^<c7> is a naphthylalkyl group, 11 or more and 20 or less are preferable and, as for the number of carbon atoms of a naphthylalkyl group, 11 or more and 14 or less are more preferable. 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 a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. 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.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings to be condensed is set to up to three. A heterocyclyl group may be an aromatic group (heteroaryl group), or a non-aromatic contribution may be sufficient as it. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine. Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and 2 or more and 21 or less carbon atoms. A saturated aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 or more and 20 or less carbon atoms which may have a substituent, a naphthyl group which may have a substituent, naph which may have a substituent A toyl group, a C11 or more and 20 or less naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as for R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc. can be heard

When the phenyl group, naphthyl group and heterocyclyl group included in R ^c7 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 or more carbon atoms. A saturated aliphatic acyl group of 7 or less, an alkoxycarbonyl group of 2 or more and 7 or less, a saturated aliphatic acyloxy group of 2 or more and 7 or less of carbon atoms, a monoalkylamino group having an alkyl group of 1 or more and 6 or less of carbon atoms, a carbon atom and a dialkylamino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group having 1 or more and 6 or less alkyl groups. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but preferably 1 or more and 4 or less. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a nitro group or a group represented by R ^c12 -CO- because the sensitivity tends to improve. R ^c12 is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of the group suitable as 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 heterocyclyl group. Among these groups as R ^c12 , a 2-methylphenyl group, a thiophen-2-yl group and an α-naphthyl group are particularly preferable.

Moreover, transparency tends to become favorable that R ^c7 is a hydrogen atom, and it is preferable. In addition, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b), the transparency tends to be more favorable.

In formula (c4), R ^c8 and R ^c9 each represent 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, a chain alkyl group which may have a substituent as R ^c8 and R ^c9 is preferable. 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.

R ^c8 and when R ^c9 is a chain alkyl group having no substituent, 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, and particularly preferably 1 or more and 6 or less. Specific examples when R ^c8 and R ^c9 are a chain alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pene Tyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, iso A nonyl group, an n-decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c8 and R ^c9 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c8 and R ^c9 are a chain alkyl group having a substituent, 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, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain|strand-chain alkyl group which has a substituent is linear.

The substituent which an alkyl group may have is not specifically limited in the range which does not impair 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. A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as suitable examples in the case where R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as suitable examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and linear is preferable. 1 or more and 10 or less are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1 or more and 6 or less are more preferable.

When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of 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, 1 or more and 10 or less are preferable, and 1 or more and 6 or less are more preferable.

R ^c8 and when R ^c9 is a cyclic organic group, the cyclic organic group may have either an alicyclic contribution or an aromatic contribution. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are a cyclic organic group, the substituent which the cyclic organic group may have is the same as when R ^c8 and R ^c9 are a chain alkyl group.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring included in the aromatic hydrocarbon group is not particularly limited, and preferably 3 or less, more preferably 2 or less, and 1 is particularly desirable. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^c8 and R ^c9 are an aliphatic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3 or more and 20 or less are preferable, and 3 or more and 10 or less are more preferable. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group , a tetracyclododecyl group, and an adamantyl group.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring to be. When the heterocyclyl group is a condensed ring, the number of rings to be condensed is set to up to three. A heterocyclyl group may be an aromatic group (heteroaryl group), or a non-aromatic contribution may be sufficient as it. Heterocycles constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine. Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr talazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.

R ^c8 and R ^c9 may be bonded to each other to form a ring. The group consisting of a ring formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

When the group formed by bonding R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with the cycloalkylidene group 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, a thiophene ring, a pyrrole ring, a pyridine ring , a pyrazine ring, and a pyrimidine ring.

Among R ^c8 and R ^c9 described above, examples of suitable groups include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a straight-chain alkylene 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.

1 or more and 10 or less are preferable and, as for the number of carbon atoms of the linear alkylene group of A ¹ , 1 or more and 6 or less are more preferable. When ^A2 is an alkoxy group, linear or branched form may be sufficient as an alkoxy group, and linear form is preferable. 1 or more and 10 or less are preferable and, as for the number of carbon atoms of an alkoxy group, 1 or more and 6 or less are more preferable. When ^A2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A2 is ^a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable and, as for the halogen atom contained in a halogenated alkyl group, a fluorine atom, a chlorine atom, and a bromine atom are more preferable. The halogenated alkyl group may be linear or branched, and linear is preferable. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups which R ^c8 and R ^c9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups which R ^c8 and R ^c9 have as a substituent.

Suitable specific examples of R ^c8 and R ^c9 include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3- Methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8- Methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n Alkoxyalkyl groups such as hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano- Cyanoalkyl groups such as n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group ; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group and phenylalkyl groups such as 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group , 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclo Cyclos such as pentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group Alkylalkyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-me Toxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n- Propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group and alkoxycarbonylalkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-phene Tyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8- Chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n- Hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5- Halogenated alkyl groups, such as a heptafluoro-n-pentyl group, are mentioned.

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

Examples of a suitable organic group for ^{R c10} include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenyl group which may have a substituent, A phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent , an optionally substituted heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ^c7 . Moreover, as R<^c10> , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl 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 or cycloalkylalkyl group, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and the 2-methylphenyl group is more preferable. 5 or more and 10 or less are preferable, as for the number of carbon atoms of the cycloalkyl group contained in a cycloalkylalkyl group, 5 or more and 8 or less are more preferable, 5 or 6 are especially preferable. 1 or more and 8 or less are preferable, as for the number of carbon atoms of the alkylene group contained in a cycloalkylalkyl group, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. 1 or more and 8 or less are preferable, as for the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferable.

Moreover, as R ^c10 , the group represented by -A ³ -CO-OA ⁴ is preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. ^A4 is a monovalent organic group, and it is preferable that it is a monovalent|monohydric hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When A ³ is an alkylene group, 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkylene group, 1 or more and 6 or less are more preferable, and their 1 or more and 4 or less are especially preferable.

Suitable examples of A ⁴ 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 ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, and a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

Suitable specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxy group Carbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n- Propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycar A bornyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned. have.

Although R ^c10 has been described above, as R ^c10 , a group represented by the following formula (c4a) or (c4b) is preferable.

(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 may 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 (n6+3) or less, and R ^c15 is organic)

Examples of the organic group for R ^c13 and R c14 in the formula ( ^c4a ) are the same as for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. 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 1 is most preferable. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As the group represented by the formula (c4a), suitable examples of the group in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In said formula (c4a), n6 is an integer of 0 or more and 4 or less, It is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the formula (c4b), R ^c15 is an organic group. Examples of the organic group include the same groups as the organic groups described for R ^c7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1 or more and 10 or less are preferable, as for the number of carbon atoms of an alkyl group, 1 or more and 5 or less are more preferable, 1 or more and 3 or less are especially preferable. R ^c15 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and among these, a methyl group is more preferable.

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

In formula (c4), R ^c11 is a hydrogen atom, an optionally substituted C1-C11 alkyl group, or an optionally substituted aryl group. When R ^c11 is an alkyl group, a phenyl group, a naphthyl group, etc. are preferably exemplified as the substituent which may be included. Moreover, as a substituent which you may have when R ^<c7> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In formula (c4), R ^c11 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc., among these, A methyl group or a phenyl group is more preferable.

The compound represented by the formula (c4) converts an oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (c5) to an oxime ester group represented by >C=NO-COR ^c11 Manufactured by a method comprising a process. R ^c11 is the same as R ^c11 in formula (c4).

Conversion of an oxime group (>C=N-OH) to the oxime ester group represented by >C=NO-COR ^c11 is performed by making the compound represented by Formula (c5) mentioned above and an acylating agent react.

Examples of the acylating agent that imparts the acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

The compound represented by the general formula (c4) can be synthesized according to, for example, Scheme 3 below when n5 is 0. In Scheme 3, a fluorene derivative represented by the following formula (c3-1) is used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1) is a fluorene derivative in which the 9th position is substituted with R ^c8 and R ^c9 by a known method with a substituent R ^c7 can be obtained by introducing A fluorene derivative substituted with R ^c8 and R ^c9 at position 9 is, for example, when R ^c8 and R ^c9 are an alkyl group, as described in Japanese Patent Application Laid-Open No. Hei 06-234668, in the presence of an alkali metal hydroxide It can be obtained by reacting fluorene with an alkylating agent in an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to perform an alkylation reaction. , 9,9-alkyl substituted fluorene can be obtained.

The fluorene derivative represented by the formula (c3-3) can be obtained by introducing an acyl group represented by -CO-CH ₂ -R ^c10 to the fluorene derivative represented by the formula (c3-1) by Friedel-Crafts reaction. have. The acylating agent for introducing the acyl group represented by -CO-R ^c10 may be a halocarbonyl compound or an acid anhydride. As an acylating agent, the halocarbonyl compound represented by Formula (c3-2) is preferable. In formula (c3-2), Hal is a halogen atom. The position at which the acyl group is introduced onto the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or protecting and deprotecting at another position at the acylated position.

Next, the group represented by -CO-R ^c10 in the fluorene derivative represented by formula (c3-3) obtained is converted into a group represented by -C(=N-OH)-R ^c10 to obtain formula (c3-4) to obtain an oxime compound represented by The method for 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 formula (c3-4) and the acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5) or the acid halide (R ^c11 COHal, Hal) represented by the following formula (c3-6) is a halogen atom) to obtain a compound represented by the following formula (c3-7).

In addition, 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 in formula (c4).

Moreover, in Scheme 3, R ^c10 contained in each of Formula (c3-2), Formula (c3-3), and Formula (c3-4) may be same or different. That is, R ^c10 in the formulas (c3-2), (c3-3) and (c3-4) may undergo chemical modification in the synthesis process shown as Scheme 3. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. Chemical formulas that R ^c10 may accept are not limited to these.

<Scheme 3>

When n5 is 1, the compound represented by formula (c4) can be synthesized according to, for example, Scheme 4 below. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. The fluorene derivative represented by formula (c4-1) is acyl represented by -CO-CH ₂ -R ^c10 by Friedel-Crafts reaction with the compound represented by formula (c3-1) by the same method as in Scheme 3 It can be obtained by introducing The acylating agent is preferably a carboxylic acid halide represented by the formula (c3-8): Hal-CO-CH ₂ -R ^c10 . Then, the methylene group present between R ^c10 and the carbonyl group in the compound represented by the formula (c4-1) is oximelated to obtain a ketoxime compound represented by the following formula (c4-3). The method for oximating the methylene group is not particularly limited, but a method of reacting a nitrite ester represented by the following general formula (c4-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid is desirable. Then, the ketooxime compound represented by the following formula (c4-3) and the acid anhydride (R ^c11 CO) ₂ O) represented by the following formula (c4-4) or an acid represented by the following formula (c4-5) A compound represented by the following formula (c4-6) can be obtained by reacting a halide (R ^c11 COHal, Hal is a halogen atom). In addition, in the following formulas (c4-1), (c4-3), (c4-4), (c4-5) and (c4-6), R ^c7 , R ^c8 , R ^c9 , R ^c10 and R ^c11 is the same as in formula (c4).

When n5 is 1, there exists a tendency which generation|occurrence|production of the foreign material in the pattern formed using the photosensitive composition containing the compound represented by Formula (c4) can be reduced more.

Moreover, in Scheme 4, R ^c10 contained in each of Formula (c3-8), Formula (c4-1), and Formula (c4-3) may be same or different. That is, R ^c10 in formulas (c3-8), (c4-1), and (c4-3) may undergo chemical modification in the synthesis process shown in Scheme 4. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. Chemical formulas that R ^c10 may accept are not limited to these.

<Scheme 4>

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

As described above, the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. For this reason, the amount of chloride ions in a photoinitiator (C) also needs to be reduced to some extent.

In this point, an oxime ester compound (C1) originates in the manufacturing method, and especially tends to contain a chloride ion. For this reason, purification of an oxime ester compound (C1) is important.

As a method of reducing the amount of chloride ions in the oxime ester compound (C1),

1) synthesizing the oxime ester compound (C1) by a method including a step of conducting a Friedel Crafts reaction using aluminum chloride, and adjusting the amount of aluminum chloride used so that the chloride ion content of the oxime ester compound is reduced Way,

2) a method of using an acid containing no chlorine atom in the synthesis of the compound represented by the oxime ester compound (C1);

3) In the synthesis of the compound represented by the oxime ester compound (C1), a method of using an acid anhydride as an acylating agent in a Friedel-Crafts acylation reaction or acylation of an oxime group;

4) a method of purifying the crude purified product of the compound represented by the oxime ester compound (C1) by at least one method selected from the group consisting of distillation, recrystallization, washing and column chromatography;

5) a method of recovering the compound represented by the oxime ester compound (C1) from the washed solution after washing a solution in which a prepared product of the compound represented by the oxime ester compound (C1) is dissolved in a hydrophobic organic solvent; and

6) A method of recovering the oxime ester compound (C1) after treating a solution obtained by dissolving a prepared product of the compound represented by the oxime ester compound (C1) in a hydrophobic organic solvent with an anion exchange resin.

(Compound (C2))

A photosensitive composition contains compounds (C2) other than an oxime ester compound with the oxime ester compound (C1) mentioned above as a photoinitiator (C). The kind of compound (C2) is not specifically limited as long as it is not an oxime ester compound but can act as a photoinitiator.

Specifically, as the compound (C2), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) )phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4- dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-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-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulf Feed, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid , benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro- 4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercapto Benzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, 2-(o-chlorophenyl)-4 , 5-diphenylimidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzo Phenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, Benzoinbutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p -Dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenyla Creidine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p- Methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5) -Methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis( Trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2 -(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis (trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl -6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-tri and azine and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. These photoinitiators can be used individually or in combination of 2 or more types.

Among them, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, 2-( imidazole compounds such as o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 2-methyl-1-[4-(methyl Alkylphenone compounds such as thio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one are preferred. Among the alkylphenone compounds, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) ?-aminoalkylphenone compounds such as )-butan-1-one are preferred.

It is preferable to refine|purify similarly to an oxime ester compound (C1) with respect to a compound (C2), and to reduce a chloride ion.

The content of the photoinitiator (C) is preferably 0.5 wt% or more and 30 wt% or less, more preferably 1 wt% or more and 20 wt% or less, based on the weight of the photosensitive composition excluding the weight of the solvent (S) to be described later. By making content of a photoinitiator (C) into said range, the photosensitive composition which the defect of a pattern shape does not produce easily can be obtained.

The content of the oxime ester compound (C1) in the photoinitiator (C) is preferably 10% by weight or more and 99.5% by weight or less with respect to the weight of the photoinitiator (C) from the viewpoint of making it easy to achieve both good sensitivity and good resolution, 30 wt% or more and 97 wt% or less are more preferable, and 50 wt% or more and 95 wt% or less are particularly preferable. The content of the compound (C2) in the photoinitiator (C) is preferably 0.5 wt% or more and 90 wt% or less, more preferably 1 wt% or more and 60 wt% or less, and particularly preferably 10 wt% or more and 40 wt% or less do.

Moreover, you may combine a photoinitiation adjuvant with a photoinitiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10 -diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxy Thiol compounds, such as benzothiazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, etc. are mentioned. These photoinitiation adjuvants can be used individually or in combination of 2 or more types.

<Colorant (D)>

The photosensitive composition may contain the coloring agent (D). It does not specifically limit as a coloring agent (D). As the colorant (D), for example, a compound classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colorists), specifically, the color index (C.I.) number as follows It is preferable to use the attached compound.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and only numbers are 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 can be heard

Examples of orange pigments that can be suitably used include C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, and only numbers are 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 purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the numbers are described), 19, 23, 29, 30, 32,36, 37, 38, 39, 40, and 50 are mentioned.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only numbers are 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 C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the numbers are described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66 can be heard

Examples of pigments other than the above that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Black pigments, such as Pigment Black 7, are mentioned.

Moreover, the photosensitive composition may contain the light-shielding agent as a coloring agent (D). The photosensitive composition containing a light shielding agent is used suitably for formation of the black matrix or black column spacer in a liquid crystal display panel, and bank formation for the light emitting layer division in organic electroluminescent element.

When using a colorant (D) as a light-shielding agent, it is preferable to use a black pigment or a purple pigment as a light-shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides such as silver, complex oxides, metal sulfides, Various pigments are mentioned regardless of organic substances, such as a metal lactate and a metal carbonate, and an inorganic substance.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used. Moreover, you may use resin-coated carbon black.

As carbon black, carbon black which has been subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity according to Bronsted's definition. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation which forms a salt with an acidic group is not specifically limited in the range which does not impair the objective of this invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions and lithium ions and ammonium ions are preferable.

Among the carbon blacks subjected to the treatment for introducing an acidic group described above, from the viewpoint of achieving high resistance of a light-shielding cured film formed using the photosensitive composition, from the group consisting of a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, and a sulfonic acid base Carbon black having one or more selected functional groups is preferred.

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

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

2) A method of diazo coupling an organic compound having an amino group and an acid group and carbon black.

3) A method in which an organic compound having a halogen atom and an acid group and carbon black having a hydroxyl group are reacted by the etherification method of Williamson.

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

5) A method in which a Friedel-Crafts reaction is performed on carbon black using an organic compound having an acidic group protected by a halocarbonyl group and a protecting group, followed by deprotection.

Among these methods, method 2) is preferable because the acidic group introduction treatment is easy and safe. As the organic compound having an amino group and an acid group used in method 2), a compound in which an amino group and an acid group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acid, such as sulfonyl acid, or aminobenzoic acid, such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. 1 mmol or more and 200 mmol or less are preferable with respect to 100 g of carbon black, and, as for the mole number of the acidic group introduce|transduced into carbon black, 5 mmol or more and 100 mmol or less are more preferable.

The carbon black into which an acidic group has been introduced may be coated with a resin.

When using the photosensitive composition containing carbon black coat|covered with resin, it is excellent in light-shielding property and insulation, and it is easy to form the light-shielding cured film with low surface reflectance. Moreover, the adverse effect with respect to the dielectric constant of the light-shielding cured film formed using the photosensitive composition by the coating process with resin in particular does not arise. Examples of the resin that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate , polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyallylate, polyether and thermoplastic resins such as ether ketone. As for the coating amount of resin with respect to carbon black, 1 weight% or more and 30 weight% or less are preferable with respect to the sum total of the weight of carbon black and weight of 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) can be heard In a commercial item, product names K0084 and K0086 by BASF Corporation, Pigment Black 21, 30, 31, 32, 33, 34, etc. can be used preferably as a perylene type pigment.

In the 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 acetyl group. .

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 or an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S or P. When R ^d7 and R ^d8 are an alkyl group, the alkyl group 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) include, for example, Japanese Patent Application Laid-Open No. 62-1753; It can be synthesized using the method described in Japanese Patent Application Laid-Open No. 63-26784. That is, using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials, heating reaction is performed in water or an organic solvent. Then, the target product can be obtained by recrystallizing the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to disperse the perylene-type pigment favorably in the photosensitive composition, it is preferable that the average particle diameters of a perylene-type pigment are 10 nm or more and 1000 nm or less.

Moreover, a lactam type pigment can also be included as a light-shielding agent. As a lactam 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 each independently represents an E or Z form as a geometric isomer, and R ^d9 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, or chlorine An atom, a fluorine atom, a carboxy group or a sulfo group is represented, 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) can be used individually or in combination of 2 or more type.

R ^d9 is preferably bonded to the 6th position of the dihydroindrone ring from the viewpoint of easy preparation of the compound represented by the formula (d-4), and R ^d11 is preferably bonded to the 4th position of the dihydroindrone ring. 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 form, a ZZ form, and an EZ form as geometric isomers, but any single compound of these may be used, or a mixture of these geometric isomers may be sufficient.

The compound represented by a formula (d-4) can be manufactured by the method of international publication 2000/24736 and international publication 2010/081624, for example.

In order to disperse|distribute the lactam type pigment favorably in a composition, it is preferable that the average particle diameter of a lactam type pigment is 10 nm or more and 1000 nm or less.

Further, fine particles containing a silver tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as a light-shielding agent. This AgSn alloy fine particle is preferably an AgSn alloy as a main component, and Ni, Pd, Au, etc. may be contained as another metal component, for example.

As for the average particle diameter of this AgSn alloy fine particle, 1 nm or more and 300 nm or less are preferable.

When the AgSn alloy is represented by the formula AgxSn, the range of x in which a chemically stable AgSn alloy is obtained is 1≤x≤10, and the range of x in which chemical stability and blackness are obtained simultaneously is 3≤x≤4.

Here, if the weight ratio of Ag in the AgSn alloy is obtained in the range of x,

For x=1, Ag/AgSn = 0.4762

For x=3, 3 Ag/Ag3Sn = 0.7317

For x=4, 4 Ag/Ag4Sn = 0.7843

For x=10, 10 Ag/Ag10Sn = 0.9008

becomes this

Therefore, this AgSn alloy is chemically stable when it contains 47.6 wt% or more and 90 wt% or less of Ag, and when it contains 73.17 wt% or more and 78.43 wt% or less of Ag, chemical stability and blackness are effectively improved with respect to the amount of Ag. can be obtained

These AgSn alloy fine particles can be produced using a normal fine particle synthesis method. Examples of the method for synthesizing the fine particles include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

Although the insulation of AgSn alloy fine particles is high, depending on the use of the photosensitive composition, in order to further improve insulation, you may make it cover the surface with an insulation film. A metal oxide or an organic polymer compound is suitable as a material for such an insulating film.

As the metal oxide, a metal oxide having insulating properties, for example, silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc. are preferably used. .

Moreover, as an organic high molecular compound, resin which has insulation, for example, polyimide, polyether, polyacrylate, a polyamine compound, etc. are used suitably.

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

The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, the use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform thickness can be formed at a relatively low temperature.

As a light-shielding agent, the above-mentioned perylene-type pigment, a lactam-type pigment, and AgSn alloy microparticles|fine-particles may be used individually, and you may use these in combination.

In addition, the light-shielding agent may contain the pigment|dye of hues, such as red, blue, green, and yellow, with said black pigment and a purple pigment for the objective of color tone adjustment etc. The pigment|dye of a color other than a black pigment and a purple pigment can be suitably selected from well-known pigment|dye. For example, as a pigment|dye of color other than a black pigment or a purple pigment, the said various pigment can be used. 15 weight% or less is preferable with respect to the total weight of a light-shielding agent, and, as for the usage-amount of the pigment|dye of other colors other than a black pigment and a purple pigment, 10 weight% or less is more preferable.

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

Moreover, it originates in decomposition|disassembly of a dispersing agent, and a corrosive gas may generate|occur|produce from the cured film of a photosensitive composition. For this reason, it is preferable that a coloring agent be disperse|distributed without using a dispersing agent.

In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, respectively, but when used in combination, the organic pigment is used in the range of 10 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the total amount of the inorganic pigment and the organic pigment. It is preferable, and it is more preferable to use in the range of 20 weight part or more and 40 weight part or less.

In addition, the photosensitive composition can use dye other than a pigment as a coloring agent (D). What is necessary is just to select this dye suitably from well-known materials.

As the dye applicable to the photosensitive composition of the present embodiment, for example, azo dye, metal complex salt azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, cyanine dye, naphthoquinone dye, quinoneimine dye, methine A dye, a phthalocyanine dye, etc. are mentioned.

Moreover, about these dyes, it can be disperse|distributed to an organic solvent etc. by laking (salt formation), and this can be used as a coloring agent (D).

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

These dyes can also be used in combination with the above-mentioned pigments (for example, perylene pigments, lactam pigments, AgSn alloy fine particles, etc.).

The amount of the colorant (D) used in the photosensitive composition can be appropriately selected within a range that does not impair the object of the present invention, and typically 5% by weight or more and 70% by weight or less with respect to the total weight of the solid content of the photosensitive composition, and , more preferably 25% by weight or more and 60% by weight or less.

It is preferable to add a colorant (D) to the photosensitive composition after setting it as a dispersion liquid disperse|distributed to the appropriate density|concentration in the presence or absence of a dispersing agent.

In addition, in this specification, about the usage-amount of the above-mentioned coloring agent (D), it can be defined as a value including this existing dispersing agent.

As described above, the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. For this reason, the amount of chloride ions in a coloring agent (D) also needs to 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. When the colorant is a dye, the amount of chloride ions can be reduced also by recovering the dye from the solution after preparing a solution of the dye and contacting the obtained solution with an anion exchange resin.

<Amine (E)>

The photosensitive composition comprises an amine (E). When the photosensitive composition contains an amine (E), it is easy to prepare the photosensitive composition which has favorable resolution which can resolve a fine pattern.

An amine (E) may be mix|blended with the photosensitive composition independently, and may be mix|blended with the photosensitive composition as an impurity contained in components other than an amine (E).

The impurity containing the amine (E) includes, for example, an alkali-soluble resin (A) containing a nitrogen atom in the form of an amide bond, a photopolymerizable compound (B) containing a nitrogen compound, and a nitrogen compound a photopolymerization initiator (C), a colorant containing a nitrogen-containing compound (D), an amide bond (-CO-NH-), a urethane bond (-O-CO-NH-), a ureido bond (-NH-CO -NH-) etc., additives for coloring agents (D), such as resin containing an additive, dispersing aids, etc., and a solvent (S) containing a nitrogen-containing polar organic solvent, etc. are mentioned.

When the amine (E) is incorporated into the photosensitive composition as an impurity contained in the photopolymerization initiator (C), it is preferable to use an imidazole compound or an α-aminoalkylphenone compound which is an alkylphenone compound as the compound (C2).

Suitable embodiments of the amine (E) include ammonia, methylamine, ethylamine, ethanolamine, propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, dimethylamine, 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, hexylamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, Chain aliphatic amines such as 1,5-pentanediamine and 1,6-hexanediamine; Dry amines such as pyrrolidine, piperizine, piperazine, morpholine, pyrrole and imidazole; aniline, toluidine and phenylenediamine, etc. and aromatic amines.

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

5000 weight ppm or less is preferable and, as for content of the amine (E) in the photosensitive composition, 3000 weight ppm or less is more preferable. 2000 weight ppm or less may be sufficient as content of the amine (E) in the photosensitive composition, and 1000 weight ppm or less may be sufficient as it, and 500 weight ppm or less may be sufficient as it.

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

When content of the amine (E) in the photosensitive composition is 5000 weight ppm or less, it will be easy to make small the dispersion|variation in the film thickness of a coating film at the time of forming a coating film 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 improvement of applicability|paintability, or viscosity adjustment. In addition, a liquid amine compound is not contained in the solvent (S).

Specifically as the solvent (S), 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, (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene (poly)alkylene glycol monoalkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Other ethers such as ethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. of lactic acid alkyl esters; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethoxyethyl acetate; Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate , n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n propionic acid -Butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyrvate, ethyl pyrvate, n-propyl pyrvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc. other esters of; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N ,N-diethylacetamide, N,N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N,N,N',N'-tetra nitrogen-containing polar organic solvents such as methylurea; and the like.

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

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

These solvents can be used individually or in combination of 2 or more types.

Among the above 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 methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferred, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferred.

The content of the solvent (S) preferably has a solid content concentration of 5% by weight or more and 99% by weight or less, more preferably 15% by weight or more and 50% by weight or less.

As described above, the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. For this reason, the amount of chloride ions in the solvent (S) also needs to be reduced to some extent.

Distillation, treatment with an anion exchange resin, etc. are mentioned as a method of reducing the amount of chloride ions in the solvent (S).

<Other ingredients>

The photosensitive composition can contain additives, such as surfactant, an adhesive improving agent, a thermal-polymerization inhibitor, an antifoamer, and a silane coupling agent, as needed. As any additive, a conventionally well-known thing can be used.

It is preferable that the photosensitive composition contains a silane coupling agent at the point which a shape is favorable and it is easy to form the cured film excellent in adhesiveness with respect to a board|substrate. The silane coupling agent may be used without any particular limitation known in the prior art.

The surfactant includes compounds such as anionic, cationic, and nonionic, the polymerization inhibitor includes hydroquinone and hydroquinone monoethyl ether, and the defoaming agent includes silicone and fluorine compounds.

<The preparation method of the photosensitive composition>

The photosensitive composition demonstrated above can be obtained by mixing each said component by predetermined amount, respectively, and mixing uniformly with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become more uniform.

Moreover, in order to reduce the chloride ion content of the photosensitive composition to a desired value, you may process the 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|membrane formed using the photosensitive composition, respectively mentioned above alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (S) and an amine (E). The photosensitive composition may further contain arbitrary components, such as a coloring agent (D).

When the amount of the chloride ion in the photosensitive composition is 1000% by weight or less, the generation of foreign substances in the film formed using the photosensitive composition is suppressed.

The number of foreign substances is the number of foreign substances detected by a foreign substance detector in a film having a thickness of 1 µm which is dried after spin-coating the photosensitive composition on a 10 cm x 10 cm substrate.

According to the said method, the number of the foreign material demonstrated above is suppressed to less than 1000.

≪Method of forming a cured film≫

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

An insulating film is mentioned as a use of a cured film. 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 black barrier ribs and black column spacers in a black matrix provided with various types of panels for image display devices.

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

For example, the color filter containing said black matrix or a chromatic cured film is used suitably with respect to various display apparatuses.

As a suitable manufacturing method of a cured film,

Forming a coating film by applying the above-described photosensitive composition on a substrate;

The method including exposing a coating film is mentioned.

To form a cured film using the photosensitive composition, the photosensitive composition is applied on a substrate selected according to the purpose of the cured film to form a coating film. Although the method of forming the coating film is not particularly limited, for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used.

The applied photosensitive composition is dried as needed to constitute a coating film. The drying method is not particularly limited, and for example, (1) a method of drying at a temperature of 80° C. or more and 120° C. or less, preferably 90° C. or more and 100° C. or less, on a hot plate for 60 seconds or more and 120 seconds or less, (2 ) left at room temperature for more than a few hours and not more than a few days, (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for more than a few tens of minutes and less than a few hours.

Then, the coating film is exposed. Exposure is performed by irradiating active energy rays, such as an ultraviolet-ray and an excimer laser beam. The exposure may be positionally selective, for example, by a method of exposing through a negative mask. Although the energy dose to irradiate changes with the composition of the photosensitive resin composition, for example, about 40 mJ/cm<2> or more and 200 mJ/cm<2> or less is preferable.

When the coating film is exposed positionally, the film after exposure is developed with a developer to pattern it into a desired shape. The developing method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. The developer is appropriately selected depending on the composition of the photosensitive composition. As a developing solution, basic aqueous solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt, can be used, for example.

The cured film formed by full surface exposure or the developed patterned cured film is post-baked at a temperature of 120°C or higher and 250°C or lower as necessary.

Since the cured film formed as mentioned above has little content of a foreign material and can be patterned finely, it is used suitably for various uses.

[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 weight of the oxime ester compound (C1) of the kind shown in Table 1, 25 parts by weight of the compound (C2) of the kind described in Table 1, alkali-soluble resin (solid content 55 wt%, Solvent 3-methoxybutyl acetate) 310 parts by weight, dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 175 parts by weight and carbon black dispersion (CF black, Mikuni Pigment Co., Ltd.) 450 parts by weight To the mixture, 3-methoxybutyl acetate was added so that the solid content was 15% by weight, and the mixture was stirred until uniform, to obtain a photosensitive composition.

As alkali-soluble resin, the same resin as resin A-1 of Paragraph [0063] of Unexamined-Japanese-Patent No. 2010-32940 - [0064] was used.

About the obtained photosensitive composition, content of an amine was measured by ion chromatography, and content of chloride ion was measured by ion chromatography. Table 1 lists the amine content and the chloride ion content of each photosensitive composition.

Types E1, E2, and E3 of the amines 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 with the grade of refinement|purification of compound (C2).

The amine content in the photosensitive composition of Example 4, Example 5, and Comparative Example 7 was adjusted by adding a predetermined amount of triethylamine to the photosensitive composition using the compound (C2) which does not contain an amine substantially.

Moreover, chloride ion content in each photosensitive composition was adjusted with the grade of refinement|purification of an 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 compound (C2).

C2a: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-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, the following method evaluated a foreign material, resolution, a sensitivity, and applicability|paintability. Table 1 lists these evaluation results.

(Foreign matter evaluation)

The photosensitive resin composition was apply|coated to 10 cm x 10 cm glass using the spin coater, and the coating film was formed. Then, the coating film was heated with a hot plate at 100 degreeC for 120 second, the solvent was removed from the coating film, and the coating film with a film thickness of 1 micrometer was obtained.

The number of foreign substances in the obtained coating film was measured with a foreign substance detector, the number of foreign substances 1000 or more was judged as x, and the number of foreign substances less than 100 was judged as (circle).

(Resolution evaluation)

The photosensitive resin composition was apply|coated to 10 cm x 10 cm glass using the spin coater, and the coating film was formed. Then, the coating film was heated with a hot plate at 100 degreeC for 120 second, the solvent was removed from the coating film, and the coating film with a film thickness of 1 micrometer was obtained.

The obtained coating film was exposed with an exposure amount of 50 mJ/cm 2 through a photomask in which lines having 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 an aqueous KOH solution having a concentration of 0.05% by weight to confirm the minimum line width in the drawn pattern.

The case where the minimum line|wire width was 10 micrometers or more was judged as x, and the case where the minimum line|wire width was less than 10 micrometers was determined as (circle).

(sensitivity evaluation)

The photosensitive resin composition was apply|coated to 10 cm x 10 cm glass using the spin coater, and the coating film was formed. Then, the coating film was heated with a hot plate at 100 degreeC for 120 second, the solvent was removed from the coating film, and the coating film with a film thickness of 1 micrometer was obtained.

The obtained coating film was exposed with an exposure amount of 50 mJ/cm 2 through a photomask in which a line having a line width of 20 µm was drawn.

After exposure, the coating film was developed for 60 seconds using an aqueous KOH solution having a concentration of 0.05% by weight to confirm the drawn pattern.

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

The case where the pattern of the desired dimension was obtained with the exposure amount of 75 mJ/cm<2> or more was judged as x, and the case where the pattern of the desired dimension was obtained with the exposure amount of 50 mJ/cm<2> or less was judged as (circle).

(Evaluation of applicability)

The film thickness of the coating film used for the foreign material measurement was measured 10 points|pieces, and the difference between the maximum film thickness and the minimum film thickness was computed. Moreover, applicability|paintability is the level which does not have a problem also about any photosensitive composition. This evaluation is a comparison of the superiority and inferiority of applicability|paintability within the range where there is no problem.

The case where the film thickness difference was 0.1 micrometer or more was judged as (circle), and the case where the film thickness difference was less than 0.1 micrometer was determined as (double-circle).

oxime
ester
compound
(C1) compound
(C2) amine
content
(weight ppm) Cl ^-
content evaluation type weight
ppm weight
ppm alien substance resolution Sensitivity applicability Example 1 C1a C2a E1 6110 170 ○ ○ ○ ○ Example 2 C1a C2a E1 4470 890 ○ ○ ○ ◎ Example 3 C1a C2a E1 260 180 ○ ○ ○ ◎ Comparative Example 1 C1a C2a E1 5870 1610 × ○ ○ ○ Comparative Example 2 C1a C2a E1 4010 1580 × ○ ○ ◎ Comparative Example 3 C1a C2a E1 200 2150 × ○ ○ ◎ Comparative Example 4 C1a - - non-detection 1700 ○ × ○ ◎ Comparative Example 5 C1a - - non-detection 170 ○ × ○ ◎ Comparative Example 6 - C2a E1 210 60 ○ × × ◎ Example 4 C1a C2a E2 7020 190 ○ ○ ○ ○ Example 5 C1a C2a E2 250 750 ○ ○ ○ ◎ Comparative Example 7 C1a C2a E2 3640 1490 × ○ ○ ◎ Example 6 C1b C2a E1 6500 310 ○ ○ ○ ○ Example 7 C1b C2a E1 220 930 ○ ○ ○ ◎ Comparative Example 8 C1b C2a E1 3440 1770 × ○ ○ ◎ Example 8 C1a C2b E1 5430 440 ○ ○ ○ ○ Example 9 C1a C2b E1 200 960 ○ ○ ○ ◎ Comparative Example 9 C1a C2b E1 3710 2250 × ○ ○ ◎ Comparative Example 10 - C2b E1 320 40 ○ × × ◎ Example 10 C1a C2c E3 6430 710 ○ ○ ○ ○ Example 11 C1a C2c E3 250 890 ○ ○ ○ ◎ Comparative Example 11 C1a C2c E3 4650 2130 × ○ ○ ◎ Comparative Example 12 - C2c E3 230 720 ○ × × ◎

According to Table 1, as a photosensitive composition containing alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), a solvent (S), and an amine (E), a photoinitiator (C) In the photosensitive composition of Examples containing the 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 ppm by weight or less, it was found that suppression of foreign substances and good resolution are compatible. can

Claims (6)

A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), a solvent (S), and an amine (E),
The said photoinitiator (C) contains an oxime ester compound (C1) and a compound (C2) other than the said oxime ester compound,
The compound (C2) is at least one selected from the group consisting of an alkylphenone compound and an imidazole compound,
The photosensitive composition wherein the amount of chloride ions in the photosensitive composition is 1000 ppm by weight or less. The method according to claim 1,
Further, a photosensitive composition comprising a colorant (D). The method according to claim 1 or 2,
The photosensitive composition whose content of the said amine (E) in the said photosensitive composition is 5000 weight ppm or less. Forming a coating film by applying the photosensitive composition according to claim 1 or 2 on a substrate,
The formation method of the cured film including exposing the said coating film. 5. The method according to claim 4,
The coating film is positionally exposed,
Further, the method of forming a cured film comprising developing the exposed coating film. delete