KR102429751B1 - Photosensitive resin composition, cured film, color filter and manufacturing method of cured film - Google Patents

Abstract

[Problem] The photosensitive resin composition which is hard to flow excessively by the heating at the time of post-baking and can form the colored cured film finely patterned to a desired size, the manufacturing method of the cured film using the said photosensitive resin composition, and the said photosensitive resin composition To provide a cured film formed by curing a color filter provided with the cured film.
[Solution means] A photosensitive resin composition comprising (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photoinitiator, and (D) pigment, wherein (A) alkali-soluble resin is a novolak resin and (B) a dendritic polymer having two or more ethylenically polymerizable groups at the terminal as the photopolymerizable compound.

Description

The photosensitive resin composition, a cured film, a color filter, and the manufacturing method of a cured film TECHNICAL FIELD

The present invention relates to a negative photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, a color filter provided with the cured film, and a method for producing a cured film using the negative photosensitive resin composition described above.

BACKGROUND ART A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes that are opposite to each other are formed. A color filter having pixels made of each color such as red (R), green (G), and blue (B) is formed inside one of the substrates. And, in this color filter, in order to prevent color mixing of different colors in each pixel or to hide patterns of electrodes, a black matrix arranged on a matrix to partition pixels of each color R, G, and B is usually formed. is becoming

In general, the color filter is formed by a lithographic method. Specifically, a black matrix is formed by first coating, exposing, and developing a black photosensitive composition on a substrate. Then, by repeating application, exposure, and development for each photosensitive composition of each color of red (R), green (G), and blue (B), a pattern of each color is formed at a predetermined position to form a color filter do.

As a formation method of the colored film which comprises a color filter, the method of using a negative photosensitive resin composition with respect to the formation method of a black matrix is proposed, for example.

Specifically, the use of a negative photosensitive resin composition containing a photopolymerizable compound, a photoinitiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, and a solvent has been proposed (refer to Patent Document 1).

In addition, in recent years, a technology for blending a dendritic polymer having a specific structure as a photosensitive resin composition for black resist containing a light-shielding component such as a black organic pigment or a dispersion resin composition containing a colorant has been pioneered. have.

According to this technique, it is believed that a resin composition having a smooth coating film surface and no deterioration in surface roughness due to thermal curing shrinkage, or a composition excellent in adhesion and pattern shape at the time of development can be achieved (Patent Documents 2 and 3) Reference).

Japanese Patent Laid-Open No. 2011-170075 Japanese Patent Laid-Open No. 2012-27448 Japanese Patent Laid-Open No. 2012-93591

In patent document 1, use of resin-coated carbon black is proposed as a black pigment mix|blended with a negative photosensitive resin composition. When resin-coated carbon black is used as a light-shielding agent, it is easy to form a black matrix with a high resistance value.

However, when resin-coated carbon black is used as a light-shielding agent, it is difficult to form a black matrix having a high optical density (OD).

In order to form a cured film with a high resistance value, solving the problem with such a low optical density, using a pigment with a small secondary particle diameter is considered.

However, when a pigment having a small secondary particle diameter is used, the colored cured film constituting a color filter such as a black matrix flows excessively by heating in a post-baking performed after exposure and development, and thus the cured film is not acceptable. There are cases where a shape change to a degree that there is no degree of change occurs.

In addition, it is generally required that the patterned colored film constituting the color filter is accurately formed to the size as designed.

In the case of using the composition disclosed in Patent Document 2 or Patent Document 3, it is difficult to form a pattern having a size as designed, although it exhibits a certain inhibitory effect on the shape change of the cured film described above.

The present invention has been made in view of the above problems, a photosensitive resin composition capable of forming a colored cured film that is difficult to flow excessively by heating during post-baking and finely patterned to a desired size, and curing using the photosensitive resin composition It aims at providing the color filter provided with the manufacturing method of a film|membrane, the cured film formed by hardening the said photosensitive resin composition, and the said cured film.

The present inventors have a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photoinitiator, and (D) a pigment, (A) a novolac resin as the alkali-soluble resin Moreover, it discovered that said subject could be solvable by using the dendritic polymer which has two or more ethylenically polymerizable groups at the terminal as (B) a photopolymerizable compound, and came to complete this invention. Specifically, the present invention provides the following.

A first aspect of the present invention is

(A) an alkali-soluble resin;

(B) a photopolymerizable compound;

(C) a photoinitiator;

(D) In the photosensitive resin composition containing the pigment,

(A) the alkali-soluble resin comprises a novolac resin,

(B) It is a photosensitive resin composition in which a photopolymerizable compound contains the dendritic polymer which has two or more ethylenic polymeric groups at the terminal.

A 2nd aspect of this invention is a cured film formed by hardening|curing the photosensitive resin composition which concerns on a 1st aspect.

A 3rd aspect of this invention is a color filter provided with the cured film which concerns on a 2nd aspect.

A 4th aspect of this invention is the process of forming a coating film by apply|coating the photosensitive resin composition which concerns on 1st aspect,

a step of positionally selectively exposing the coating film;

A process of forming a patterned cured film by developing the exposed coating film;

It is a manufacturing method of the cured film including the process of baking the patterned cured film.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is hard to flow excessively by the heating at the time of post-baking, and can form the colored cured film finely patterned to a desired size, the manufacturing method of the cured film using the said photosensitive resin composition, and the said photosensitivity The cured film formed by hardening a resin composition, and the color filter provided with the said cured film can be provided.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on preferred embodiments. In addition, in this specification, "-" represents from above (lower limit) to below (upper limit), unless there is a special indication.

«Photosensitive resin composition»

The photosensitive resin composition contains (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photoinitiator, and (D) pigment.

The photosensitive resin composition contains a novolak resin as (A) alkali-soluble resin. Moreover, the photosensitive resin composition contains the dendritic polymer which has two or more ethylenically polymerizable groups at the terminal as a (B) photopolymerizable compound.

When the photosensitive resin composition contains said novolak resin and a dendritic polymer, it is hard to flow excessively by the heating at the time of a post-baking, and it is easy to form the colored cured film finely patterned to a desired size.

Hereinafter, the essential or arbitrary components contained in the photosensitive resin composition, and the preparation method of the photosensitive resin composition are demonstrated.

<(A) alkali-soluble resin>

The photosensitive resin composition contains (A) alkali-soluble resin.

Here, in this specification, (A) alkali-soluble resin refers to resin provided with the functional group (For example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) which gives alkali solubility in a molecule|numerator.

(A) Alkali-soluble resin contains (A1) novolak resin. When the photosensitive resin composition contains (A1) novolak resin as (A) alkali-soluble resin, it is easy to form the cured film which does not easily flow excessively by overheating at the time of a post-baking.

Hereinafter, (A1) novolak resin and alkali-soluble resin other than (A1) novolak resin are demonstrated.

[(A1) novolac resin]

(A1) As the novolac resin, various novolac resins conventionally blended with the photosensitive resin composition can be used. (A1) The novolak resin is preferably obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes under an acid catalyst.

(phenols)

(A1) As phenols used when producing a novolak resin, For example, phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol silenols; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and fluoroglycinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol and alkylhydroquinone (any alkyl group having 1 or more and 4 or less carbon atoms); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used independently and may be used in combination of 2 or more type.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. In this case, various characteristics, such as heat resistance of the cured film formed using the photosensitive resin composition, can be adjusted by adjusting the compounding ratio of both.

Although the mixing ratio of m-cresol and p-cresol is not specifically limited, 3/7 or more and 8/2 or less are preferable in molar ratio of m-cresol/p-cresol. By using m-cresol and p-cresol in the ratio of such a range, the photosensitive resin composition which can form the cured film excellent in heat resistance is easy to be obtained.

Moreover, a novolak resin manufactured using m-cresol and 2,3,5-trimethylphenol together is also preferable. When using such a novolac resin, it is easy to obtain especially the photosensitive resin composition which can form the cured film which does not easily flow excessively by the heating at the time of a post-baking.

Although the blending ratio of m-cresol and 2,3,5-trimethylphenol is not specifically limited, As a molar ratio of m-cresol/2,3,5-trimethylphenol, 70/30 or more and 95/5 or less are preferable.

(aldehydes)

(A1) As aldehydes used when producing a novolak resin, formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. are mentioned, for example. These aldehydes may be used independently and may be used in combination of 2 or more type.

(acid catalyst)

(A1) As an acid catalyst used when producing a novolak resin, For example, Inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used independently and may be used in combination of 2 or more type.

(Molecular Weight)

(A1) The polystyrene conversion weight average molecular weight of the novolak resin (Mw; hereinafter simply referred to as "weight average molecular weight") is a lower limit from the viewpoint of resistance to flow by heating of a cured film formed using the photosensitive resin composition. 2,000 is preferable, 5,000 is more preferable, 10,000 is particularly preferable, 15,000 is more preferable, 20,000 is most preferable, 50,000 is preferable as an upper limit, 45,000 is more preferable, 40,000 is more preferable, 35,000 is Most preferred.

(A1) As a novolak resin, at least 2 types of things from which the weight average molecular weight in terms of polystyrene differ can be used in combination. By using the thing from which a weight average molecular weight differs in some combination, the developability of the photosensitive resin composition, and the heat resistance of the cured film formed using the photosensitive resin composition can be balanced.

[(A2) resin having cardo structure]

The photosensitive resin composition contains (A2) resin having a cardo structure as (A) alkali-soluble resin (hereinafter, also referred to as "(A2) cardo resin") from the viewpoint of further improving flow resistance to a cured film. may do it

(A2) As resin which has cardo frame|skeleton, it has cardo frame|skeleton in the structure, and resin which has predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. In addition, the 2nd annular structure and the 3rd annular structure may be the same structure or different structures may be sufficient as them.

A typical example of the cardo skeleton is a skeleton in which two aromatic rings (eg, a benzene ring) are bonded to a carbon atom in the 9th position of the fluorene ring.

(A2) It does not specifically limit as cardo structure resin, Conventionally well-known resin can be used. Among these, resin represented by the following formula (a-1) is preferable.

In formula (a-1), X ^a represents group represented by following formula (a-2). m1 represents the integer of 0-20.

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 R ^a3 is each Independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^a represents a group represented by the following formula (a-3).

In formula (a-2), as R ^a3 , an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms is particularly Preferably, an ethane-1,2-diyl group, a propane-1,2-diyl group and a propane-1,3-diyl group are most preferable.

Ring A in Formula (a-3) represents the aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.

Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.

An aromatic hydrocarbon ring or an aromatic heterocyclic ring may be sufficient as the aromatic ring which may be condensed to an aliphatic ring, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

Preferred examples of the divalent group represented by the formula (a-3) include the following groups.

The divalent group Xa in formula ( ^a -1) is introduce|transduced in (A1) cardo resin by making tetracarboxylic dianhydride which gives residue Za react with the diol compound represented by following formula ( ^a -2a).

In formula (a-2a), R ^a1 , R ^a2 , R ^a3 and m2 are the same as those described for formula (a-2). Ring A in formula (a-2a) is the same as that described for formula (a-3).

The diol compound represented by Formula (a-2a) can be manufactured by the following method, for example.

First, a hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) is substituted with a group represented by -R ^a3 -OH according to a conventional method if necessary, and then glycated using epichlorohydrin or the like. It sidylates to obtain the epoxy compound represented by the following formula (a-2c).

Then, the diol compound represented by Formula (a-2a) can be obtained by making the epoxy compound represented by Formula (a-2c) react with acrylic acid or methacrylic acid.

In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 and m2 are the same as those described for formula (a-2). Ring A in formulas (a-2b) and (a-2c) is the same as that described for formula (a-3).

In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to said method.

The following diol compounds are mentioned as a preferable example of the diol compound represented by Formula (a-2b).

In the formula (a-1), R ^a0 is a hydrogen atom or a group represented by -CO-Ya-COOH. Here, Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic 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 tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride represented by the following formula (a-4). can be heard

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

(in formula (a-4), R ^a4 , R ^a5 and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and m3 is 0 to 12 represents the integer of )

The alkyl group which may be selected for R ^a4 in formula (a-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms included in the alkyl group within this range, the heat resistance of the resulting carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and more preferably 1 to 3 from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. This is particularly preferred.

When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

R ^a4 in the formula (a-4) is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms each independently from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. R ^a4 in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

It is preferable that several R ^a4 in Formula (a-4) is the same group because preparation of highly purified tetracarboxylic dianhydride is easy.

m3 in Formula (a-4) represents the integer of 0-12. By setting the value of m3 to 12 or less, purification of tetracarboxylic dianhydride can be facilitated.

From the point that refinement|purification of tetracarboxylic dianhydride is easy, 5 is preferable and, as for the upper limit of m3, 3 is more preferable.

From the point of the chemical stability of tetracarboxylic dianhydride, 1 is preferable and, as for the minimum of m3, 2 is more preferable.

As for m3 in Formula (a-4), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms which may be selected as R ^a5 and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms which may be selected as R ^a4 .

R ^a5 and R ^a6 represent hydrogen atoms or 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4) from the viewpoint of easy purification of tetracarboxylic dianhydride. , It is particularly preferably an alkyl group of 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

As tetracarboxylic dianhydride represented by Formula (a-4), For example, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"- norbornane-5,5" ,6,6"-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2"-norbornane-5,5",6,6-tetra carboxylic acid dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-(methylnorbornane)-5,5",6,6-tetracarboxylic dianhydride; Norbornane-2-spiro-α-cyclohexanone-α'-spiro-2"-norbornane-5,5",6,6-tetracarboxylic dianhydride (also known as "norbornane-2-spiro-" 2'-cyclohexanone-6'-spiro-2"-norbornane-5,5",6,6-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclohexanone- α′-spiro-2″-(methylnorbornane)-5,5″,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α′-spiro-2″ -Norbornane-5,5",6,6"-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2"-norbornane-5,5" ,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride; Norbornane-2-spiro-α-cyclooctanone-α'-spiro-2"-norbornane-5,5",6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α- Cyclononanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α′-spiro-2 "-Norbornane-5,5",6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2"-norbornane-5,5" ,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride; norbornane-2-spiro-α-cyclotridecanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride; Norbornane-2-spiro-α-cyclotetradecanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α -Cyclopentadecanone-α′-spiro-2″-norbornane-5,5″,6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α '-spiro-2"-norbornane-5,5",6,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2"- norbornane-5,5",6,6-tetracarboxylic dianhydride etc. are mentioned.

(A2) It is preferable that it is 1,000-40,000, and, as for the weight average molecular weight of cardo resin, it is more preferable that it is 2,000-30,000. By setting it as said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

[Other alkali-soluble resins]

(A) Alkali-soluble resin may contain other alkali-soluble resin other than (A1) novolak resin and (A2) cardo resin in the range which does not impair the objective of this invention. Other alkali-soluble resin will not be specifically limited if it is resin which has predetermined alkali solubility, It can suitably use from the various resin conventionally mix|blended with the photosensitive resin composition.

As other alkali-soluble resins, (A3) acrylic resin is preferable from the viewpoint that adjustment of the various characteristics of resin containing alkali solubility is easy, etc.

(A3) As acrylic resin, the thing containing the structural unit derived from (meth)acrylic acid, and/or other monomers, such as (meth)acrylic acid ester, can be used. (meth)acrylic acid is acrylic acid or methacrylic acid. The (meth)acrylic acid ester is represented by the following formula (a-5), and is not particularly limited as long as the object of the present invention is not impaired.

In the formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Moreover, any of linear, branched, and cyclic|annular form may be sufficient as this organic group.

Substituents other than the hydrocarbon group in the organic group of R ^a8 are not particularly limited as long as the effects of the present invention are not impaired, and a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanate group, Isocyanate group, thiocyanate group, isothiocyanate group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group , acyloxy group, sulfino group, sulfur group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, an aryl thioether group, an amino group (-NH ₂ , -NHR, -NRR': R and R' each independently represent a hydrocarbon group); and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. Moreover, any of linear, branched and cyclic|annular form may be sufficient as the hydrocarbon group contained in the said substituent.

R ^a8 is preferably an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. Moreover, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When an alkyl group is a linear or branched thing, 1-20 are preferable, as for the number of carbon atoms, 1-15 are more preferable, and 1-10 are especially preferable. Examples of preferred alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group , tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isode and the like.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, the preferable alicyclic group included in the alkyl group is a monocyclic alicyclic group such as a cyclopentyl group and a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, and a tricyclo Polycyclic alicyclic groups, such as a nonyl group, a tricyclodecyl group, and a tetracyclododecyl group, are mentioned.

Moreover, what polymerized monomers other than (meth)acrylic acid ester may be sufficient as (A3) acrylic resin. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These monomers can be used individually or in combination of 2 or more types.

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 unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and the like.

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

Examples of vinyl ethers include hexylvinyl ether, octylvinyl ether, decylvinyl ether, ethylhexylvinyl ether, methoxyethylvinyl ether, ethoxyethylvinyl ether, chloroethylvinyl ether, 1-methyl-2,2-dimethylpropylvinyl. Ether, 2-ethylbutylvinyl ether, hydroxyethylvinyl ether, diethyleneglycolvinyl ether, dimethylaminoethylvinyl ether, diethylaminoethylvinyl ether, butylaminoethylvinyl ether, benzylvinyl ether, tetrahydrofurfurylvinyl ether alkyl vinyl ethers such as; vinylaryl ethers such as vinylphenyl ether, vinyltolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinylnaphthyl ether, and vinylentranyl ether; and the like.

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl acetate. , vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetracrotobenzoate, 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 , alkyl styrenes such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3- methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro halostyrenes such as methylstyrene and 4-fluoro-3-trifluoromethylstyrene; and the like.

(A3) The quantity of the structural unit derived from (meth)acrylic acid in acrylic resin, and the quantity of the structural unit derived from another monomer are not specifically limited in the range which does not impair the objective of this invention. (A3) 5-50 weight% is preferable with respect to the weight of acrylic resin, and, as for the quantity of the structural unit derived from (meth)acrylic acid in acrylic resin, 10-30 weight% is more preferable.

(A3) It is preferable that it is 2,000-50,000, and, as for the weight average molecular weight of acrylic resin, it is more preferable that it is 5,000-30,000. By setting it as said range, there exists a tendency which is easy to take the balance of the film-forming ability of the photosensitive resin composition, and the developability after exposure.

(A) It is preferable that it is 10-65 weight% with respect to the weight of the whole solid content of the photosensitive resin composition, and, as for content of alkali-soluble resin, it is more preferable that it is 15-50 weight%. By setting it as said range, it is easy to obtain the photosensitive resin composition excellent in developability.

Further, (A1) the content of the novolak resin is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, furthermore preferably 1.2 to 5% by weight, based on the total weight of the solid content of the photosensitive resin composition. desirable. By setting it as said range, the cured film which does not easily flow excessively by the heating at the time of a post-baking can be formed, and the photosensitive resin composition excellent in developability is easy to be obtained.

Moreover, when using (A2) cardo resin, it is preferable that the content is 5-40 weight% with respect to the weight of the whole solid content of the photosensitive resin composition, It is more preferable that it is 10-35 weight%, It is 15-30 weight. % is more preferable. By setting it as said range, the cured film which does not easily flow excessively by the heating at the time of a post-baking can be formed, and the photosensitive resin composition excellent in developability is easy to be obtained.

<(B) photopolymerizable compound>

The photosensitive resin composition contains (B) a photopolymerizable compound. (B) As a photopolymerizable compound, the compound which has an ethylenic polymeric group can be used preferably.

Moreover, (B) photopolymerizable compound contains the dendritic polymer which has two or more ethylenically polymerizable groups at the terminal.

Here, although it is not certain about the point which the photosensitive resin composition of this embodiment can solve the subject concerning this invention, the following mechanisms are conceivable.

That is, when the photosensitive resin composition contains the above-mentioned dendritic polymer as the (B) photopolymerizable compound, curing of the photosensitive resin composition proceeds favorably during exposure, and excessive heat flow of the cured film even when post-baking the cured film is performed. is difficult to occur

On the other hand, when the photosensitive resin composition contains a dendritic polymer, hardening by exposure advances excessively, and the pattern which has a larger width|variety and diameter than a desired size may be formed after image development.

However, when the photosensitive resin composition contains the above-mentioned (A1) novolac resin and dendritic polymer in combination, (A1) the novolac resin appropriately traps radicals during the curing reaction by exposure to light, thereby preventing the curing reaction during exposure. Excessive progression is suppressed.

For this reason, (A1) when the photosensitive resin composition containing a combination of a novolak resin and a dendritic polymer is used, it is difficult to flow excessively due to heating during post-baking, and it is considered that it is easy to form a fine pattern having a desired size and shape. .

[dendritic polymer]

As described above, the photosensitive resin composition contains (B) a multi-branched dendritic polymer having two or more ethylenically polymerizable groups at a terminal thereof as the photopolymerizable compound.

The dendritic polymer has in its structure branching points that extend the molecular chain in three or more directions. The number of branch points in one molecule of the dendritic polymer is 3 or more, and 4 or more is preferable.

For example, the number of branching points which dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylate has is 2. For this reason, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate do not correspond to a dendritic polymer.

In addition, when the tolerance with respect to the heat flow and hydrolysis of the cured film formed using the photosensitive resin composition is considered, it is preferable that a dendritic polymer does not contain a urethane bond.

Although it is preferable that the ethylenic polymeric group which a dendritic polymer has is what originates in a (meth)acrylate compound, it is not limited to this.

The multi-branched dendritic polymer is not particularly limited as long as it has a dendritic multi-branched structure and has two or more ethylenically polymerizable groups at the terminal thereof.

As such a dendritic polymer, a polymer called a so-called dendrimer or a hyperbranched polymer is preferably used.

Examples of commercially available dendritic polymers having an ethylenic polymerizable group at the terminal include Biscoat #1000 (trade name), Viscote #1020 (trade name) and STAR 501 (SIRIUS 501, SUBARU 501) (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd. can be heard

Biscoat #1000 and Viscote #1020 are mainly composed of multi-branched (dendrimer-type) polyester acrylates having acrylate groups at the ends. Moreover, the molecular weight of biscoat #1000 is about 1,000-2,000, and the molecular weight of biscoat #1020 is about 1,000-3,000.

STAR-501 contains a core derived from dipentaerythritol and has a dipentaerythritol hexaacrylate (DPHA)-linked multi-branched polyacrylate having an acrylate group at the terminal as a main component. The molecular weight of STAR 501 is about 16,000 to 24,000.

Moreover, the polymer prepared using the dendrimer or hyperbranched polymer which has a hydroxyl group, an amino group, or a carboxy group at the terminal may be sufficient as a dendritic polymer.

Substitution of a hydrogen atom contained in a hydroxyl group or an amino group at the terminal of the dendrimer or hyperbranched polymer with an alkenyl group having a double bond at the terminal such as an acryloyl group, a methacryloyl group or an allyl group in a desired amount according to a known method By doing so, the dendritic polymer used as (B) a photopolymerizable compound can be obtained.

In addition, by esterifying or amidating the carboxyl group at the terminal of the dendrimer or hyperbranched polymer using an alcohol or amine having an ethylenic double bond at the terminal according to a known method, (B) a dendritic polymer used as a photopolymerizable compound can be obtained As alcohol or amine which has an ethylenic double bond at the terminal, 2-hydroxyethyl (meth)acrylate, allyl alcohol, 2-aminoethyl (meth)acrylate, allyl amine, etc. are mentioned, for example.

As the dendrimer having a hydroxyl group, an amino group or a carboxy group at the terminal, for example, a polyamide amine dendrimer having a terminal amino group known as PAMAM; a PAMAM-type dendrimer in which the terminal amino group is converted to a hydroxyalkylamino group such as a 2-hydroxyethylamino group; a PAMAM-type dendrimer in which the terminal amino group is converted to a carboxyalkyl amide group such as a succinic acid group (-NH-CO-CH ₂ CH ₂ -COOH); poly(glycerol-succinic acid) dendrimer having a hydroxyl group at the terminal which is a copolymerized polyester of glycerol and succinic acid; a poly(glycerol-succinic acid) dendrimer having a carboxyl group at the terminal, which is a copolymer of glycerol and succinic acid; and a dendrimer having a hydroxyl group at the terminal, which is a homopolyester of 2,2-bis(hydroxymethyl)propanoic acid (bis-MPA).

As a preferable dendritic polymer, the polymer demonstrated below is mentioned.

First, the ethylenic polymerizable group is a group having a carbon-carbon double bond, and in a conjugated compound such as an α,β-unsaturated carbonyl compound in which a carbonyl group is bonded to this carbon-carbon double bond, a nucleophilic agent such as a mercapto compound It is known that Michael addition reaction occurs at the vinyl group, which has the strongest interaction with 核劑).

Therefore, when a compound having a plurality of ethylenically polymerizable groups, such as an α,β-unsaturated carbonyl compound, and a compound having a plurality of nucleophilic groups, such as a polyvalent mercapto compound, are reacted, an addition reaction occurs at the carbon on the β position to the carbonyl group. When there are many groups in which an addition reaction occurs, many branches are formed to form a dendritic polymer. Such dendritic polymers are known by International Publication No. 2008/47620 and the like, and can be obtained by the methods described in these documents.

As the dendritic polymer, Michael addition of a polyfunctional (meth)acrylate compound represented by the following formula (1) and a polyvalent mercapto compound represented by the following formula (2) (carbon-carbon double on α, β-position with respect to the carbonyl group) Adducts polymerized by addition to bonds) are preferred.

(in formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is an ester bond in formula (1) with n hydroxy groups out of m hydroxy groups of the polyhydric alcohol R ₃ (OH) _m is an n-valent residue given in, m and n are each independently an integer of 2 to 20, and m≥n)

(HS-CH ₂ -) _p -R ⁴ (2)

(In formula (2), R ⁴ is a single bond or a hydrocarbon group containing 2 to 6 valent C1 to 6 carbon atoms, p is 2 when R ⁴ is a single bond, and R ⁴ is 2 to 6 valent In the case of a hydrocarbon group-containing group, it is an integer of 2 to 6)

Here, the Michael addition of the polyvalent mercapto compound represented by the formula (2) to the polyfunctional (meth)acrylate compound represented by the formula (1) results in the resulting dendritic polymer still undergoing radiation polymerization based on a carbon-carbon double bond after that. It is preferable to carry out so that the carbon-carbon double bond possessed by the compound represented by formula (1) remains in the range of 0.1 to 50 mol% as a whole.

For example, the carbon-carbon double bond of the mercapto group of the polyvalent mercapto compound represented by Formula (2) and the polyfunctional (meth)acrylate compound represented by Formula (1) (in Formula (1), CH ₂ =C (R ¹ ) refers to the double bond represented by -, and in the case of calculating the molar ratio, it is referred to as a double bond) The addition ratio is preferably 1/100 to 1/3 in the molar ratio of the mercapto group/double bond, and 1 It is more preferable to be set to /50 to 1/5, and particularly preferably to be 1/20 to 1/8.

Moreover, it is preferable that a dendritic polymer has a sufficient amount of functional groups for polymerizing favorably by exposure. For this purpose, the molecular weight of the dendritic polymer is preferably in the range of 100 to 10,000 as a molecular weight per mole of carbon-carbon double bonds. The preferred weight average molecular weight (Mw) of the dendritic polymer is 8,000 to 40,000, more preferably 15,000 to 25,000.

In the formula (1), preferably R ³ (OH) _m is a polyhydric alcohol based on a non-aromatic straight-chain or branched hydrocarbon backbone having 2 to 8 carbon atoms, or a plurality of molecules of the polyhydric alcohol are alcohols polyhydric alcohol ethers formed by linking through ether bonds by dehydration condensation of

In said Formula (1), although m and n independently represent the integer of 2-20, m≥n. Preferably, m and n are integers from 2 to 10, and m≥n.

As a preferable specific example of the polyfunctional (meth)acrylate compound represented by Formula (1), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra Ethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri ( meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylic rate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin-modified hexahydrophthalate di(meth)acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane Tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, alkoxy modified trimethylolpropane (meth)acrylic acid esters such as tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, and ditrimethylolpropanetetra(meth)acrylate can These compounds may be used individually by 1 type, and may use 2 or more types together.

In formula (2), preferably R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms which may have a single bond or a substituent, or a hydrocarbon group which may further contain an oxygen atom in the skeleton of the hydrocarbon group, It may be linear or branched.

Moreover, these hydrocarbon group-containing groups may have a carbonyloxy group couple|bonded with a part of thiomethyl group (HS-CH2-) shown in Formula ( ₂ ) further. In addition, when an oxygen atom is included in the skeleton of the hydrocarbon group, both ends are preferably a hydrocarbon group. p represents an integer of 2 to 6, and corresponds to the valence of R ⁴ .

Therefore, when R ⁴ represents a single bond, p is 2, when R ⁴ has 1 carbon atom, p is 2 to 4, and when R ⁴ has 2 to 6 carbon atoms, p is 2 to 6. .

Examples of the polyvalent mercapto compound represented by formula (2) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethylolpropane tri(mercaptoacetate). ), trimethylolpropane tri (mercaptopropionate), pentaerythritol tetra (mercapto acetate), pentaerythritol tri (mercapto acetate), pentaerythritol tetra (mercapto propionate), dipentaerythritol Hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. are mentioned.

In synthesizing the dendritic polymer, a polymerization inhibitor can be added as needed. As the polymerization inhibitor, a hydroquinone-based compound or a phenol-based compound generally used for preventing polymerization of a (meth)acrylate compound can be used in the present invention as well. Specific examples thereof include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT), and the like. , but are not limited thereto.

Confirmation of completion of the dendritic polymer synthesis can be confirmed by liquid chromatography, gel filtration chromatography, or other analysis using general analytical instruments.

When synthesizing a dendritic polymer, a Michael addition reaction occurs in which the polyvalent mercapto compound represented by the formula (2) is added to the double bond of the polyfunctional (meth)acrylate compound represented by the formula (1). This reaction can be carried out by mixing a polyfunctional (meth)acrylate compound and a polyvalent mercapto compound, and adding a basic catalyst at room temperature to 100°C. Although reaction time is not specifically limited, Usually, it is 30 minutes - 20 hours, Preferably it is 6-12 hours.

[Other photopolymerizable compounds]

In the range which does not impair the objective of this invention, you may contain various photopolymerizable compounds conventionally mix|blended with the photosensitive resin composition for the purpose of improving resolution other than the above-mentioned dendritic polymer in the range which does not impair the objective of this invention.

As another photopolymerizable compound, the monomer which has an ethylenically unsaturated group is preferable. Such monomers include monofunctional monomers and polyfunctional monomers.

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, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acryl Rate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) ) acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, the half (meth)acrylate of a phthalic acid derivative, etc. are mentioned. 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 Oxydiethoxyphenyl)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 polyglycidyl Ether poly (meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate reactants), methylenebis (meth) ) polyfunctional monomers, such as acrylamide, (meth)acrylamide methylene ether, and the condensate of a 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, from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition, a trifunctional or higher polyfunctional monomer is preferable, and a tetrafunctional or higher polyfunctional monomer is more It is preferable, and a polyfunctional monomer more than 5 functional is more preferable.

Specifically, it is preferable that a dendritic polymer and a polyfunctional monomer having more than pentafunctionality are used in combination, and it is preferable that a dendritic polymer and dipentaerythritol penta (meth) acrylate and/or dipentaerythritol hexa (meth) acrylate are used in combination. more preferably.

(B) 1-50 weight% is preferable with respect to the weight of the whole solid content of the photosensitive resin composition, and, as for content in the photosensitive resin composition of a photopolymerizable compound, 5-40 weight% is more preferable. By setting it as said range, there exists a tendency for a sensitivity, developability, and the balance of resolution to be easy to take.

0.1 to 30 weight% is preferable with respect to the weight of the whole solid content of the photosensitive resin composition, and, as for content in the photosensitive resin composition of a dendritic polymer, 0.5 to 25 weight% is more preferable. By setting it as said range, it is hard to flow excessively by the heating at the time of a post-baking, and it is easy to obtain the photosensitive resin composition which is easy to form the fine pattern which is a desired size and shape.

Moreover, the ratio (Wn:Wd) of the content Wn [g] of the novolak resin and the content Wd [g] of the dendritic polymer in the photosensitive resin composition is preferably within the range of 20:1 to 1:20, and 18:1 to The inside of the range of 1:18 is more preferable, it is especially preferable that it exists in the range of 15:1-1:15, The inside of the range of 5:1-1:12 is the most preferable.

<(C) Photoinitiator>

(C) It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used.

(C) Photoinitiator, specifically 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dode Sylphenyl)-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, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl )[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1- Octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4 -Butyl dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propane Dione-2-(O-ethoxycarbonyl)oxime, o-benzoylbenzoate methyl, 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, benzophenone, 2-chlorobenzophenone, p ,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzo Phosphorus, benzoinmethyl ether, benzoinethyl ether, benzoinisopropyl ether, benzoin-n-butyl ether, benzoinisobutyl 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, dibenzosuberone, pentyl-4-dimethylaminobenzo Eight, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl) nyl) 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-tri azine, 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) and styrylphenyl-s-triazine 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 these, it is especially preferable from the point of a sensitivity to use the photoinitiator of an oxime system. Particularly preferred among the oxime-based photopolymerization initiators are O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, and 1-[9 -Ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) and 2-(benzoyloxyimino)-1-[4-(phenylthio) ) phenyl]-1-octanone.

As a photoinitiator, it is also preferable to use the oxime type 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 from 0 to 4, n2 is 0 or 1, and R ^c2 may have a substituent a phenyl group or a carbazolyl group which may have a substituent, and R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 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. Preferred examples of 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 Group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino group , 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 to 4, 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 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. In addition, when R ^c1 is an alkyl group, it may be linear or branched. 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 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. In addition, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples when R ^c1 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 ^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 methoxy group. A propyloxy group etc. are mentioned.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples when R ^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 to 20 carbon atoms are preferable, and 2 to 7 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 to 20 carbon atoms are preferable, and 2 to 7 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-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group and isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Moreover, when R ^c1 is a naphthylalkyl group, 11 to 20 carbon atoms are preferable, and 11 to 14 carbon atoms are more preferable. When R ^c1 is a phenylalkyl group, specific examples thereof 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 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, it is assumed that the number of rings is up to 3. 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, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 20 carbon atoms. An actual group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a substituent and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may have Specific examples of these preferred organic groups are the same as those of 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. can

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 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 to 7 carbon atoms. of a saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained 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 1-4. 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.

Among R ^c1 , it is chemically stable, has little steric hindrance, and is easy to synthesize an oxime ester compound. A group selected from the group consisting of saturated aliphatic acyl groups is preferred, alkyl having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

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

R ^c2 is an optionally substituted phenyl group or an optionally substituted carbazolyl group. 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 a preferable substituent 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, and the number of carbon atoms. A cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, 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, the carbon atom which may have a substituent 7-20 phenylalkyl group, the naphthyl group which may have a substituent, the naphthoxy group which may have a substituent, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphtho which may have a substituent A yloxy group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, or an amino group substituted with an organic group of 1 or 2 , a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of the preferable substituent which the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 20 carbon atoms. Saturated aliphatic acyl group of Having a phenylalkyl group of 20, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a substituent The heterocyclyl group which may have an optional heterocyclyl group, 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 substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; and cyano groups. 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 within the range that does not impair the object of the present invention, but 1-4 desirable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c2 , the group represented by the following formula (c2) or (c3) is 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, and the group represented by the following formula (c2) is In the group represented, the group wherein 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 to 4)

(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. Preferred examples of 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; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; and cyano groups.

Among R ^c4 , a benzoyl group; naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a 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; A 4-(phenyl)phenylcarbonyl group is more preferable.

Moreover, in Formula (c2), the integer of 0-3 is preferable, as for n3, the integer of 0-2 is more preferable, It is especially preferable that it is 0 or 1. When n3 is 1, it is preferable that the position at which R ^c4 is bonded 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 within the range which does not impair the objective of this invention. Preferred 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, an alkoxycarbonyl group having 2 to 20 carbon atoms, a substituent having The phenyl group which may have a substituent, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the C7-C20 phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the naphth which may have a substituent a toyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. can

In R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in the 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 preferable 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 , a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 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 carbon A saturated aliphatic acyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a carbon atom and a dialkylamino group having 1 to 6 alkyl groups, 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 ^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 1-4 desirable. 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 formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

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

Moreover, the oxime ester compound represented by a 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 an optionally substituted chain alkyl group, an optionally substituted cyclic organic group 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 a hydrogen atom, 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 an integer of ∼4, and n5 is 0 or 1)

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

(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 bonds to the second position in the fluorene ring from the viewpoint of facilitating 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. Preferred 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 and a heterocyclylcarbonyl group which may have, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, 1-20 are preferable and, as for the number of carbon atoms of an alkyl group, 1-6 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, 1-20 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. In addition, when R ^c7 is an alkoxy group, it may be linear or branched. 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 methoxy group. A propyloxy group etc. are mentioned.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3-6 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 of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. 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, 2-20 are preferable and, as for the number of carbon atoms of an alkoxycarbonyl group, 2-7 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, 7-20 are preferable and, as for the number of carbon atoms of a phenylalkyl group, 7-10 are more preferable. Moreover, when R ^<c7> is a naphthylalkyl group, 11-20 are preferable and, as for the number of carbon atoms of a naphthylalkyl group, 11-14 are more preferable. Specific examples of the case where 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 of the case where 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, it is assumed that the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. 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, piperizine, piperazine, morpholine, piperizine, 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, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 21 carbon atoms. An actual group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a substituent and a naphthylalkyl group and heterocyclyl group having 11 to 20 carbon atoms which may have Specific examples of these preferred organic groups are the same as those of 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. can

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c7 further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 7 carbon atoms. A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms and a dialkylamino group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group and cyano group having 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 1-4 are preferable. 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 preferable 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, if R ^c7 is a hydrogen atom, since transparency tends to become favorable, it is preferable. In addition, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by a formula (c4a) or (c4b) described later, the transparency tends to be better.

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 combine with 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.

When R ^c8 and R ^c9 are a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. 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 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. 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. Preferred 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 preferred 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 preferred examples in the case where 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. 1-10 are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1-6 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 1-20, 1-10 are preferable and 1-6 are more preferable.

When R ^c8 and R ^c9 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. 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 is 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 alicyclic 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, 3-20 are preferable and 3-10 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, O, or heterocyclyl obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring it's gi When the heterocyclyl group is a condensed ring, it is assumed that the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. 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, piperizine, piperazine, morpholine, piperizine, tetrahydropyran, tetrahydrofuran, and the like.

R ^c8 and R ^c9 may combine with each other to form a ring. The group formed from the 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, a pyrimidine ring, etc. are mentioned.

Among the above-described R ^c8 and R ^c9 , preferred examples of the group include a group represented by the formula -A ¹ -A ² . In the formula, A ¹ is a straight-chain alkylene group, and A ² is, for example, an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group or an alkoxycarbonyl group.

1-10 are preferable and, as for the number of carbon atoms of the linear alkylene group of A< ¹ >, 1-6 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. 1-10 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 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.

Preferred 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 group -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phene alkoxyalkyl groups such as a tyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group and an 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group cyanoalkyl groups such as -n-heptyl and 8-cyano-n-octyl; 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 group -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pene cycloalkylalkyl groups such as a tyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group and an 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl group -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 8- alkoxycarbonylalkyl groups such as ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl 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.

Preferred groups among the above 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 -It is a pentyl group.

Examples of the preferable 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 optionally having a substituent, and a substituent as in R ^c7 It has an optionally phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, an optionally substituted phenylalkyl group, an optionally substituted naphthyl group, a substituent The naphthoxy group which may have a substituent, 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 heterooxy which may have a substituent A kryl group, the heterocyclylcarbonyl group which may have a substituent, the amino group substituted by 1 or 2 organic groups, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned. 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, a phenyl group or cycloalkylalkyl group which may have a substituent, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and a 2-methylphenyl group is more preferable. 5-10 are preferable, as for the carbon atom number of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, 5 or 6 are especially preferable. 1-8 are preferable, as for carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. 1-8 are preferable, as for the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 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 ^A3 is an alkylene group, 1-10 are preferable, as for the number of carbon atoms of an alkylene group, 1-6 are more preferable, and 1-4 are especially preferable.

Preferred 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.

Preferred 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 , a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

Preferred examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, and 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 Bornyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned. .

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

(In formulas (c4a) and (c4b), R ^c13 and R ^c14 are each an organic group, n6 is an integer from 0 to 4, and when R ^c13 and R ⁸ are adjacent to each other on the benzene ring, R ^c13 and R ^c14 may combine with each other to form a ring, n7 is an integer from 1 to 8, n8 is an integer from 1 to 5, n9 is an integer from 0 to (n8+3), and R ^c15 is an organic group )

Examples of the organic group for R ^c13 and R c14 in the formula (c4a) are the same as for ^Rc7 . 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 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. 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. In the group represented by the formula (c4a), preferred examples of the group in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group. can In said formula (c4a), n6 is an integer of 0-4, It is preferable that it is 0 or 1, 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. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 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 said formula (c4b), n8 is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable. In said formula (c4b), n9 is 0-(n8+3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, 1 or 2 is especially preferable.

In formula (c4), R ^c11 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. 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) is a step of converting the oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (c5) into an oxime ester group represented by >C=NO-COR ^c11 prepared by a method comprising R ^c11 is the same as R ^c11 in formula (c4).

The conversion of the oxime group (>C=N-OH) to the oxime ester group represented by >C=NO-COR ^c11 is carried out by reacting the compound represented by the aforementioned formula (c5) with an acylating agent.

Examples of the acylating agent giving 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).

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

(C) It is preferable that it is 0.5 to 30 weight% with respect to the weight of the whole solid content of the photosensitive resin composition, and, as for content of a photoinitiator, it is more preferable that it is 1 to 20 weight%. (C) By making content of a photoinitiator into said range, the photosensitive resin composition which the defect of a pattern shape does not produce easily can be obtained.

Moreover, you may combine a photoinitiator adjuvant with (C) a photoinitiator. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 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-methyl Thiol compounds, such as oxybenzothiazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, a pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate, etc. are mentioned. These photoinitiator adjuvants can be used individually or in combination of 2 or more types.

<(D) Pigment>

The photosensitive resin composition contains (D) a pigment. (D) Although it does not specifically limit as a pigment, For example, in the color index (C.I.; published by The Society of Dyers and Colorists), the compound classified as a pigment (Pigment), specifically, the following Those to which a color index (C.I.) number is assigned can be used.

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

Examples of orange pigments that can be preferably used include C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, and only the 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 preferably 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 the red pigment that can be preferably used include C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only the 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 preferably 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

Examples of pigments having a color different from the above that can be preferably 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, it is preferable that the photosensitive resin composition contains a black pigment as (D) pigment. Light-shielding property is provided to the cured film formed by using the photosensitive resin composition containing a black pigment. For this reason, the photosensitive resin composition containing a black pigment is used suitably for formation of the black matrix or black column spacer in a liquid crystal display panel, and formation of the bank for division of the light emitting layer in organic electroluminescent element.

Examples of the black pigment include carbon black, perylene-based pigment, lactam-based pigment, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, complex oxides, metal sulfides, metal sulfates, or Various pigments are mentioned regardless of organic substances, such as a metal carbonate, and an inorganic substance. Among these black pigments, carbon black is preferable because it is easy to obtain and easily forms a cured film having excellent light-shielding properties and high electrical resistance.

In addition, the hue of a black pigment is not limited to black which is an achromatic color in color theory, The black turning purple, black turning blue, or black turning red may be sufficient.

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 to which the process for introduce|transducing an acidic group was given is also preferable. The acidic group introduced into carbon black is a functional group exhibiting acidity as defined by Brensted. 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 forming 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, and ammonium ions, and alkali metal ions and ammonium ions such as sodium ion, potassium ion and lithium ion 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 resin composition, a carboxylic acid group, a carboxylic acid base, a sulfonic acid group and a sulfonic acid base are selected from the group consisting of Carbon black having at least one functional group used is preferred.

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

1) A method of introducing a sulfonic acid group 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 or hydrogen sulfite salt.

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 Williamson's etherification method.

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 of performing a Friedel-Crafts reaction 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 it is easy and safe to introduce an acidic group. 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 acids such as sulfanilic acid or aminobenzoic acids 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. 1-200 mmol 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, 5-100 mmol are more preferable.

The carbon black to which an acidic group has been introduced may be coated with a resin. When using the photosensitive resin 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 a low surface reflectance. In addition, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using the photosensitive resin 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, glyphthalate resin, epoxy resin, and alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate. , polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyether and thermoplastic resins such as ether ketone. The coating amount of the resin with respect to the carbon black is preferably 1 to 30% by weight with respect to the total of the weight of the carbon black and the weight of the resin.

Moreover, as a black pigment, a perylene type pigment can also be used preferably. 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 represents an alkylene group having 1 to 7 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) are, for example, JP-A-62-1753, JP It can be synthesized using the method described in Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the 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 resin composition, it is preferable that the average particle diameter of a perylene-type pigment is 10-1,000 nm.

Moreover, you may make it contain a lactam type pigment as a light-shielding agent. As a lactam type pigment, the compound represented by following formula (d-4) is mentioned, for example.

In the formula (d-4), X ^d represents a double bond and 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 sulfur 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 dihydroindolone ring from the viewpoint of easy production of the compound represented by the formula (d-4), and R ^d11 is preferably bonded to the 4th position of the dihydroindolone 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.

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

In order to disperse|distribute a lactam type pigment favorably in the photosensitive resin composition, it is preferable that the average particle diameter of a lactam type pigment is 10-1,000 nm.

In addition, 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 the black pigment. The AgSn alloy fine particles may have an AgSn alloy as a main component, and may contain, for example, Ni, Pd, Au or the like as other metal components.

As for the average particle diameter of this AgSn alloy fine particle, 1-300 nm is preferable.

When AgSn alloy is represented by the formula AgxSn, the range of x in which 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

When x=3, 3 Ag/Ag3Sn=0.7317

When x=4, 4 Ag/Ag4Sn=0.7843

In the case of x=10, 10·Ag/Ag10Sn=0.9008.

Therefore, this AgSn alloy becomes chemically stable when it contains 47.6 to 90% by weight of Ag, and when it contains 73.17 to 78.43% by weight of Ag, chemical stability and blackness can be effectively obtained with respect to the amount of Ag.

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 AgSn alloy microparticles|fine-particles are a thing with high insulation, depending on the use of the photosensitive resin composition, in order to further improve insulation, you may make it cover the surface with an insulating film. As a material of such an insulating film, a metal oxide or an organic high molecular compound is preferable.

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 preferably.

The thickness of the insulating film is preferably 1 to 100 nm, more preferably 5 to 50 nm, in order to sufficiently increase 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 film thickness can be formed at a relatively low temperature.

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

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

In order to disperse|distribute the (D) pigment demonstrated above uniformly in the photosensitive resin 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 (D), when carbon black is used as the pigment, it is preferable to use an acrylic resin-based dispersant as the dispersant.

In addition, the corrosive gas resulting from a dispersing agent may generate|occur|produce from a cured film. For this reason, it is also preferable that the (D) pigment is disperse|distributed, without using a dispersing agent.

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

In addition, the photosensitive resin composition WHEREIN: You may use (D) a pigment in combination with dye. What is necessary is just to select this dye suitably from well-known materials.

Dyes applicable to the photosensitive resin composition include, for example, azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, 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 (D) a pigment.

In addition to these dyes, for example, the dyes described in JP2013-225132A, JP2014-178477A, JP2013-137543A, JP2011-38085A, JP2014-197206A, etc. etc. can also be used preferably.

The amount of (D) pigment used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and typically 2 to 75 wt% is preferable with respect to the total weight of the solid content of the photosensitive resin composition, 3 -70 weight % is more preferable.

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

In addition, in this specification, it can define as a value including this existing dispersing agent with respect to the usage-amount of the pigment (D) mentioned above.

<(S) organic solvent>

It is preferable that the photosensitive resin composition contains the (S) organic solvent for the improvement of applicability|paintability and viscosity adjustment.

As the organic solvent (S), specifically, 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 (poly)alkylene glycol monoalkyl ethers, such as ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (polyethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. ) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methylethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, ethoxyethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate , other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; 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-diethyl nitrogen-containing polar organic solvents such as formamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine and N,N,N',N'-tetramethylurea; and the like.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers, alkyl lactate esters, and other esters described above are preferable. Other ethers and other esters mentioned above, such as benzyl acetate, are more preferable.

Moreover, it is also preferable that the (S) organic solvent contains the nitrogen-containing polar organic solvent from points, such as solubility of each component and the dispersibility of (D) a pigment. As the nitrogen-containing polar organic solvent, N,N,N',N'-tetramethylurea or the like can be used.

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

(S) Content of the organic solvent is not specifically limited, It sets suitably according to the coating film thickness at the density|concentration which can be apply|coated to a board|substrate etc. It is preferable that it is 5-500 cp, and, as for the viscosity of the photosensitive resin composition, it is more preferable that it is 10-50 cp, It is more preferable that it is 20-30 cp. Moreover, it is preferable that it is 5 to 100 weight%, and, as for solid content concentration, it is more preferable that it is 15 to 50 weight%.

<Other ingredients>

The photosensitive resin 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 resin composition contains a silane coupling agent because a shape is favorable and it is easy to form a cured film excellent in adhesiveness to a board|substrate. As the silane coupling agent, any conventionally known coupling agent may be used without any particular limitation.

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

<The preparation method of the photosensitive resin composition>

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

≪Method for producing a cured film≫

As a manufacturing method of a cured film, the manufacturing method of the conventionally well-known cured film using the photosensitive resin composition containing (B) a photopolymerizable compound is employable without limitation in particular.

As a preferable manufacturing method of a cured film,

The process of forming a coating film by apply|coating the above-mentioned photosensitive resin composition;

a step of positionally selectively exposing the coating film;

A process of forming a patterned cured film by developing the exposed coating film;

The method including the process of baking the patterned cured film is mentioned.

In order to form a cured film using the photosensitive resin composition, first, the photosensitive resin composition is apply|coated on the board|substrate selected according to the use of a cured film, and a coating film is formed. The method for forming the coating film is not particularly limited, but 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 resin 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 to 120° C., preferably 90 to 100° C. on a hot plate for 60 to 120 seconds, (2) at room temperature for several hours to several days. The method of leaving to stand, (3) the method of putting in a warm air heater or an infrared heater for several tens of minutes - several hours, the method of removing a solvent, etc. are mentioned.

Then, the coating film is exposed. The exposure is performed by irradiating active energy rays such as ultraviolet rays or excimer laser light. The exposure is position-selectively performed, for example, by a method of performing exposure through a negative-type mask. Although the energy dose to irradiate also changes with the composition of the photosensitive resin composition, for example, about 40-200 mJ/cm<2> is preferable.

In addition, when exposure is performed on the entire surface of the coating film, an unpatterned cured film having a shape according to the shape of the coating film is formed.

When a coating film is position-selectively exposed, an unexposed part melt|dissolves in a developing solution, and is removed by developing the film after exposure with a developing solution, and the patterned cured film is formed. The developing method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. The developer is appropriately selected according to the composition of the photosensitive resin 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.

Then, baking (post-baking) is performed on the patterned cured film. Although baking temperature is not specifically limited, 180-250 degreeC is preferable and 220-230 degreeC is more preferable. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes.

By baking as mentioned above, the cured film of the photosensitive resin composition can be obtained.

The colored cured film containing the (D) pigment formed in this way can be preferably used as a colored film, such as a black matrix or RGB in a color filter, according to the hue of (D) pigment, for example.

Hereinafter, although an Example is shown and this invention is demonstrated more concretely, the scope of the present invention is not limited to these Examples.

[Preparation Example 1]

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethyl ammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were placed in a 500 ml four-necked flask. The mixture was heated and dissolved at 90 to 100°C while blowing air into it at a rate of 25 ml/min. Then, while the solution was in a cloudy state, the temperature was gradually raised and heated to 120° C. to completely dissolve it. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. 12 hours were required for the acid value to reach the target value. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula which is colorless and transparent and is solid.

Next, 600 g of 3-methoxybutyl acetate was added and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way, and 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. , and the temperature was gradually increased and the reaction was carried out at 110 to 115°C for 4 hours. After confirming disappearance of an acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and it was made to react at 90 degreeC for 6 hours, and resin A-1 was obtained. The disappearance of the acid anhydride group was confirmed by the IR spectrum.

[Example 1, Example 2 and Comparative Examples 1-3]

In Examples and Comparative Examples, (A) as alkali-soluble resin, novolak resin, cardo resin, and acrylic resin were used.

TO-547 (trade name) manufactured by Sumitomo Bakelit Co., Ltd. was used as the novolak resin. TO-547 is a cresol novolac resin having a Mw of 30,000 obtained by adding oxalic acid and formalin at a concentration of 37% by weight to a mixture of 90 mol% of m-cresol and 10 mol% of 2,3,5-trimethylphenol, followed by a condensation reaction according to a conventional method.

As the cardo resin, Resin A-1 obtained in Preparation Example 1 was used.

As the acrylic resin, a resin containing 20 mol% of a structural unit derived from methacrylic acid and 80 mol% of a structural unit derived from styrene (manufactured by Shin-Nakamura Chemical Co., Ltd., NCF-3 (trade name), Mw=10,000) was used. .

In Examples and Comparative Examples, as the (B) photopolymerizable compound, a dendritic polymer and a polyfunctional monomer other than the dendritic polymer were used.

As the dendritic polymer, SIRIUS501 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used.

As a polyfunctional monomer other than the dendritic polymer, DPHA (dipentaerythritol hexaacrylate) was used.

In Examples and Comparative Examples, (C) OXE-02 (trade name, manufactured by BASF, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3- as a photopolymerization initiator) general] ethanone oxime) was used.

In Examples and Comparative Examples, (D) carbon black was used as the pigment.

As the carbon black, as D-A, carbon black manufactured by Daido Chemical Industry Co., Ltd. (pigment A (dispersion)), and as D-B, carbon black (pigment B (dispersion)) manufactured by Mikuni Color Co., Ltd. were used.

In addition, in Table 1 of this Example, the numerical value is described with respect to the sum of the solid content of this pigment and a dispersing agent.

Each of (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photoinitiator, and (D) pigment in the amounts shown in Table 1 are dissolved in (S) organic solvent so that the solid content concentration is 15% by weight , to obtain a photosensitive resin composition of each Example and Comparative Example.

(S) As the organic solvent, a mixed solvent of 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: cyclohexanone = 40:35:25 (weight ratio) was used.

Using the obtained photosensitive resin composition, the following method evaluated the difficulty of flow (flow resistance) by heating of a cured film, CD (Critical Dimension) of the patterned cured film, and the fine wire adhesiveness of a cured film.

<Evaluation of flow resistance>

First, a 100 mm square glass substrate was washed with pure water and dried in an oven at 160°C. The photosensitive resin composition obtained by the Example and the comparative example was apply|coated to the dry glass substrate, and it heated for 2 minutes on a 100 degreeC hotplate, and volatilized the solvent. Subsequently, after exposure using a 5 μm line mask, development was performed for 70 seconds with a 0.04% KOH developer.

The patterned substrate was divided in half, and the half was kept in an oven heated to 230° C. for 20 minutes. After the substrate heated in this way was taken out from the oven and cooled, the patterned portion was divided and the cross-section was observed by SEM.

For this item, the deformation (flow) due to heat was confirmed by comparing the substrates that were not heated in the oven.

In this item, evaluation was performed based on the following criteria.

○: When observing the round side of the upper part of the pattern, the taper angle of the pattern, and the protrusion from the lower part of the pattern, the pattern maintains a rectangular shape, or there is no significant difference between the heated substrate and the non-heated substrate. is in a state

△: Although not at a level that poses a problem in terms of quality, when observing the round side of the upper part of the pattern, the taper angle of the pattern, and the oozing out from the lower part of the pattern, a slight difference (shape collapse) is observed between the heated substrate and the non-heated substrate. .

x: When observing the round side of the upper part of the pattern, the taper angle of the pattern, and the oozing out from the lower part of the pattern, a clear difference (shape collapse) can be seen between the heated substrate and the non-heated substrate.

<CD evaluation>

Developing operation was carried out in the same manner as in <flow resistance evaluation> described above, and after that, the patterned substrate was divided in half, and the half was held in an oven heated to 230°C for 20 minutes.

Thereafter, the patterned portion was confirmed under a microscope, and evaluation was performed based on the following criteria.

○: A pattern is formed within ±10% of the mask width.

×: A pattern is formed in a dimension of more than +10% or less than -10% of the mask width. Alternatively, film reduction is evidently caused by development.

<fine wire adhesion evaluation>

With respect to the mask, the exposure operation was performed in the same manner as in the <flow resistance evaluation> described above, except for using a mask having a width of 3 to 20 µm on one side. Thereafter, development was performed for 80 seconds with a developer solution of 0.04% KOH, and whether there was peeling of the patterned portion was confirmed under a microscope, and evaluation was performed based on the following criteria.

(circle): Peeling is not observed also in the pattern part of 3 micrometers width.

x: Peeling will be observed in the pattern part of 3 micrometers width.

According to an embodiment, (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photoinitiator, and (D) a pigment, (A) a novolac resin as an alkali-soluble resin, In addition, (B) as a photopolymerizable compound, if it is a photosensitive resin composition containing a dendritic polymer having two or more ethylenically polymerizable groups at the terminal, it is difficult to excessively flow by heating, so a cured film patterned to a predetermined dimension can be formed. can be known

On the other hand, according to Comparative Examples 1 and 3, when the photosensitive resin composition does not contain a novolak resin, it turns out that formation of the cured film patterned by predetermined dimensions is difficult.

Moreover, according to the comparative example 2, when the photosensitive resin composition does not contain the dendritic polymer which has two or more ethylenic polymeric groups at the terminal, it turns out that the cured film formed is easy to flow by heating.

Claims (10)

(A) an alkali-soluble resin;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) a photosensitive resin composition comprising a pigment,
The (A) alkali-soluble resin comprises a novolak resin,
The (B) photopolymerizable compound contains a dendritic polymer having two or more ethylenically polymerizable groups at the terminal thereof,
The photosensitive resin composition, wherein the dendritic polymer comprises a dipentaerythritol hexaacrylate (DPHA)-linked multi-branched polyacrylate including a core derived from dipentaerythritol and having an acrylate group at the terminal. The method according to claim 1,
The dendritic polymer has the following formula (1):

(in formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is an ester bond in formula (1) with n hydroxy groups out of m hydroxy groups of the polyhydric alcohol R ³ (OH) _m is an n-valent residue given in, m and n are each independently an integer of 2 to 20, and m≥n)
A polyfunctional (meth)acrylate compound represented by the following formula (2):
(HS-CH ₂ -)pR ⁴ (2)
(In formula (2), R ⁴ is a single bond or a hydrocarbon group containing 2 to 6 valent C1 to 6 carbon atoms, p is 2 when R ⁴ is a single bond, and R ⁴ is 2 to 6 valent In the case of a hydrocarbon group-containing group, it is an integer of 2 to 6)
A photosensitive resin composition which is an adduct of a polyvalent mercapto compound represented by . The method according to claim 1,
The photosensitive resin composition in which the said (A) alkali-soluble resin further contains resin which has a cardo structure. The method according to claim 1,
The photosensitive resin composition of which the weight average molecular weight of the said novolak resin is 2,000 or more and 50,000 or less. The method according to claim 1,
The photosensitive resin composition in which the said (D) pigment is a black pigment. 6. The method of claim 5,
The photosensitive resin composition in which the said black pigment is carbon black. The method according to claim 1,
The photosensitive resin composition whose ratio (Wn:Wd) of content Wn [g] of the said novolak resin and content Wd [g] of the said dendritic polymer exists in the range of 20:1 - 1:20. The cured film formed by hardening|curing the photosensitive resin composition in any one of Claims 1-7. A color filter provided with the cured film of Claim 8. The process of forming a coating film by apply|coating the photosensitive resin composition of any one of Claims 1-7;
a step of positionally selectively exposing the coating film;
Developing the exposed coating film to form a patterned cured film;
The manufacturing method of the cured film including the process of baking the said patterned cured film.