JP2018013716A - Photosensitive resin composition, cured film, color filter, and method for producing cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can form a colored cured film that is prevented from excessively flowing due to heating in post baking and is finely patterned in a desired size, a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a color filter containing the cured film.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pigment. As (A) alkali-soluble resin used is a novolac resin, and as (B) photopolymerizable compound used is a dendritic polymer having two or more ethylenic polymerizable groups at a terminal.SELECTED DRAWING: None

Description

  The present invention uses a negative photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, a color filter including the cured film, and the negative photosensitive resin composition described above. The present invention relates to a method for producing a cured film.

  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 a pair of electrodes facing each other is formed. A color filter having pixels of red (R), green (G), blue (B) and the like is formed inside one substrate. In this color filter, in order to prevent color mixing of different colors in each pixel or to conceal the electrode pattern, the color filter is usually arranged in a matrix so as to partition the pixels of R, G, and B colors. A black matrix is formed.

  Generally, the color filter is formed by a lithography method. Specifically, first, a black photosensitive composition is applied to a substrate, exposed and developed to form a black matrix. Then, for each of the photosensitive compositions of red (R), green (G), and blue (B), coating, exposure, and development are repeated to form a pattern of each color at a predetermined position, thereby forming a color filter. Form.

As a method for forming a colored film constituting a color filter, for example, a method using a negative photosensitive resin composition has been proposed as a method for forming a black matrix.
Specifically, use of a negative photosensitive resin composition including a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion in which acrylic resin fine particles are dispersed, and a solvent has been proposed. (See Patent Document 1).

In recent years, a technology for blending a dendritic polymer having a specific structure as a photosensitive resin composition for a black resist containing a light-shielding component such as a black organic pigment or a dispersion resin composition containing a colorant. Has been pioneered.
According to such a technique, it is said that a resin composition having a smooth coating film surface and no deterioration of surface roughness due to thermosetting shrinkage, or a composition excellent in adhesion and pattern shape during development can be achieved ( (See Patent Documents 2 and 3).

JP 2011-170075 A JP 2012-27448 A JP 2012-93591 A

Patent Document 1 proposes the use of resin-coated carbon black as a black pigment to be blended in 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 having 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 having a high resistance value while eliminating the problem of low optical density, it is conceivable to use a pigment having a small secondary particle diameter.
However, when using a pigment with a small secondary particle size, the colored cured film constituting the color filter such as a black matrix flows excessively by heating in post-baking performed after exposure and development, An unacceptable shape change may occur in the cured film.

Furthermore, it is generally required that the patterned colored film constituting the color filter is accurately formed with the designed size.
In the case of using the compositions disclosed in Patent Document 2 and Patent Document 3, it is difficult to form a pattern having the size as designed, although a certain suppression effect is shown with respect to the shape change of the cured film described above. Met.

  The present invention has been made in view of the above problems, and is a photosensitive resin composition that is difficult to flow excessively by heating during post-baking and can form a colored cured film that is finely patterned with a desired size. Another object is to provide a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a color filter including the cured film.

  In the photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pigment, The present invention has found that the above-mentioned problems can be solved by using a novolak resin as the alkali-soluble resin and using a dendritic polymer having two or more ethylenic polymerizable groups as the photopolymerizable compound (B). It came to complete. Specifically, the present invention provides the following.

The first aspect of the present invention is:
(A) an alkali-soluble resin;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) a pigment;
A photosensitive resin composition comprising:
(A) the alkali-soluble resin includes a novolac resin;
(B) The photopolymerizable compound is a photosensitive resin composition containing a dendritic polymer having two or more ethylenic polymerizable groups at its terminals.

  The second aspect of the present invention is a cured film formed by curing the photosensitive resin composition according to the first aspect.

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

According to a fourth aspect of the present invention, there is provided a step of forming a coating film by applying the photosensitive resin composition according to the first aspect;
A step of selectively exposing the coating film;
Developing the exposed coating film to form a patterned cured film; and
And baking the patterned cured film. A method for producing the cured film.

  According to the present invention, a photosensitive resin composition that is difficult to flow excessively by heating during post-baking and can form a colored cured film that is finely patterned with a desired size, and the photosensitive resin composition are used. The manufacturing method of a cured film, the cured film formed by hardening the said photosensitive resin composition, and a color filter provided with the said cured film can be provided.

  Hereinafter, the present invention will be described based on preferred embodiments. In the present specification, “to” represents the above (lower limit value) to the following (upper limit value) unless otherwise specified.

≪Photosensitive resin composition≫
The photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pigment.
The photosensitive resin composition contains a novolac resin as the (A) alkali-soluble resin. Moreover, the photosensitive resin composition contains the dendritic polymer which has a 2 or more ethylenic polymeric group at the terminal as (B) photopolymerizable compound.
When the photosensitive resin composition contains the above-described novolak resin and the dendritic polymer, it forms a colored cured film that is difficult to flow excessively by heating during post-baking and is finely patterned in a desired size. Cheap.

  Hereinafter, essential or optional components contained in the photosensitive resin composition and a method for preparing the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
The photosensitive resin composition contains (A) an 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 a cured film that hardly flows excessively due to overheating during post-baking.
Hereinafter, (A1) novolak resin and (A1) alkali-soluble resin other than novolak resin will be described.

[(A1) Novolac resin]
(A1) As the novolak resin, various novolak resins conventionally blended in the photosensitive resin composition can be used. (A1) As the novolak resin, those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst are preferable.

(Phenols)
(A1) Examples of phenols used in preparing the novolak resin include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2 Xylenols such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; 2-isopropyl Alkylphenols such as phenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4,5 -Trimethylphe Trialkylphenols such as alcohol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phlorogricinol; alkyl polyphenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (any The alkyl group also has 1 to 4 carbon atoms.); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as heat resistance of a cured film formed using the photosensitive resin composition can be adjusted by adjusting the blending ratio of the two.
The blending ratio of m-cresol and p-cresol is not particularly limited, but the molar ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a cured film having excellent heat resistance.

Moreover, the novolak resin manufactured combining m-cresol and 2,3,5-trimethylphenol is also preferable. When such a novolak resin is used, it is particularly easy to obtain a photosensitive resin composition that can form a cured film that hardly flows excessively by heating during post-baking.
The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol / 2,3,5-trimethylphenol is 70/30 or more and 95/5 or less. Is preferred.

(Aldehydes)
(A1) Examples of aldehydes used when producing a novolak resin include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(Acid catalyst)
(A1) Examples of the acid catalyst used in preparing the novolak resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluene And organic acids such as sulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular weight)
(A1) The polystyrene-reduced weight average molecular weight (Mw; hereinafter, also simply referred to as “weight average molecular weight”) of the novolak resin is a viewpoint of resistance to a flow caused by heating of a cured film formed using the photosensitive resin composition. Therefore, the lower limit is preferably 2000, more preferably 5000, particularly preferably 10,000, further preferably 15000, most preferably 20000, more preferably 50000, more preferably 45000, still more preferably 40000, and most preferably 35000. .

  (A1) As the novolac resin, those having different polystyrene-reduced weight average molecular weights can be used in combination of at least two kinds. By using a combination of different weight average molecular weights, it is possible to balance the developability of the photosensitive resin composition and the heat resistance of the cured film formed using the photosensitive resin composition.

[(A2) resin having cardo structure]
In the photosensitive resin composition, from the viewpoint of further improving the flow resistance of the cured film, (A) a resin having an (A2) cardo structure as an alkali-soluble resin (hereinafter also referred to as “(A2) cardo resin”). Can also be included.

(A2) As the resin having a cardo skeleton, a resin having a cardo skeleton in its structure and having a predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. The second annular structure and the third annular structure may be the same structure or different structures.
A typical example of a cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the 9-position carbon atom of a fluorene ring.

  The (A2) cardo structure resin is not particularly limited, and a conventionally known resin can be used. Among these, the resin represented by the following formula (a-1) is preferable.

Wherein ^{(a-1), X} a represents a group represented by the following formula (a-2). m1 represents an integer of 0 to 20.

In the formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 independently represents a hydrogen atom or a methyl group. , R ^a3 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), R ^a3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 6 carbon atoms. Most preferred are ethane-1,2-diyl, propane-1,2-diyl, and propane 1,3-diyl.

Ring A in Formula (a-3) represents an aliphatic ring that 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 include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

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

Divalent X ^a in the formula (a-1), by reacting a tetracarboxylic acid dianhydride which gives a residue Z ^a, a diol compound represented by the following formula (a-2a), ( A1) Introduced into cardo resin.

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

The diol compound represented by the formula (a-2a) can be produced, for example, by the following method.
First, after substituting the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2b) with a group represented by —R ^a3 —OH, if necessary, according to a conventional method, Glycidylation using epichlorohydrin or the like is performed to obtain an epoxy compound represented by the following formula (a-2c).
Next, the diol compound represented by the formula (a-2a) is obtained by reacting the epoxy compound represented by the formula (a-2c) with acrylic acid or methacrylic acid.
In formula (a-2b) and formula (a-2c), R ^a1 , R ^a3 , and m2 are as described for formula (a-2). Ring A in formula (a-2b) and formula (a-2c) is as described for formula (a-3).
In addition, the manufacturing method of the diol compound represented by a formula (a-2a) is not limited to said method.

Preferable examples of the diol compound represented by the formula (a-2b) include the following diol compounds.

In the above formula (a-1), R ^a0 is a hydrogen atom or a group represented by —CO—Y ^a —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 acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include tetracarboxylic dianhydrides represented by the following formula (a-4), pyromellitic dianhydrides, benzophenone tetracarboxylic dianhydrides, and biphenyltetracarboxylic dianhydrides. Products, biphenyl ether tetracarboxylic dianhydride and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

（式（ａ−４）中、Ｒ^ａ４、Ｒ^ａ５、及びＲ^ａ６は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍ３は、０〜１２の整数を示す。）

(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. M3 represents an integer of 0 to 12.)

The alkyl group that can be selected as 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, more preferably 1 to 3, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. Is particularly preferred.
When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

As R ^{a4 in} formula (a-4), a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is more preferable independently from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. R ^{a4 in} 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.
A plurality of R ^a4 in the formula (a-4) are preferably the same group because preparation of a highly pure tetracarboxylic dianhydride is easy.

M3 in Formula (a-4) represents an integer of 0 to 12. By making the value of m3 12 or less, purification of tetracarboxylic dianhydride can be facilitated.
In view of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3.
From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2.
M3 in formula (a-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^a5 and R ^{a6 in} formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^a4 .
R ^a5 and R ^a6 are each a hydrogen atom or a carbon atom number of 1 to 10 (preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 5) from the viewpoint of easy purification of tetracarboxylic dianhydride. The alkyl group is preferably 1 to 4, particularly preferably 1 to 3), and particularly preferably a hydrogen atom or a methyl group.

  Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -Tetracarboxylic dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-(methylnorbornane) -5,5 '', 6,6 ''-tetra Carboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane- 2-spiro-2'-siku Hexanone-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 Product, norbornane-2- Pyro-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 Thing, 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. The.

  (A2) The weight average molecular weight of the cardo resin is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

[Other alkali-soluble resins]
The (A) alkali-soluble resin may contain other alkali-soluble resins other than (A1) novolak resin and (A2) cardo resin as long as the object of the present invention is not impaired. The other alkali-soluble resin is not particularly limited as long as it is a resin having a predetermined alkali solubility, and can be appropriately selected from various resins conventionally blended in the photosensitive resin composition.
As the other alkali-soluble resin, (A3) acrylic resin is preferable because adjustment of various properties of the resin containing alkali solubility is easy.

  (A3) As an acrylic resin, what contains the structural unit derived from (meth) acrylic acid and / or the structural unit derived from 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 above formula (a-5), R ^a7 is a hydrogen atom or a methyl group, and R ^a8 is a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

The substituent other than a hydrocarbon group in the organic group R ^a8, the effect is not particularly limited as long as they do not impair the present invention, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, hydroxyimino group, alkyl ether group, an alkyl thioether group, an aryl ether group, aryl thioether group, an amino group (-NH _2, -NHR, -NRR ': R and R 'Each independently represents a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

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. 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 the alkyl group is linear or branched, the number of carbon atoms is preferably 1-20, more preferably 1-15, and particularly preferably 1-10. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 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, An isodecyl group etc. are mentioned.

  When the alkyl group is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups contained in the alkyl group include a monocyclic alicyclic group such as a cyclopentyl group and a cyclohexyl group, And an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Moreover, (A3) acrylic resin may be obtained by polymerizing monomers other than (meth) acrylic acid ester. Examples of such monomers include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers can be used alone or in combination of two or more.

  (Meth) acrylamides include (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 and the like.

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

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

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

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetracrotobenzoate, vinyl naphthoate, and the like.

  Styrenes 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, ethoxy Alkyl styrene such as methyl styrene and 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-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from another monomer in the (A3) acrylic resin are not particularly limited as long as the object of the present invention is not impaired. (A3) The amount of the structural unit derived from (meth) acrylic acid in the acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 30% by mass with respect to the mass of the acrylic resin.

  (A3) The weight average molecular weight of the acrylic resin is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  (A) The content of the alkali-soluble resin is preferably 10 to 65% by mass and more preferably 15 to 50% by mass with respect to the mass of the entire solid content of the photosensitive resin composition. By setting it as said range, it is easy to obtain the photosensitive resin composition excellent in developability.

  Further, the content of (A1) novolak resin is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass with respect to the mass of the entire solid content of the photosensitive resin composition. More preferably, the content is 1.2 to 5% by mass. By setting it as said range, the hardened | cured film which cannot flow easily excessively by the heating at the time of post-baking can be formed, and it is easy to obtain the photosensitive resin composition excellent in developability.

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

<(B) Photopolymerizable compound>
The photosensitive resin composition contains (B) a photopolymerizable compound. (B) As the photopolymerizable compound, a compound having an ethylenic polymerizable group can be preferably used.
The photopolymerizable compound (B) includes a dendritic polymer having two or more ethylenic polymerizable groups at its terminals.

Here, although it is not certain that the photosensitive resin composition of the present embodiment can solve the problems according to the present application, the following mechanism is conceivable.
That is, when the photosensitive resin composition contains the above-described dendritic polymer as the photopolymerizable compound (B), curing of the photosensitive resin composition proceeds well during exposure, and post-baking is performed on the cured film. However, an excessive heat flow of the cured film hardly occurs.
On the other hand, when the photosensitive resin composition contains a dendritic polymer, curing by exposure proceeds excessively, and a pattern having a width or diameter larger than a desired size may be formed after development.
However, when the photosensitive resin composition contains a combination of the above-mentioned (A1) novolak resin and a dendritic polymer, (A1) the novolak resin appropriately traps radicals during the progress of the curing reaction by exposure, and exposure Excessive progress of the curing reaction at the time is suppressed.
For this reason, when a photosensitive resin composition containing a combination of (A1) novolac resin and a dendritic polymer is used, it is difficult to flow excessively due to heating during post-baking, and a fine pattern having a desired size and shape is formed. It is thought that it is easy to form.

[Dendritic polymer]
As described above, the photosensitive resin composition includes a multi-branched dendritic polymer having two or more ethylenic polymerizable groups as terminals (B) as a photopolymerizable compound.
The dendritic polymer has a branch point in its structure that extends the molecular chain in three or more directions. The number of branch points in one molecule of the dendritic polymer is 3 or more, preferably 4 or more.
For example, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate have two branch points. For this reason, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate do not correspond to dendritic polymers.
In view of heat resistance and hydrolysis resistance of a cured film formed using the photosensitive resin composition, the dendritic polymer preferably does not contain a urethane bond.

The ethylenic polymerizable group of the dendritic polymer is preferably derived from a (meth) acrylate compound, but is not limited thereto.
The hyperbranched dendritic polymer is not particularly limited as long as it has a dendritic hyperbranched structure and has two or more ethylenic polymerizable groups at its terminals.
As such a dendritic polymer, a polymer called a dendrimer or a hyperbranched polymer is preferably used.

Examples of commercially available dendritic polymers having an ethylenically polymerizable group include Biscoat # 1000 (trade name), Biscoat # 1020 (trade name), and STAR 501 (SIRIUS 501) manufactured by Osaka Organic Chemical Industry Co., Ltd. , SUBARRU 501) (trade name) and the like.
Biscote # 1000 and Biscote # 1020 are mainly composed of a multi-branched (dendrimer type) polyester acrylate having an acrylate group at the terminal. The molecular weight of biscoat # 1000 is about 1000 to 2000, and the molecular weight of biscoat # 1020 is about 1000 to 3000.
STAR-501 contains a dipentaerythritol hexaacrylate (DPHA) -linked multi-branched polyacrylate having a core derived from dipentaerythritol and having an acrylate group at the terminal. The molecular weight of STAR 501 is about 16000 to 24000.

The dendritic polymer may be a polymer prepared using a dendrimer or hyperbranched polymer having a hydroxyl group, an amino group, or a carboxy group at the terminal.
An alkenyl group having a double bond at the terminal, such as a desired amount of an acryloyl group, a methacryloyl group, or an allyl group, according to a known method, for a hydrogen atom contained in a hydroxyl group or amino group at the end of a dendrimer or hyperbranched polymer (B) A dendritic polymer used as a photopolymerizable compound is obtained.
Alternatively, the carboxy group at the end of the dendrimer or hyperbranched polymer may be esterified or amidated using an alcohol or amine having an ethylenic double bond at the end according to a known method. A dendritic polymer used as a photopolymerizable compound is obtained. Examples of alcohols and amines having an ethylenic double bond at the terminal include 2-hydroxyethyl (meth) acrylate, allyl alcohol, 2-aminoethyl (meth) acrylate, and allylamine.

Examples of the dendrimer having a hydroxyl group, an amino group, or a carboxy group at the terminal include:
A polyamidoamine dendrimer having a terminal amino group known as PAMAM;
PAMAM type dendrimer in which the terminal amino group is converted to a hydroxyalkylamino group such as 2-hydroxyethylamino group;
A PAMAM type dendrimer in which a terminal amino group is converted to a carboxyalkylamide group such as a succinamic acid group (—NH—CO—CH ₂ CH ₂ —COOH);
A poly (glycerol-succinic acid) dendrimer having a terminal hydroxyl group, which is a copolyester of glycerol and succinic acid;
A copolyester of glycerol and succinic acid, a poly (glycerol-succinic acid) dendrimer having a terminal carboxy group; and a homopolyester of 2,2-bis (hydroxymethyl) propanoic acid (bis-MPA); Examples include dendrimers having a hydroxyl group at the terminal.

Preferred dendritic polymers include the polymers described below.
First, the ethylenically 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 the carbon-carbon double bond. It is known that a Michael addition reaction occurs in a vinyl group having the strongest interaction with a nucleophile such as a mercapto compound.
Accordingly, if 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, carbonyl If there is an addition reaction at the β-position carbon relative to the group and there are a plurality of groups where the addition reaction occurs, a large number of branches are produced, resulting in a dendritic polymer. Such dendritic polymers are known from WO 2008/47620 and can be obtained by the methods described in such documents.

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

（式（１）中、Ｒ_１は、水素原子、又は炭素原子数１〜４のアルキル基であり、Ｒ^２は多価アルコールＲ_３（ＯＨ）_ｍのｍ個のヒドロキシ基のうちｎ個のヒドロキシ基を式（１）中のエステル結合に供したｎ価の残基であり、ｍ及びｎはそれぞれ独立に２〜２０の整数であり、ｍ≧ｎである。）

(In formula (1), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² is n of m hydroxy groups of polyhydric alcohol R ₃ (OH) _m . (The hydroxyl group is an n-valent residue subjected to an ester bond in formula (1), and 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 2-6 valent hydrocarbon group-containing group having 1 to 6 carbon atoms, p is 2 when R ⁴ is a single bond, and R ⁴ Is a 2-6 valent hydrocarbon group-containing group, it is an integer of 2-6.)

  Here, Michael addition of the polyvalent mercapto compound represented by the formula (2) to the polyfunctional (meth) acrylate compound represented by the formula (1) indicates that the resulting dendritic polymer is still a carbon-carbon double The carbon-carbon double bond of the compound represented by the formula (1) should be kept in the range of 0.1 to 50 mol% as a whole so that radiation polymerization based on the bond can be performed. Is preferred.

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

  The dendritic polymer preferably has a sufficient amount of functional groups to be polymerized satisfactorily by exposure. For this purpose, the molecular weight of the dendritic polymer is preferably in the range of 100 to 10,000 as the molecular weight per mole of carbon-carbon double bonds. The preferred weight average molecular weight (Mw) of the dendritic polymer is 8000 to 40000, more preferably 15000 to 25000.

In the above formula (1), preferably, R ³ (OH) _m is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, A polyhydric alcohol ether in which plural molecules of a monohydric alcohol are linked via an ether bond by dehydration condensation of the alcohol, or an ester of these polyhydric alcohol or polyhydric alcohol ether and a hydroxy acid.
In said formula (1), m and n represent the integer of 2-20 independently, but it is m> = n. Preferably, m and n are integers of 2 to 10, where m ≧ n.

Preferable specific examples of the polyfunctional (meth) acrylate compound represented by the formula (1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolethanetri (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) a Relate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone Modified dipentaerythritol hexa (meth) acrylate, epichlorohydrin modified hexahydrophthalic acid di (meth) acrylate, hydroxypivalic acid neopentyl 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 tri Mention may be made of (meth) acrylic acid esters such as methylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. . These compounds may be used individually by 1 type, and may use 2 or more types together.

In the formula (2), preferably, R ^{4 further} includes a single bond or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent or an oxygen atom in the skeleton of the hydrocarbon group. A good hydrocarbon group, which may be linear or branched.
In addition, these hydrocarbon group-containing groups may further have a carbonyloxy group bonded to a part of the thiomethyl group (HS—CH ₂ —) appearing in the formula (2). In addition, when an oxygen atom is included in the skeleton of the hydrocarbon group, both ends are preferably hydrocarbon groups. 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 will be 2-6.

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

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

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

  When synthesizing a dendritic polymer, a Michael addition reaction occurs in which the polyvalent mercapto compound represented by the above formula (2) is added to the double bond of the polyfunctional (meth) acrylate compound represented by the above 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. The reaction time is not particularly limited, but is usually 30 minutes to 20 hours, preferably 6 to 12 hours.

[Other photopolymerizable compounds]
In the photosensitive resin composition, in addition to the dendritic polymer described above, various kinds of light conventionally added to the photosensitive resin composition for the purpose of improving the resolution, etc., as long as the object of the present invention is not impaired. A polymerizable compound may be included.
Other photopolymerizable compounds are preferably monomers having an ethylenically unsaturated group. 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, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) 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 Examples include (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  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 (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) 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, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate), methylenebis (meth) acrylamide, (meth) acrylamide Examples thereof include polyfunctional monomers such as methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer has a tendency to increase the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition. Is preferable, a polyfunctional monomer having 4 or more functional groups is more preferable, and a polyfunctional monomer having 5 or more functional groups is more preferable.
Specifically, it is preferable that a dendritic polymer and a polyfunctional monomer having 5 or more functional groups are used in combination, and the dendritic polymer, dipentaerythritol penta (meth) acrylate, and / or dipentaerythritol hexa (meth). It is more preferable to use acrylate together.

  (B) 1-50 mass% is preferable with respect to the mass 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 mass% is more preferable. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

The content of the dendritic polymer in the photosensitive resin composition is preferably from 0.1 to 30 mass%, more preferably from 0.5 to 25 mass%, based on the mass of the entire solid content of the photosensitive resin composition. By setting it as said range, it is easy to obtain the photosensitive resin composition which is hard to flow excessively by the heating at the time of post-baking, and is easy to form the fine pattern which is a desired size and shape.
The ratio (Wn: Wd) of the novolak resin content Wn [g] to the dendritic polymer content Wd [g] in the photosensitive resin composition is within the range of 20: 1 to 1:20. In the range of 18: 1 to 1:18, more preferably in the range of 15: 1 to 1:15, and most preferably in the range of 5: 1 to 1:12.

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

  (C) Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl]. 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 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, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4 -Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamyl Benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimi Sol, 2-mercaptobenzoxazole, 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, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropi Phenone, 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-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) ) Pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (to Chloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2- Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-) Methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo -4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime and ethanone are particularly preferable. , 1- [9-ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 2- (benzoyloxyimino) -1- [4 -(Phenylthio) phenyl] -1-octanone.

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０〜４の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１〜６のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group;
n1 is an integer of 0 to 4,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent,
R ^c3 is 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 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, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Examples include an amino group substituted with an mino group, 1 or 2 organic groups, a morpholin-1-yl group, 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. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, 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, and an 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, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c1 is an alkyl group, the alkyl group may include 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. Further, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples when R ^c1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c1 is an alkoxy group, the alkoxy group may include 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 methoxypropyloxy group.

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 in the case where 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 in the case where 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 acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. 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-dimethylpropanoyloxy 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 and the like.

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 methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an 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. Further, when R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples when R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of 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 monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon A saturated aliphatic acyl group having 2 to 20 atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenyl having 7 to 20 carbon atoms which may have a substituent Examples thereof include an alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. It is done. Specific examples of these suitable organic groups are the same as those for 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-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent, the substituent is as follows: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon atom A monoalkylamino group having 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, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , since it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound, an alkyl group having 1 to 6 carbon atoms, 1 to 1 carbon atoms, and the like. A group selected from the group consisting of 6 alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferred, alkyls having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.

Position R ^c1 is bonded to the phenyl group, the phenyl group R ^c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group that may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms. -10 cycloalkyl group, C3-C10 cycloalkoxy group, C2-C20 saturated aliphatic acyl group, C2-C20 alkoxycarbonyl group, C2-C20 saturated Aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Naphthyl A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have a group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1 or 2 organic groups Examples include an amino group substituted with a group, 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 suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a substituent. A phenoxycarbonyl group which may have, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent; Heterogeneity And a krylcarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. With respect to an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with one or two organic groups , R ^c1 .

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or the carbazolyl group has in R ^c2 further have a substituent include an alkyl group having 1 to 6 carbon atoms An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; Benzoyl group; benzoyl group; benzoyl substituted by a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Examples include a holin-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 the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０〜４の整数である。）

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

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

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

When R ^c4 in formula (c2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. In the formula (c2), when R ^c4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic group having 2 to 7 carbon atoms. An acyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms; A benzoyl group substituted by a group selected from the group consisting of a -1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; 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.

In ^Rc4 , substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

R ^c5 in formula (c3) can be selected from various organic groups as long as the object of the present invention is not ^impaired . Preferable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkoxycarbonyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, carbon atoms which may have a substituent 7 ~ 20 phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among 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 formula (c3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. The heterocyclyl group which may be sufficient is mentioned. Among these groups, R ^c6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

^Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. 6 alkoxy groups, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl having 1 to 6 carbon atoms And a monoalkylamino group having a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^c3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

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

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

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０〜４の整数であり、ｎ５は０又は１である。）

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

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

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

(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 , one of the one or more R ^c7 is a fluorene ring because synthesis of the compound represented by the formula (c4) is easy. Bonding at the 2-position is preferable. If R ^c7 is more, a plurality of R ^c7 is independently in 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, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, Examples include a heterocyclylcarbonyl group which may have a substituent, 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, the number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-6. Further, when R ^c7 is an alkyl group, it may be linear or branched. 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, and an 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, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c7 is an alkyl group, the alkyl group may include 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, the alkoxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples when R ^c7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c7 is an alkoxy group, the alkoxy group may include 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 methoxypropyloxy group.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of 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, and more preferably 2 to 7. Specific examples when R ^c7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. 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-dimethylpropanoyloxy 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 and the like.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. 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 contained in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and carbon atoms. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. . Specific examples of these suitable organic groups are the same as those for R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c7 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 a carbon atom. A monoalkylamino group having 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, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included 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 be improved. 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 groups suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. As R ^c12 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.
Moreover, it is preferable that R ^c7 is a hydrogen atom because transparency tends to be good. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by the following formula (c4a) or (c4b), the transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 each represent a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, as R ^c8 and R ^c9 , a chain alkyl group which may have a substituent is preferable. When R ^c8 and R ^c9 are chain alkyl groups 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 chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Specific examples when R ^c8 and R ^c9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and 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, isodecyl group and the like. When R ^c8 and R ^c9 are alkyl groups, 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 chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In 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 the 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 the preferred examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number 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 substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, and more preferably 1-6.

When R ^c8 and R ^c9 are cyclic organic groups, 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 cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? A group formed by condensation of a plurality of benzene rings is preferred. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable 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 aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done.

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

When the group formed by combining 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 that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

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

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of an alkoxy group, 1-6 are more preferable. When A ² 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 A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that 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 group that R ^c8 and R ^c9 have as a substituent.

Preferable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n − Cyanoalkyl groups such as an nyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopent Cycloalkylalkyl groups such as ru-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-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-ethoxy Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 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-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ^c8 and R ^c9 , preferred groups among the above 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-hepta A fluoro-n-pentyl group;

Examples of suitable organic groups for R ^c10 are the same as for R ^c7 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^c7 . R ^c10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ^c7 may have.

Among organic groups, as R ^c10 , an alkyl group, a cycloalkyl group, an ^optionally substituted phenyl group, or a cycloalkylalkyl group, or an optionally substituted phenylthio group on an aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number 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, a 2- (4-chlorophenylthio) ethyl group is preferable.

In addition, as R ^c10 , a group represented by —A ³ —CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. If A ³ is an alkylene group, number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, 1 to 4 are particularly preferred.

Preferable 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 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, and n-hexyl. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferred examples of the group represented by —A ³ —CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl 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-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｃ１３及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｃ１５は有機基である。） ^Having described ^{R c10,} as the ^{R c10,} preferably a group represented by the following formula (C4a) or (C4b).

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

Examples of the organic group for R ^c13 and R ^{c14 in} formula (c4a) are the same as those for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 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. Preferred examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group, 1,2,3,4- And tetrahydronaphthalen-5-yl group. In said formula (c4a), n6 is an integer of 0-4, It is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include the same groups as those described for R ^c7 . Of the organic groups, an alkyl group is preferred. 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. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, 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, and 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, and 1 or 2 is especially preferable.

In formula (c4), R ^c11 represents 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. Preferred examples of the substituent that may be present when R ^c11 is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that may be present when R ^c7 is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

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

The compound represented by the formula (c4) represents an oxime group (> C═N—OH) contained in the compound represented by the above formula (c5) by> C═N—O—COR ^c11. It is produced by a method including a step of converting to an oxime ester group. R ^c11 are 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═N—O—COR ^c11 involves conversion of the compound represented by the above formula (c5), an acylating agent, It is performed by reacting.
The acylating agent to give the acyl group represented by -COR ^{c11, (R c11} _CO) or an acid anhydride represented by ₂ ^O, R c11 COHal (Hal is a halogen atom) include acid halide represented by It is done.

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

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

  Further, (C) a photoinitiator may be combined with the photopolymerization initiator. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 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-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

<(D) Pigment>
The photosensitive resin composition contains (D) a pigment. (D) The pigment is not particularly limited. For example, in the color index (CI; issued by The Society of Dyers and Colorists), a compound classified as a pigment, specifically, A color index (C.I.) number such as is attached.

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

  Examples of orange pigments that can be suitably used include C.I. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, and 73.

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

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 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, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7.

  Moreover, it is preferable that the photosensitive resin composition contains a black pigment as (D) pigment. By using a photosensitive resin composition containing a black pigment, light shielding properties are imparted to the formed cured film. For this reason, the photosensitive resin composition containing a black pigment is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel, or forming a bank for partitioning a light emitting layer in an organic EL element.

Examples of black pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides Various pigments can be mentioned regardless of organic substances and inorganic substances such as organic substances, metal sulfates or metal carbonates. Among these black pigments, carbon black is preferable because it is easily available and easily forms a cured film having excellent light shielding properties and high electrical resistance.
Note that the hue of the black pigment is not limited to black, which is an achromatic color, and may be violet black, bluish black, or reddish black.

  As the carbon black, known carbon black such as channel black, furnace black, thermal black, lamp black and the like can be used. Resin-coated carbon black may also be used.

  As the carbon black, carbon black subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity according to the Bronsted definition. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation that forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ion, potassium ion, lithium ion, and ammonium ion are preferable.

  Among the carbon blacks that have been treated to introduce acidic groups as described above, carboxylic acid groups and carboxylic acids are used from the viewpoint of achieving high resistance of a light-shielding cured film formed using the photosensitive resin composition. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid group is preferable.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
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 sulfite, bisulfite, or the like.
2) A method of diazo coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of performing deprotection after performing a Friedel-Crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

  Among these methods, the method 2) is preferred because the acidic group introduction treatment is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzene sulfonic acids such as sulfanilic acid and 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 is preferable with respect to 100 g of carbon black, and, as for the number of moles of the acidic group introduce | transduced into carbon black, 5-100 mmol is more preferable.

Carbon black introduced with acidic groups may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. In addition, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using a photosensitive resin composition does not produce especially by the coating process by resin. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

  In addition, a perylene pigment can also be preferably used as the black pigment. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (d-1), the perylene pigment represented by the following formula (d-2), and the following formula (d-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

式（ｄ−１）中、Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｄ３及びＲ^ｄ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

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

式（ｄ−２）中、Ｒ^ｄ５及びＲ^ｄ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

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

式（ｄ−３）中、Ｒ^ｄ７及びＲ^ｄ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｄ７及びＲ^ｄ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

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

  Examples of the compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

  In order to satisfactorily disperse the perylene pigment in the photosensitive resin composition, the average particle size of the perylene pigment is preferably 10 to 1000 nm.

  Moreover, a lactam pigment can also be included as a light-shielding agent. As a lactam pigment, the compound represented by a following formula (d-4) is mentioned, for example.

In formula (d-4), X ^d represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and R ^d9 each independently represents a hydrogen atom, a methyl group, a nitro group, methoxy Group, bromine atom, chlorine atom, fluorine atom, carboxy group, or sulfo group, R ^d10 independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 each independently represents a hydrogen atom. Represents a methyl group or a chlorine atom.
The compound represented by Formula (d-4) can be used alone or in combination of two or more.
R ^d9 is preferably bonded to the 6-position of the dihydroindolone ring from the viewpoint of easy production of the compound represented by formula (d-4), and R ^d11 is bonded to the 4-position of the dihydroindolone ring. It is preferable to do this. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.
The compound represented by the formula (d-4) has EE, ZZ, and EZ isomers as geometric isomers, and may be any one of these compounds, or these geometric isomers. It may be a mixture of
The compound represented by the formula (d-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

  In order to satisfactorily disperse the lactam pigment in the photosensitive resin composition, the average particle size of the lactam pigment is preferably 10 to 1000 nm.

Furthermore, fine particles mainly composed of a silver tin (AgSn) alloy (hereinafter referred to as “AgSn alloy fine particles”) are also preferably used as the black pigment. The AgSn alloy fine particles may be composed mainly of an AgSn alloy, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle diameter of the AgSn alloy fine particles is preferably 1 to 300 nm.

When the AgSn alloy is represented by the chemical formula AgxSn, the x range in which a chemically stable AgSn alloy is obtained is 1 ≦ x ≦ 10, and the x range in which chemical stability and blackness are simultaneously obtained is 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is determined in the range of x,
When x = 1, Ag / AgSn = 0.4762
In the case of x = 3, 3 · Ag / Ag3Sn = 0.7317
When x = 4, 4 · Ag / Ag4Sn = 0.7843
When x = 10, 10 · Ag / Ag10Sn = 0.008
It becomes.
Therefore, this AgSn alloy becomes chemically stable when Ag is contained in an amount of 47.6 to 90% by mass, and effective when Ag is contained in an amount of 73.17 to 78.43% by mass. Chemical stability and blackness can be obtained.

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

Although the AgSn alloy fine particles have high insulating properties, depending on the use of the photosensitive resin composition, the surface may be covered with an insulating film in order to further improve the insulating properties. As a material for such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc. is preferably used. It is done.
In addition, as the organic polymer compound, an insulating resin such as polyimide, polyether, polyacrylate, polyamine compound, or the like is preferably used.

The thickness of the insulating film is preferably 1 to 100 nm, and more preferably 5 to 50 nm, in order to sufficiently enhance the surface insulation 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, use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform thickness can be formed at a relatively low temperature.

As the black pigment, the above-described perylene pigment, lactam pigment, AgSn alloy fine particles may be used alone, or a combination thereof may be used.
In addition, the black pigment may contain a pigment having a hue such as red, blue, green, and yellow for the purpose of adjusting the color tone. The pigment of the other hue of the black pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as a pigment having another hue of a black pigment. The amount of the pigment having another hue of the black pigment used is preferably 15% by mass or less, and more preferably 10% by mass or less based on the total mass of the black pigment.

In order to uniformly disperse the pigment (D) described above in the photosensitive resin composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the (D) pigment, it is preferable to use an acrylic resin-based dispersant as the dispersant.
In addition, corrosive gas resulting from the dispersant may be generated from the cured film. For this reason, it is also preferable that the (D) pigment is dispersed without using a dispersant.

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when used in combination, the organic pigment is used in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. Preferably, it is used in the range of 20 to 40 parts by mass.

In the photosensitive resin composition, the (D) pigment may be used in combination with a dye. This dye may be appropriately selected from known materials.
Examples of dyes that can be applied to the photosensitive resin composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. Can be mentioned.
Further, these dyes can be dispersed in an organic solvent or the like by lake formation (chlorination) and used as (D) pigment.
In addition to these dyes, for example, JP 2013-225132 A, JP 2014-178477 A, JP 2013-137543 A, JP 2011-38085 A, JP 2014-197206 A, and the like. The dyes described can also be preferably used.

  The amount of the (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 is typically 2 to 2% by mass relative to the total solid content of the photosensitive resin composition. 75 mass% is preferable and 3-70 mass% is more preferable.

(D) It is preferable to add the pigment to the photosensitive resin composition after preparing a dispersion in which the pigment is dispersed at an appropriate concentration in the presence or absence of a dispersant.
In addition, in this specification, it can define as a value also including this dispersing agent about the usage-amount of the above-mentioned (D) pigment.

<(S) Organic solvent>
The photosensitive resin composition preferably contains (S) an organic solvent for improving coatability and adjusting viscosity.

  Specific examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -N-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Ether acetates; Other ethers such as lenglycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-Methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate , Ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate etc. Esters; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N, N-diethylacetamide N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-yl Dazorijinon, pyridine, and N, N, N ', N'- tetramethylurea nitrogen-containing polar organic solvent; and the like.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above such as benzyl acetate are more preferred.
Moreover, it is also preferable that the (S) organic solvent contains a nitrogen-containing polar organic solvent in terms of solubility of each component, (D) pigment dispersibility, and the like. As the nitrogen-containing polar organic solvent, N, N, N ′, N′-tetramethylurea or the like can be used.
These solvents can be used alone or in combination of two or more.

  The content of the (S) organic solvent is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 15-50 mass%.

<Other ingredients>
The photosensitive resin composition can contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, an antifoaming agent, and a silane coupling agent as necessary. Any additive can be used as the additive.
Since the photosensitive resin composition has a good shape and can easily form a cured film having excellent adhesion to the substrate, it preferably contains a silane coupling agent. A conventionally known silane coupling agent can be used without particular limitation.
Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine. Compounds and the like.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition described above can be obtained by mixing each of the above components in a predetermined amount and then uniformly mixing with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become a more uniform thing.

≪Method for producing cured film≫
As a method for producing a cured film, a conventionally known method for producing a cured film using a photosensitive resin composition containing a photopolymerizable compound (B) can be employed without any particular limitation.

As a suitable manufacturing method of the cured film,
A step of forming a coating film by applying the photosensitive resin composition described above;
A step of selectively exposing the coating film;
Developing the exposed coating film to form a patterned cured film; and
And baking the patterned cured film.

  In order to form a cured film using the photosensitive resin composition, first, the photosensitive resin composition is applied on a substrate selected according to the use of the cured film to form a coating film. The method for forming the coating film is not particularly limited. For example, the coating film is formed using 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 called.

  The applied photosensitive resin composition is dried as necessary to form a coating film. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, (2) several hours at room temperature Examples include a method of leaving for several days, and (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is exposed. The exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The exposure is performed position-selectively by, for example, a method of performing exposure through a negative mask. Although the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, for example, about 40 to 200 mJ / cm ² is preferable.
When exposure is performed on the entire surface of the coating film, an unpatterned cured film having a shape corresponding to the shape of the coating film is formed.

  When the coating film is exposed in a position-selective manner, the exposed film is developed with a developing solution, whereby the unexposed portion is dissolved and removed in the developing solution to form a patterned cured film. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive resin composition. As the developer, for example, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, or a quaternary ammonium salt can be used.

Next, baking (post-baking) is performed on the patterned cured film. The baking temperature is not particularly limited, but is preferably 180 to 250 ° C, more preferably 220 to 230 ° C. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes.
By baking as described above, a cured film of the photosensitive resin composition can be obtained.

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

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

[Preparation Example 1]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours 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 a colorless and transparent solid.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin A-1. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[Example 1, Example 2, and Comparative Examples 1-3]
In Examples and Comparative Examples, (A) novolac resin, cardo resin, and acrylic resin were used as the alkali-soluble resin.
As a novolac resin, TO-547 (trade name) manufactured by Sumitomo Bakelite Co., Ltd. was used. TO-547 was obtained by adding oxalic acid and a concentration of 37% by weight formalin to a mixture of 90 mol% of m-cresol and 10 mol% of 2,3,5-trimethylphenol, and condensing reaction by a conventional method. It is a novolac resin.
As the cardo resin, the resin A-1 obtained in Preparation Example 1 was used.
As the acrylic resin, a resin containing 20 mol% of structural units derived from methacrylic acid and 80 mol% of structural units derived from styrene (made by Shin-Nakamura Chemical Co., Ltd., NCF-3 (trade name), Mw = 10000) is used. Using.

In Examples and Comparative Examples, as the photopolymerizable compound (B), a dendritic polymer and a polyfunctional monomer other than the dendritic polymer were used.
As the dendritic polymer, SIRIUS 501 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used.
DPHA (dipentaerythritol hexaacrylate) was used as a polyfunctional monomer other than the dendritic polymer.

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

In Examples and Comparative Examples, carbon black was used as the (D) pigment.
As carbon black, D-A, carbon black (pigment A (dispersion liquid)) manufactured by Daido Kasei Kogyo Co., Ltd., and D-B, carbon black (pigment B (dispersion liquid)) manufactured by Gokoku Color Co., Ltd. Using.
In addition, in Table 1 of this Example item, the numerical value is described about the total value of solid content of this pigment and a dispersing agent.

Each of (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, and (D) pigment in the amounts shown in Table 1 are solidified in (S) organic solvent. It dissolved and disperse | distributed so that it might become a partial concentration of 15 mass%, and the photosensitive resin composition of each Example and the comparative example was obtained.
(S) As the organic solvent, a mixed solvent of 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: cyclohexanone = 40: 35: 25 (mass ratio) was used.
Using the obtained photosensitive resin composition, according to the following method, the difficulty of flow by heating of the cured film (flow resistance), the patterned cured film CD (Critical Dimension), and the cured film of Fine wire adhesion was evaluated.

<Flow resistance evaluation>
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 with a 100 degreeC hotplate, and volatilized the solvent. Subsequently, after exposure using Mask of 5 μm line, development was performed with a KOH 0.04% developer for 70 seconds.
The patterned substrate was divided in half, and the half was held in an oven heated to 230 ° C. for 20 minutes. The substrate thus heated was taken out of the oven and cooled, and then the patterning portion was broken and the cross section was observed with an SEM.
As this item, a substrate that was not heated in an oven was compared, and deformation (flow) due to heat was confirmed.
This item was evaluated based on the following criteria.
○: When observing the roundness of the upper part of the pattern, the taper angle of the pattern, and the seepage from the pattern hem, the pattern has a rectangular shape, or there is no significant difference between the heated substrate and the unheated substrate. Is in a state.
Δ: Not a quality problem, but when observing how the upper part of the pattern is rounded, the taper angle of the pattern, and the seepage from the pattern hem, there is a slight difference between the heated substrate and the unheated substrate (shape collapse) ) Is observed.
X: Observing the roundness of the upper part of the pattern, the taper angle of the pattern, and the bleeding from the pattern hem, a clear difference (shape collapse) is observed between the heated substrate and the unheated substrate.

<CD evaluation>
The developing operation was performed in the same manner as in the above <flow resistance evaluation>, and then the patterned substrate was divided in half and held in an oven heated to 230 ° C. for 20 minutes.
Then, the patterning part was confirmed with the microscope and evaluated based on the following criteria.
A: A pattern is formed with a dimension within ± 10% of the dimension of the Mask width.
X: A pattern is formed with a dimension of more than + 10% or less than −10% with respect to the dimension of the Mask width. Or, film loss is apparently caused by development.

<Thin wire adhesion evaluation>
The mask was subjected to the exposure operation by the same method as the above <flow resistance evaluation> except that a mask having a width of 3 to 20 μm was used on one surface. Thereafter, development was performed with a 0.04% KOH developer for 80 seconds, and the presence or absence of peeling of the patterned portion was confirmed with a microscope, and evaluation was performed based on the following criteria.
○: No peeling is observed even in a pattern portion having a width of 3 μm.
X: Peeling is observed in the pattern portion having a width of 3 μm.

According to the examples, (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a pigment, (A) a novolac resin as an alkali-soluble resin And (B) a photosensitive resin composition containing a dendritic polymer having two or more ethylenic polymerizable groups at its ends as a photopolymerizable compound, it is difficult to flow excessively by heating, and has a predetermined dimension. It can be seen that a cured film patterned with can be formed.
On the other hand, according to Comparative Examples 1 and 3, it can be seen that when the photosensitive resin composition does not contain a novolac resin, it is difficult to form a cured film patterned with a predetermined dimension.
Further, according to Comparative Example 2, when the photosensitive resin composition does not include a dendritic polymer having two or more ethylenic polymerizable groups at its ends, the formed cured film is likely to flow by heating. I understand.

Claims (10)

(A) an alkali-soluble resin;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) a pigment;
A photosensitive resin composition comprising:
The (A) alkali-soluble resin contains a novolac resin,
The photosensitive resin composition in which the (B) photopolymerizable compound contains a dendritic polymer having two or more ethylenic polymerizable groups at its terminals. The dendritic polymer is represented by 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 n of m hydroxy groups of polyhydric alcohol R ³ (OH) _m . (The hydroxyl group is an n-valent residue subjected to an ester bond in formula (1), and m and n are each independently an integer of 2 to 20, and m ≧ n.)
And a polyfunctional (meth) acrylate compound represented by the following formula (2):
_{(HS-CH 2 -) p} -R 4 (2)
(In Formula (2), R ⁴ is a single bond or a 2-6 valent hydrocarbon group-containing group having 1 to 6 carbon atoms, p is 2 when R ⁴ is a single bond, and R ⁴ Is a 2-6 valent hydrocarbon group-containing group, it is an integer of 2-6.)
The photosensitive resin composition of Claim 1 which is an adduct with the polyvalent mercapto compound represented by these.   The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin further contains a resin having a cardo structure.   The photosensitive resin composition of any one of Claims 1-3 whose weight average molecular weights of the said novolak resin are 2000-50000.   The photosensitive resin composition of any one of Claims 1-4 whose said (D) pigment is a black pigment.   The photosensitive resin composition of Claim 5 whose said black pigment is carbon black.   The ratio (Wn: Wd) of the content Wn [g] of the novolak resin and the content Wd [g] of the dendritic polymer is in the range of 20: 1 to 1:20. 6. The photosensitive resin composition according to any one of 6 above.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-7.   A color filter comprising the cured film according to claim 8. A step of forming a coating film by applying the photosensitive resin composition according to any one of claims 1 to 7,
Exposing the coating film in a position-selective manner;
Developing the exposed coating film to form a patterned cured film; and
Baking the patterned cured film. A method for producing a cured film.