JP2021110806A - Self-luminous photosensitive resin composition, color filter, and image display device - Google Patents

Abstract

To provide a self-luminous photosensitive resin composition that exhibits a high quantum yield and has a short dissolution time in a developer.SOLUTION: The self-luminous photosensitive resin composition comprises (A) a fluorescent compound represented by general formula (1), (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photoinitiator.SELECTED DRAWING: None

Description

The present invention relates to a self-luminous photosensitive resin composition, a color filter, and an image display device.

In recent years, color filters used in flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices have been required to have higher brightness and wider color gamut from the viewpoint of energy saving and high color reproducibility. Has been done.

In general, a method of replacing a pigment used in a color filter with a dye having a higher transmittance has been studied for these problems, but on the other hand, as described in Patent Document 1, for example. , A method of laminating a color conversion layer containing a fluorescent substance on a conventional color filter has been proposed.

The color material used for the color conversion layer is preferably a fluorescent substance that absorbs the light of the backlight and emits light of a desired wavelength and has a high quantum yield. For example, a phosphor, a quantum dot, or a fluorescence. Dyes and the like have been studied. However, it is difficult to obtain a phosphor having a particle size smaller than the thickness of the color filter, and quantum dots have insufficient durability against the firing process in the manufacturing process of the color filter. Therefore, it is possible to use a fluorescent dye. It can be said that it is desirable.

As the fluorescent dye, a self-luminous photosensitive resin composition using a perylene-based compound as described in Patent Document 2, for example, has been reported from the viewpoint of quantum yield and durability.

Korean Publication No. 10-2016-0112479 Japanese Unexamined Patent Publication No. 2018-124553

However, according to the studies by the present inventors, in the self-luminous photosensitive resin composition containing a perylene-based compound as a fluorescent dye, the perylene-based compound has high hydrophobicity, so that it is added to a developing solution in the manufacturing process of a color filter. It has been found that there is a problem that the dissolution time becomes long and the production efficiency is low.

Therefore, it is an object of the present invention to provide a self-luminous photosensitive resin composition showing a high quantum yield and a short dissolution time in a developing solution.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by including a specific fluorescent compound, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] A self-luminous photosensitive resin composition containing (A) a fluorescent compound, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator.
A self-luminous photosensitive resin composition, wherein the fluorescent compound (A) contains a fluorescent compound represented by the following general formula (1).

(In the formula (1), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ³ represents any monovalent group, including hydrophilic groups.
n represents an integer of 2 to 6.
The benzene ring in the formula (1) may be further substituted with an arbitrary substituent. )

[2] The self-luminous photosensitive resin composition according to [1], wherein the fluorescent compound represented by the general formula (1) is a fluorescent compound represented by the following general formula (2).

(In the formula (2), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^{4 to} R ⁷ each independently represent any monovalent group, including a hydrophilic group.
The benzene ring in the formula (2) may be further substituted with an arbitrary substituent. )

[3] The self-luminous photosensitive resin composition according to [2], ^{wherein R 4 to} R ⁷ are all the same group in the above formula (2).

[4] The self-luminous photosensitive resin composition according to [2], wherein the fluorescent compound represented by the general formula (2) is a fluorescent compound represented by the following general formula (3).

(In the formula (3), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ is a monovalent group represented by the following general formula (4), and all are the same. )

(In the formula (4), X ^{1 to} X ⁵ each independently represent an arbitrary monovalent group including a hydrogen atom, an alkyl group which may have a substituent, or a hydrophilic group, and X ^{At least one of 1 to} X ⁵ represents any monovalent group, including hydrophilic groups.)

[5] In the formula (4), the hydrophilic group is a hydroxyl group, an alkoxy group, an alkylthio group, a carboxyl group, an acyl group, an ester group, an amino group, an alkylamino group, an amide group, an imide group, a carbamate group, The self-luminous photosensitive resin composition according to [4], which is one or more selected from the group consisting of a urea group and a urea group.

[6] The self-luminous photosensitive resin composition according to any one of [1] to [5], wherein the content ratio of the fluorescent compound (A) is 20% by mass or less in the total solid content.
[7] A color filter including a color conversion layer formed by using the self-luminous photosensitive resin composition according to any one of [1] to [6].
[8] An image display device including the color filter according to [7].

According to the present invention, it is possible to provide a self-luminous photosensitive resin composition showing a high quantum yield and a short dissolution time in a developing solution.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, "(meth) acrylic", "(meth) acrylate" and the like mean "at least one of acrylic and methacrylic", "at least one of acrylate and methacrylate" and the like, for example, "( "Meta) acrylic acid" shall mean "at least one of acrylic acid and methacrylic acid".

Further, the “total solid content” means all the components of the self-luminous photosensitive resin composition of the present invention other than the solvent component.
Further, the "aromatic ring" shall mean both an "aromatic hydrocarbon ring" and an "aromatic heterocycle". The "aryl group" means both an "aromatic hydrocarbon ring group having one free valence" and an "aromatic heterocyclic group having one free valence", and similarly, "arylene". The "group" means both "an aromatic hydrocarbon ring group having two free valences" and "an aromatic heterocyclic group having two free valences".
In addition, terms such as "CI pigment green" mean the names of color materials contained in the Color Index (CI).

[1] Components of Self-luminous Photosensitive Resin Composition Each component of the self-luminous photosensitive resin composition of the present invention will be described below. The self-luminous photosensitive resin composition according to the present invention contains (A) a fluorescent compound, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator as essential components, and further. If necessary, additives other than the above-mentioned components may be blended.
Hereinafter, each component will be described.

[1-1] (A) Fluorescent Compound The self-luminous photosensitive resin composition of the present invention contains (A) a fluorescent compound. The (A) fluorescent compound is a compound that absorbs ultraviolet or visible light and converts it into light on a longer wavelength side to emit fluorescence, and the self-luminous photosensitive resin composition of the present invention is (A) a fluorescent compound. By including, the light from the backlight can be converted to a desired wavelength with a high quantum yield.

(Fluorescent compound represented by the general formula (1))
The fluorescent compound (A) contained in the self-luminous photosensitive resin composition of the present invention may be referred to as a fluorescent compound represented by the following general formula (1) (hereinafter, referred to as “fluorescent compound (1)”). Yes.) Is included.

(In the formula (1), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ³ represents any monovalent group, including hydrophilic groups.
n represents an integer of 2 to 6.
The benzene ring in the formula (1) may be further substituted with an arbitrary substituent. )

The fluorescent compound (1) is considered to exhibit a high quantum yield by having a perylene bisimide in the matrix, and in particular, by having two or more arbitrary monovalent groups including a hydrophilic group, the fluorescent compound (1) is hydrophilic. It is considered that the quantum yield is further improved by inhibiting the formation of aggregates between perylene bisimide skeletons due to the steric disorder of the groups and preventing the anti-dimming action between the molecules.

Further, it is considered that the hydrophilic group increases the solubility in the alkaline developer and shortens the developing time.

(R ¹ , R ² )
In the general formula (1), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
Examples ^{of the alkyl group in R 1} and R ² include a linear, branched or cyclic alkyl group. The carbon number is usually 1 or more, preferably 2 or more, preferably 12 or less, and more preferably 6 or less. When it is set to the lower limit value or more, the durability tends to be high, and when it is set to the upper limit value or less, the developing time tends to be shortened.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3-. Examples thereof include a methylbutyl group and a 2-ethylhexyl group. Among these, a 2-ethylhexyl group is preferable from the viewpoint of solubility.

Examples of the substituent that the alkyl group may have include those described in the substituent group W1 described later. Specific examples of the alkyl group having a substituent include a phenethyl group, a 2-ethoxyethyl group, a 4,4,4-trifluorobutyl group and the like.

Examples of the aromatic ring group in R ¹ and R ² include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is set to the lower limit value or more, the durability tends to be high, and when it is set to the upper limit value or less, the synthesis tends to be easy.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indol ring, and a carbazole ring having one free atomic value. Rings, Pyrrolomidazole Rings, Pyrrolopyrazole Rings, Pyrrolopyrrole Rings, Thienopyrrole Rings, Thienothiophene Rings, Flopilol Rings, Flofran Rings, Thienofranc Rings, Benzisoxazole Rings, Benzimidazole Rings, Benzimidazole Rings, Pyridine Rings, Pyrazine Rings, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinolin ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, a benzene ring having one free valence is preferable from the viewpoint of durability and ease of production.

Examples of the substituent that the aromatic ring group may have include those described in the substituent group W2 described later. Among these, an alkyl group is preferable, and an isopropyl group is more preferable, from the viewpoint of durability.

From the viewpoint of durability, the ortho position is preferable as the substitution position of the substituent that the aromatic ring group may have.

Among these, from the viewpoint of durability, R ¹ and R ² are preferably aromatic ring groups which may have independent substituents, and are benzene ring groups substituted with an alkyl group. Is more preferable, and a 2,6-diisopropylphenyl group is even more preferable.

R ¹ and R ² are preferably the same from the viewpoint of ease of manufacture.

(R ³ )
In the general formula (1), R ³ represents any monovalent group including a hydrophilic group.
Any monovalent group containing a hydrophilic group includes a hydrophilic group or a divalent hydrocarbon group having a hydrophilic group at one end. This hydrocarbon group may have a substituent.

A hydrophilic group has a highly polarized structure, so that it can be electrostatically bonded to a molecule having the same highly polarized structure, or hydrogen-bonded to a molecule having a hydrogen-bonding hydrogen atom such as water. By the way, it refers to a functional group that enhances the affinity with these molecules, and in particular, means a group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom.

As hydrophilic groups, hydroxyl groups, alkoxy groups, alkylthio groups, carboxyl groups, acyl groups, ester groups (acyloxy groups and alkoxycarbonyl groups), amino groups, alkylamino groups, amide groups (acylamino groups, acylalkylamino groups, etc.) Aminocarbonyl group and alkylaminocarbonyl group), imide group (diacylamino group), carbamate group (alkoxycarbonylamino group, aminocarbonyloxy group and alkylaminocarbonyloxy group), and urea group (aminocarbonylamino group and alkylaminocarbonyl group) Amino group) and the like.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group and a vinyloxy group. Examples thereof include a group, an allyloxy group, a glycidyl group, and a polyethylene glycol group having an arbitrary length. Among these, a methoxy group is preferable from the viewpoint of ease of production.

Specific examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a t-butylthio group, a methoxymethylthio group, a methoxyethylthio group, an ethoxymethylthio group and an ethoxyethylthio group. , Allylthio group and the like. Among these, a methylthio group is preferable from the viewpoint of ease of production.

Specific examples of the group include an acetyl group, an n-propanoyl group, an isopropanoyl group, an n-butanoyl group, a t-butanoyl group, a methoxyacetyl group, an acrylic group, a methacryl group and the like. Among these, an acetyl group is preferable from the viewpoint of ease of production.

Specific examples of the ester group (acyloxy group and alkoxycarbonyl group) include an acetoxy group, an n-propanoyloxy group, an isopropanoyloxy group, an n-butanoyloxy group, a t-butanoyloxy group, and a methoxyacetyloxy group. , Acryloyloxy group, methacryloyloxy group, succinyloxy group, monomethylsuccinyloxy group, monoethylsuccinyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t -Butoxycarbonyl group, methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxymethoxycarbonyl group, ethoxyethoxycarbonyl group, vinyloxycarbonyl group, allyloxycarbonyl group, glycidyloxycarbonyl group and the like can be mentioned. Among these, an acetoxy group is preferable from the viewpoint of ease of production.

Specific examples of the alkylamino group include methylamino group, dimethylamino group, ethylamino group, ethylmethylamino group, diethylamino group, 2-ethylhexylamino group, cyclopentylamino group, cyclohexylamino group, pyrrolidyl group, piperidyl group and morpholinyl. The group and the like can be mentioned. Among these, a morpholinyl group is preferable from the viewpoint of hydrophilicity.

Specific examples of the amide group (acylamino group, acylalkylamino group, aminocarbonyl group and alkylaminocarbonyl group) include formylamino group, acetylamino group, propanoylamino group, isopropanoylamino group and n-butanoylamino. Group, t-butanoylamino group, methoxyacetylamino group, acryloylamino group, methacryloylamino group, succinylamino group, monomethylsuccinylamino group, monoethylsuccinylamino group, N-methylformylamino group, N-methylacetylamino group , N-ethylacetylamino group, aminocarbonyl group, N-methylaminocarbonyl group, N-dimethylaminocarbonyl group, N-ethylaminocarbonyl group, N-vinylaminocarbonyl group, N-allylaminocarbonyl group, 1-pyrroli Examples thereof include a dinylcarbonyl group, a 1-piperidinylcarbonyl group, an N-cyclopentylaminocarbonyl group, and an N-cyclohexylaminocarbonyl group. Among these, an acetylamino group is preferable from the viewpoint of ease of production.

Specific examples of the imide group (diacylamino group) include a diacetylamino group, an N-succinimidyl group, an N-maleimidyl group, an N-phthalimidyl group and the like. Among these, an N-maleimidyl group is preferable from the viewpoint of ease of production.

Specific examples of the carbamate group (alkoxycarbonylamino group, aminocarbonyloxy group and alkylaminocarbonyloxy group) include methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, allyloxycarbonylamino group and aminocarbonyl. Oxy group, N-methylaminocarbonyloxy group, N-dimethylaminocarbonyloxy group, N-ethylaminocarbonyloxy group, N-vinylaminocarbonyloxy group, N-allylaminocarbonyloxy group, N-cyclopentylaminocarbonyloxy group , N-cyclohexylaminocarbonyloxy group and the like. Among these, a methoxycarbonylamino group is preferable from the viewpoint of ease of production.

Specific examples of urea groups (aminocarbonylamino groups and alkylaminocarbonylamino groups) include aminocarbonylamino groups, N-methylaminocarbonylamino groups, N-dimethylaminocarbonylamino groups, N-ethylaminocarbonylamino groups, and N. -Vinylaminocarbonylamino group, N-allylaminocarbonylamino group, N-cyclopentylaminocarbonylamino group, N-cyclohexylaminocarbonylamino group and the like can be mentioned. Among these, an N-ethylaminocarbonylamino group is preferable from the viewpoint of ease of production.

Examples of the divalent hydrocarbon group include a linear, branched chain, cyclic or a combination thereof. For example, an alkylene group, an arylene group, a group in which an alkylene group and an arylene group are linked, and the like can be mentioned.

The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more, preferably 2 or more. Further, 100 or less is preferable, 50 or less is more preferable, 30 or less is further preferable, and 10 or less is particularly preferable. Within the above range, the development time tends to be shortened.

Specific examples of the alkylene group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, cyclopentylene group, n-hexylene group, cyclohexylene group, n-heptylene group and n-. Examples thereof include a decylene group, an n-undecylene group and an n-dodecylene group. Among these, an ethylene group is preferable from the viewpoint of development time.

Specific examples of the arylene group include an ortho-, meta- or para-phenylene group, a naphthylene group, a fluorene group, an indrene group, an anthracene group, a furan group, a thiophene group and the like. Among these, a poly-phenylene group is preferable from the viewpoint of ease of production.
Specific examples of the group in which the alkylene group and the arylene group are linked include a combination of the above-mentioned alkylene group and the above-mentioned phenylene group. Among these, a combination of a propylene group and a para-phenylene group is preferable from the viewpoint of ease of production.

Examples of the substituent that the divalent hydrocarbon group may have include those described in the substituent group W3 described later.

Among these, R ³ is preferably a methoxyethyl group from the viewpoint of development time and ease of production.

(N)
In the general formula (1), n represents an integer of 2 to 6.
n is preferably 3 or more from the viewpoint of development time, and is preferably 4 or less from the viewpoint of ease of production.

(Benzene ring in formula (1))
The benzene ring in the general formula (1) may be further substituted with an arbitrary substituent.
Examples of the substituent that the benzene ring in the formula (1) may have include those described in the substituent group W2 described later.

(Substituent group W1)
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; aromatic carbide such as phenyl group, mesityl group, tolyl group and naphthyl group Hydrogen ring group; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; alkylcarbonyl group having 2 to 9 carbon atoms; Fenetyl group; hydroxyethyl group; acetylamide group; dialkylaminoethyl group formed by bonding alkyl groups having 1 to 4 carbon atoms; trifluoromethyl group; trialkylsilyl group having 1 to 8 carbon atoms; nitro group; carbon number of carbon atoms 1-8 alkylthio groups.
Among them, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom are preferable. ..

(Substituent group W2)
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkyl group having 1 to 8 carbon atoms; alkenyl group having 2 to 8 carbon atoms; hydroxyl group; alkoxyl group having 1 to 8 carbon atoms: phenyl group, mesityl Aromatic hydrocarbon ring group such as group, trill group, naphthyl group; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfonic acid group; sulfamoyl group; Alkyl sulfamoyl group; carbonyl group; alkylcarbonyl group having 2 to 9 carbon atoms; hydroxyethyl group; acetylamide group; dialkylaminoethyl group formed by bonding alkyl groups having 1 to 4 carbon atoms; trifluoromethyl group; A trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkylsul having 2 to 9 carbon atoms. It is a famoyl group and a fluorine atom.

(Substituent group W3)
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkyl group having 1 to 8 carbon atoms; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; phenyl group, mesityl group, trill Aromatic hydrocarbon ring groups such as groups and naphthyl groups; cyano groups; carboxyl groups; acetyloxy groups; alkylcarbonyloxy groups with 2 to 9 carbon atoms; sulfamoyl groups; alkylsulfamoyl groups with 2 to 9 carbon atoms; carbon Alkylcarbonyl group of 2-9; phenethyl group; hydroxyethyl group; acetylamide group; dialkylaminoethyl group formed by bonding alkyl groups of 1 to 4 carbons; trifluoromethyl group; tri of 1 to 8 carbon atoms Alkylsilyl group; Nitro group; Alkylthio group having 1 to 8 carbon atoms.
Among them, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom are preferable. ..

(Fluorescent compound represented by the general formula (2))
Among the fluorescent compounds represented by the general formula (1), those represented by the following general formula (2) are preferable from the viewpoint of development time.

(In the formula (2), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^{4 to} R ⁷ each independently represent any monovalent group, including a hydrophilic group.
The benzene ring in the formula (2) may be further substituted with an arbitrary substituent. )

(R ¹ , R ² )
In the general formula (2), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. As the alkyl group which may have a substituent and the aromatic ring group which may have a substituent, those listed as ^{R 1} and R ^{2 in the general formula (1) are preferably adopted.} can.

(R ^{4 to} R ⁷ )
In the general formula (2), R ^{4 to} R ⁷ each independently represent an arbitrary monovalent group including a hydrophilic group.

As any monovalent group including a hydrophilic group, ^{those listed as R 3} in the general formula (1) can be preferably adopted, and among these, methoxy is used from the viewpoint of development time and ease of production. It is preferably an ethyl group.

Among these, from the viewpoint of ease of manufacture ^{, it is preferable that R 4 to} R ⁷ are all the same group.

(Benzene ring in formula (2))
The benzene ring in the general formula (2) may be further substituted with an arbitrary substituent.
Examples of the substituent that the benzene ring in the formula (2) may have include those described in the above-mentioned substituent group W2.

(Fluorescent compound represented by the general formula (3))
Among the fluorescent compounds represented by the general formula (2), those represented by the following general formula (3) are preferable from the viewpoint of quantum yield and ease of production.

(In the formula (3), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ is a monovalent group represented by the following general formula (4), and all are the same. )

(In the formula (4), X ^{1 to} X ⁵ each independently represent an arbitrary monovalent group including a hydrogen atom, an alkyl group which may have a substituent, or a hydrophilic group, and X ^{At least one of 1 to} X ⁵ represents any monovalent group, including hydrophilic groups.)

(R ¹ , R ² )
In the general formula (3), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. As the alkyl group which may have a substituent and the aromatic ring group which may have a substituent, those listed as ^{R 1} and R ^{2 in the general formula (1) are preferably adopted.} can.

(R ⁸ )
In the general formula (3), R ⁸ is a monovalent group represented by the general formula (4), and all are the same.

(X ^{1 to} X ⁵ )
In the general formula (4), X ^{1 to} X ⁵ each independently represent an arbitrary monovalent group including a hydrogen atom, an alkyl group which may have a substituent, or a hydrophilic group, and At ^{least one of X 1 to} X ⁵ represents any monovalent group, including hydrophilic groups.

Examples of the alkyl group in X ^{1 to X 5} include a linear, branched or cyclic alkyl group. The carbon number is usually 1 or more, preferably 2 or more, preferably 12 or less, and more preferably 6 or less. When it is set to the lower limit value or more, the durability tends to be high, and when it is set to the upper limit value or less, the developing time tends to be shortened.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3-. Examples thereof include a methylbutyl group and a 2-ethylhexyl group. Among these, a methyl group is preferable from the viewpoint of ease of production.

Examples of the substituent that the alkyl group may have include those described in the above-mentioned Substituent Group W1. Specific examples of the alkyl group having a substituent include a phenethyl group, a 2-ethoxyethyl group, a 4,4,4-trifluorobutyl group and the like.

As a specific example of any monovalent group including a hydrophilic group, ^{those listed as R 3} in the general formula (1) can be preferably adopted, and among these, from the viewpoint of development time and ease of manufacture. Therefore, it is preferably a methoxyethyl group.

At ^{least one of X 1 to} X ⁵ is an arbitrary monovalent group including a hydrophilic group, but 2 or less is preferable from the viewpoint of ease of production. Further, the substitution position of any monovalent group including the hydrophilic group is preferably ^{X 2 to} X ⁴ from the viewpoint of ease of production, and more preferably ^{X 3.}

Of X ^{1 to} X ^5, the larger the number of alkyl groups that may have substituents, the longer the absorption wavelength and emission wavelength of the fluorescent compound tend to be, and the desired absorption wavelength and emission wavelength can be obtained. In addition, the number of alkyl groups that may have substituents can be adjusted. Further, from the viewpoint of durability, the number of alkyl groups that may have a substituent is preferably 2 or less, and more preferably 1 or less.

Among these, from the viewpoint of development time and ease of manufacture, it is preferable that ^{X 3} is a methoxyethyl group and X ¹ , X ² , X ⁴ and X ^{5 are hydrogen atoms.} Further, depending on the desired absorption wavelength and emission wavelength ^{, among X 1 to} X ⁵ , it may be a methoxyethyl group, one of X ¹ or X ² may be a methyl group, and the other may be a hydrogen atom. preferable.

Specific examples of the fluorescent compound (1) include those shown below.

The method for producing the fluorescent compound (1) is not particularly limited, and the fluorescent compound (1) can be produced by a known method. For example, it can be produced by the method described in JP-A-2018-1245553.

In the self-luminous photosensitive resin composition of the present invention, one type of the fluorescent compound (1) may be used alone, or two or more types may be used in combination.

Further, the fluorescent compound (A) in the self-luminous photosensitive resin composition of the present invention contains the fluorescent compound (1), but is a fluorescent compound other than the fluorescent compound (1) (hereinafter, "other fluorescence"). It may be referred to as "sex compound").
Examples of other fluorescent compounds include xanthene dyes such as xanthene 6, xanthene 7, and xanthene 135, naphthalimide dyes such as solven yellow 43 and solven yellow 44, Lumogen F Red 305, Lumogen F Yellow 082, and Lumogen F. Perylene dyes such as Yellow 170, Lumogen F Pink 285, Lumogen F Orange 240, Lumogen F Fluoret 570, xanthene dyes such as Acid Red 52, Rhodamine B, Rhodamine 6G, benzophenoxazine dyes such as Nile Red, and bat red. Examples thereof include thioindigo dyes such as 41, pyrromethene dyes, cyanine dyes, oxadiazole dyes, and benzothiadiazole dyes.

The content ratio of the fluorescent compound (A) in the self-luminous photosensitive resin composition of the present invention is not particularly limited, but is preferably 4% by mass or more, more preferably 6% by mass or more, and 8% by mass in the total solid content. The above is further preferable, 13% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 20% by mass or less is particularly preferable. Within the above range, the emission intensity tends to be maximized.

The content ratio of the fluorescent compound (1) in the self-luminous photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass in the total solid content. The above is more preferable, 10% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 20% by mass or less is particularly preferable. When it is at least the lower limit value, the development time tends to be shortened, and when it is at least the upper limit value, the emission intensity tends to be increased.

[1-2] (B) Alkali-soluble resin The self-luminous photosensitive resin composition of the present invention contains (B) an alkali-soluble resin. By containing the alkali-soluble resin (B), both film curability by photopolymerization and solubility by a developing solution can be achieved at the same time.
Examples of the alkali-soluble resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, and JP-A-11-174224. Known polymer compounds described in JP-A-2000-563118, JP-A-2003-233179, etc. can be used, but the following (B-1) to (B-) are preferable. Examples thereof include the resin of 5).
(B-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. It may be referred to as an alkali-soluble resin (hereinafter referred to as "resin (B-1)") obtained by adding a polybasic acid anhydride to at least a part of the resin to be added or the hydroxyl group generated by the addition reaction. )
(B-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, may be referred to as "resin (B-2)").
(B-3) A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin (B-2) (hereinafter, may be referred to as "resin (B-3)").
(B-4) (Meta) acrylic resin (hereinafter, may be referred to as "resin (B-4)")
(B-5) Epoxy (meth) acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (B-5)")
Of these, resin (B-1) is particularly preferable, and will be described in detail below.

The resins (B-2) to (B-5) may be any resin as long as they are dissolved by an alkaline developer and have enough solubility to carry out the desired developing treatment. Those described as resins (C-2) to (C-5) in Japanese Patent Application Laid-Open No. 2009-025813 can be preferably adopted.

(B-1) To a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of the preferable embodiments of the alkali-soluble resin resin (B-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction, the resin is "containing an epoxy group". The copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radically polymerizable monomer is unsaturated with 10 to 100 mol% of the epoxy group contained in the copolymer. Examples thereof include a resin obtained by adding a basic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

As the other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.

In formula (V), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring.
In formula (V), the ^{ring formed by connecting R 96} and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and carbon. The number is preferably 5-6.

Among them, as the structure represented by the general formula (V), the structure represented by the following formula (Va), (Vb), or (Vc) is preferable.
By introducing these structures into the alkali-soluble resin, the hydrophobicity tends to be improved, the penetration of the developing solution is suppressed, and the quantum yield tends to be improved.

As the mono (meth) acrylate having a structure represented by the general formula (V), one type may be used alone, or two or more types may be used in combination.

As the mono (meth) acrylate having the structure represented by the general formula (V), various known mono (meth) acrylates can be used as long as they have the structure, and in particular, the mono (meth) acrylate represented by the following general formula (VI) can be used. ) Acrylate is preferred.

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following general formula (V).

In the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the content ratio of the repeating unit derived from the mono (meth) acrylate represented by the general formula (VI) is as described above. Among the repeating units derived from other radically polymerizable monomers, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. ..

The radically polymerizable monomer other than the mono (meth) acrylate represented by the general formula (VI) is not particularly limited, but specifically, for example, styrene or styrene. Vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; (meth) acrylic acid Methyl, ethyl (meth) acrylate, -n-propyl (meth) acrylate, -iso-propyl (meth) acrylate, -n-butyl (meth) acrylate, -sec-butyl (meth) acrylate, ( Meta) Acrylic acid-tert-butyl, (Meta) Pentyl acrylate, (Meta) Neopentyl acrylate, (Meta) Isoamyl acrylate, (Meta) hexyl acrylate, (Meta) -2-ethylhexyl acrylate, (Meta) Lauryl acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, Adamanthyl (meth) acrylate, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate , (Meta) salicyl acrylate, (meth) acrylate frill, (meth) acrylate flufuryl, (meth) acrylate tetrahydrofuryl, (meth) acrylate pyranyl, (meth) acrylate benzyl, (meth) acrylate phenethyl , (Meta) cresil acrylate, (meth) acrylate-1,1,1-trifluoroethyl, (meth) acrylate perfluorethyl, (meth) acrylate perfluoro-n-propyl, (meth) acrylic Perfluoro-iso-propyl acid, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, -2-hydroxy (meth) acrylate (Meta) acrylic acid esters such as ethyl, (meth) acrylic acid-2-hydroxypropyl; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N- Diethylamide, (meth) acrylic acid N, N-dipropylamide, (me (T) (Meta) acrylic acid amides such as N, N-di-iso-propylamides and (meth) acrylic acid anthracenylamides; (meth) acrylic acid anilides, (meth) acryloylnitrile, achlorine, vinyl chloride. , Vinyl compounds such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Kind: Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (meth) acryloylphthalimide and the like.

Among these other radically polymerizable monomers, from the viewpoint of hydrophobicity, it is preferable to contain at least one selected from the group consisting of styrene and benzyl (meth) acrylate. In particular, in the repeating units derived from other radically polymerizable monomers, the content ratio of the repeating units derived from one or more selected from the group consisting of these styrene and benzyl (meth) acrylate is 1 to 70 mol%. Is preferable, and 3 to 50 mol% is more preferable.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer. The solvent used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; and diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; Propropylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; benzene, toluene, xylene, octane, Hydrocarbons such as decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. Be done. These solvents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the obtained copolymer. By keeping the amount of the solvent used within the above range, it tends to be easy to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can be done. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-butylperoxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-Butyl Peroxy) Hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) par Oxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane , 1,1-Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarboxylicamide.
From these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.

The copolymerization reaction may be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature with stirring, or by adding the monomer to which the radical polymerization initiator is added. , The temperature may be raised, and the mixture may be added dropwise to the stirred solvent. Alternatively, the monomer may be dropped while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and the like. It is preferably composed of 10 to 95 mol% of the repeating unit derived from the radically polymerizable monomer of the above, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth) acrylate to the above lower limit value or more, the addition amount of unsaturated monobasic acid or polybasic acid anhydride described later tends to be sufficient, while the addition amount tends to be sufficient. Therefore, by setting the content ratio of the repeating unit derived from another radically polymerizable monomer to the above lower limit value or more, the heat resistance and strength tend to be sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radically polymerizable monomer. React with soluble component).

As the unsaturated monobasic acid added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. One of these may be used alone, or two or more thereof may be used in combination.

By adding such a component, the resin (B-1) can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. By setting the value to the lower limit or more, the stability of the self-luminous photosensitive resin composition with time tends to be improved. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include anhydrides of acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the resin (B-1).
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%. When it is set to the upper limit value or less, the residual film ratio at the time of development tends to be good, and when it is set to the lower limit value or more, the solubility tends to be sufficient. As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.

Further, in order to improve the photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. You may.
Further, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl groups, or both of them may be added.

Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group and an alkyl group. As commercially available products, for example, the product names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", and "Denacol EX-146" manufactured by Nagase ChemteX Corporation. There are "Denacol EX-171", "Denacol EX-192" and the like.

The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B-1) measured by GPC is not particularly limited, but is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. When it is at least the above lower limit value, the heat resistance and film strength tend to be good, and when it is at least the above upper limit value, the solubility in a developing solution tends to be good. As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

On the other hand, from the viewpoint of curability, among the (B) alkali-soluble resins, the (b1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferable.
(B1) The partial structure of the acrylic copolymer resin containing the side chain having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of ease of production, for example, the partial structure represented by the following general formula (I). It is preferable to have.

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. * Represents a bond.

Further, among the partial structures represented by the formula (I), the partial structure represented by the following general formula (I') is preferable from the viewpoint of sensitivity and alkali developability.

In formula (I'), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid. One or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of ease of production, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable. Preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(B1) The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, preferably 20 mol. % Or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, 70 mol% or less is further preferable, 60 mol% or less is further preferable, 50 mol% or less is particularly preferable, and 40 mol is particularly preferable. % Or less is most preferable. When it is at least the lower limit value, the curability tends to be improved, and when it is at least the upper limit value, the quantum yield tends to be improved.

(B1) The content ratio of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more. 20 mol% or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, 70 mol% or less is further preferable, 60 mol% or less is further preferable, and 50 mol% or less is particularly preferable. Most preferably 40 mol% or less. When it is at least the lower limit value, the curability tends to be improved, and when it is at least the upper limit value, the quantum yield tends to be improved.

(B1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the general formula (I), the other partial structure is not particularly limited, but from the viewpoint of hydrophobicity. Therefore, for example, it is also preferable to have a partial structure represented by the following general formula (II).

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ is an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an alkenyl group which may have.

(R ⁴ )
In the formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. ..
Examples ^{of the alkyl group in R 4} include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less. It is more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of hydrophobicity.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the aromatic ring group in R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the quantum yield due to energy transfer with the fluorescent compound tends to be improved. It tends to suppress the rate decrease.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or pyrene. Groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyroloymidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofran ring, benzoisooxazole ring, benzoiso Thiazol ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, synolin ring, quinoxaline ring, phenanthridin ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring. And so on. Among these, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable, from the viewpoint of quantum yield.
The substituents that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group and an epoxy group. , Oligoethylene glycol group, phenyl group, carboxyl group and the like, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

Examples ^{of the alkenyl group in R 4} include a linear, branched chain or cyclic alkenyl group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkenyl group include vinyl group, allyl group, 2-propen-2-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 2-pentene-1-yl group, and the like. Examples thereof include 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl and the like. Among these, a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of ease of production.

The substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

As described above, R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Among them, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of quantum yield.

(B1) The content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and 5 mol% or more. Is more preferable, 10 mol% or more is further preferable, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, 40 mol% or less is particularly preferable, and 30 mol% or less is particularly preferable. Most preferred. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

(B1) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), as the other partial structure contained, the partial structure represented by the following general formula (III) is used from the viewpoint of hydrophobicity. It is preferably contained.

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Represents an alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent. t represents an integer from 0 to 5.

(R ⁶ )
In the above formula (III), R ⁶ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, or a carboxyl group. , Halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples ^{of the alkyl group in R 6} include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, and more preferably 18 or less. It is more preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of hydrophobicity.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples ^{of the alkenyl group in R 6} include a linear, branched chain or cyclic alkenyl group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkenyl group include vinyl group, allyl group, 2-propen-2-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 2-pentene-1-yl group, and the like. Examples thereof include 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl and the like. Among these, a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of ease of production.

The substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkynyl group in R ⁶ include a linear, branched or cyclic alkynyl group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkynyl group include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butin-2-yl group, 1, Examples thereof include 4-pentaziin-3-yl group, 1,3-pentadiine-5-yl group, 1-hexin-6-yl group, and the like.

The substituents that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable from the viewpoint of storage stability of the acrylic copolymer resin.

Examples ^{of the alkoxy group in R 6} include a linear, branched chain or cyclic alkoxy group. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and the like.

The substituents that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkyl sulfide group in R ⁶ include linear, branched or cyclic alkyl sulfide groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is set to the lower limit value or more, the hydrophobicity tends to be improved and the permeation of the developing solution is suppressed to improve the quantum yield, and when it is set to the upper limit value or less, the compatibility with the fluorescent compound is improved. Tend.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group and the like. Among these, a methyl sulfide group or an ethyl sulfide group is preferable from the viewpoint of ease of production.

The substituents that the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group and a phenyl group. Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As described above, R ⁶ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and a halogen. It represents an alkylsulfide group which may have an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or a substituent. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable, from the viewpoint of hydrophobicity. preferable.

In the above formula (III), t represents an integer of 0 to 5, but from the viewpoint of ease of manufacture, t is preferably 0.

(B1) The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, preferably 20 mol% or more. Is more preferable, 30 mol% or more is further preferable, 40 mol% or more is particularly preferable, 50 mol% or more is most preferable, 80 mol% or less is preferable, and 70 mol% or less is more preferable. When the value is not less than the lower limit, the hydrophobicity tends to be improved, the penetration of the developing solution is suppressed, and the quantum yield tends to be improved, and when the value is not more than the upper limit, the developability tends to be improved.

(B1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), the other partial structure contained is the following general formula from the viewpoint of developability. It is also preferable to have a partial structure represented by (IV).

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

(B1) The content ratio of the acrylic copolymer resin having an ethylenically unsaturated group in the side chain when the partial structure represented by the general formula (IV) is contained is not particularly limited, but is preferably 5 mol% or more. 10 mol% or more is more preferable, 20 mol% or more is further preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60% mol or less is further preferable. When it is set to the lower limit value or more, the developability tends to be improved, and when it is set to the upper limit value or less, the hydrophobicity is improved, the penetration of the developing solution is suppressed, and the quantum yield tends to be improved.

On the other hand, the acid value of the alkali-soluble resin (B) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more. 50 mgKOH / g or more is particularly preferable, 110 mgKOH / g or less is preferable, 100 mgKOH / g or less is more preferable, 90 mgKOH / g or less is further preferable, and 80 mgKOH / g or less is even more preferable. When it is set to the lower limit value or more, the developability tends to be improved, and when it is set to the upper limit value or less, the hydrophobicity is improved, the penetration of the developing solution is suppressed, and the quantum yield tends to be improved.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, particularly preferably. It is 8000 or more, and is usually 30,000 or less, preferably 20,000 or less, and more preferably 15,000 or less. When the value is not less than the lower limit, the hydrophobicity tends to be improved, the penetration of the developing solution is suppressed, and the quantum yield tends to be improved, and when the value is not more than the upper limit, the developability tends to be improved.

The content ratio of the (B) alkali-soluble resin in the self-luminous photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass in the total solid content. % Or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, most preferably 45% by mass or more, and usually 80% by mass or less, preferably 70% by mass. % Or less, more preferably 60% by mass or less, still more preferably 55% by mass or less. When the value is equal to or higher than the lower limit, the quantum yield tends to be improved, and when the value is equal to or higher than the upper limit, the content ratio of the (A) fluorescent compound is relatively appropriate and the emission intensity tends to be improved. be.

[1-3] (C) Photopolymerizable Compound The self-luminous photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. The photopolymerizable compound is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “ethyleney compound”) is preferable. .. The ethylenic compound is a compound having an ethylenic double bond such that when the self-luminous photosensitive resin composition of the present invention is irradiated with active light, it is addition-polymerized by the action of a photopolymerization initiator and cured. Is. The monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. When it is set to the lower limit value or more, the sensitivity tends to be high, and when it is set to the upper limit value or less, the solubility in a solvent tends to be improved.

Examples of the ethylenic compound include unsaturated carboxylic acids, esters of monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, and unsaturated compounds. Esters obtained by esterification reaction between saturated carboxylic acid and polyvalent carboxylic acid and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound, polyisocyanate compound and (meth) acryloyl-containing hydroxy compound. Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting the above.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and other acrylic acid esters. Further, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety. Esters and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Typical examples are, for example, a condensate of acrylic acid, phthalic acid and ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid and butanediol. And a condensate of glycerin and the like.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- Examples thereof include a reaction product with a (meth) acryloyl group-containing hydroxy compound such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate are also useful.
Further, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is formed by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The provided polyfunctional monomer is preferable, and the aliphatic polyhydroxy compound in this ester is pentaerythritol and / or dipentaerythritol.

One of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more of these monomers may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When it is set to the lower limit value or more, the developing and dissolving characteristics tend to be good, and when it is set to the upper limit value or less, the production and handling tend to be good, and the curability tends to be improved. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid group as the whole polyfunctional monomer should be adjusted so as to fall within the above range. Is preferable.

In the present invention, the polyfunctional monomer having a more preferable acid group is mainly a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toa Synthetic Co., Ltd. It is a mixture as an ingredient. Other polyfunctional monomers of this polyfunctional monomer can also be used in combination. Further, those described in paragraphs [0056] and [0057] of JP2013-140346A can also be used.

The content ratio of the photopolymerizable compound in the self-luminous photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass in the total solid content. Above, more preferably 15% by mass or more, particularly preferably 20% by mass or more, usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, particularly. It is preferably 30% by mass or less. When it is set to the lower limit value or more, the penetration of the developing solution tends to be suppressed and the quantum yield tends to be improved, and when it is set to the upper limit value or less, the quantum yield tends to be improved.

[1-4] (D) Photopolymerization Initiator The self-luminous photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. By containing (D) a photopolymerization initiator, film curability by photopolymerization can be obtained.
The photopolymerization initiator (D) can also be used as a mixture (photopolymerization initiator) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as needed. The photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the photopolymerization initiator include metallocene compounds containing titanosen compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazole described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone-based compounds, oxime ester-based initiators described in JP-A-2000-80068, and the like.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5-[β- (2'-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p) -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

Ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as Benz anthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, Dicyclopentagenyl-Ti-2,6-dipuroolofeni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3 , 4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, dicyclopentagenyl-Ti-2,6-difluoro- Titanocene derivatives such as 3- (pill-1-yl) -pheni-1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. α-aminoalkylphenyl compounds;
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] -1- (O-acetyloxime), the compound described in JP-A-2004-534977, the compound described in JP-A-2000-80068, the compound described in International Publication No. 2012/45736, the international publication. The compound described in JP-A-2015 / 36910, the compound described in JP-A-2006-36750, the compound described in JP-A-2008-179611, the compound described in International Publication No. 2009/131189, JP-A-2012- Compounds described in Japanese Patent Application Laid-Open No. 526185, compounds described in Japanese Patent Application Laid-Open No. 2012-591191, compounds described in International Publication No. 2006/18973, compounds described in International Publication No. 2008/78678, JP-A-2011-132215. An oxime ester compound such as the compound described in the publication. From the viewpoint of sensitivity, N-acetoxy-N- {4-acetoxyimimino-4- [9-ethyl-6- (o-toluoil) -9H-carbazole-3-yl] butane-2-yl} acetamide, N- Acetoxy-N- {3- (acetoxyimino) -3- [9-ethyl-6- (1-naphthoyl) -9H-carbazole-3-yl] -1-methylpropyl} acetamide, 4-acetoxyimino-5- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-Methyl oxopentanoate, OXE-01, OXE-02, OXE-03, OXE-04 (manufactured by BASF) , TR-PBG-304, TR-PBG-305 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), NCI-831, NCI-930 (manufactured by ADEKA) and the like are preferable.

One of these photopolymerization initiators may be used alone, or two or more thereof may be mixed and used.

Further, in addition to the (D) photopolymerization initiator, a chain transfer agent may be further used. The chain transfer agent is a compound having a function of receiving a generated radical and transferring the radical to another compound.
As the chain transfer agent, various compounds having the above functions can be used, and examples thereof include mercapto group-containing compounds and carbon tetrachloride, and the chain transfer effect tends to be high. It is more preferable to use a compound having a mercapto group. It is considered that this is because the bond cleavage is likely to occur due to the small SH binding energy, and a hydrogen drawing reaction or a chain transfer reaction is likely to occur. It is effective for improving sensitivity and surface curability.

Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-. A mercapto group-containing compound having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decandithiol, butanediolbis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol. Bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritoltetrakis (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Butanediolbis (3-Mercaptobutyrate), Ethethyleneglycolbis (3-Mercaptobutyrate), Trimethylol Propanthris (3- Mercaptobutylate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine Examples thereof include aliphatic mercapto group-containing compounds such as −2,4,6 (1H, 3H, 5H) -trione, and a compound having a plurality of mercapto groups is particularly preferable from the viewpoint of surface smoothness.

Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and trimethylolpropanthris (3-) among the aliphatic mercapto group-containing compounds is preferable. Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutynate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) − Trions are preferred.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, and specifically, trimetylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol. Tris (3-mercaptopropionate), trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5- Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis. (3-Mercaptobutyrate) is more preferred.
These can be used alone or in admixture of two or more.

In the self-luminous photosensitive resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more in the total solid content, and 3 It is more preferably mass% or more, particularly preferably 5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and particularly preferably 7% by mass or less. When it is at least the lower limit value, the curability tends to be improved, and when it is at least the upper limit value, the quantum yield tends to be improved.

When the self-luminous photosensitive resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.3% by mass or more in the total solid content. Preferably, 0.5% by mass or more is further preferable, 0.7% by mass or more is particularly preferable, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable, 1.5% by mass or less. Mass% or less is particularly preferable. When it is at least the lower limit value, the curability tends to be improved, and when it is at least the upper limit value, the storage stability tends to be improved.

[1-5] Other Components The self-luminous photosensitive resin composition of the present invention may further contain a solid content other than the above components, if necessary. Examples of such a component include a surfactant, an antioxidant, a thermal cross-linking agent, a solvent and the like.

[1-5-1] Surfactant The self-luminous photosensitive resin composition of the present invention may contain a surfactant. The inclusion of a surfactant tends to improve the coatability of the self-luminous photosensitive resin composition.
As the surfactant, various substances such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but nonionic surfactants are unlikely to adversely affect various properties. It is preferable to use an agent.
When a surfactant is contained, its content is not particularly limited, but from the viewpoint of coatability, it is usually 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.05% by mass in the total solid content. % Or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[1-5-2] Antioxidant The self-luminous photosensitive resin composition of the present invention may contain an antioxidant. By including an antioxidant, heat resistance and light resistance tend to be improved, and the quantum yield tends to be improved.
There are no particular restrictions on the antioxidants. For example, the "Antioxidizer Handbook" published by Taiseisha (first edition published on October 25, 1976) and the "Polymer Additive Handbook" published by CMC Publishing (edited by Toru Haruna,). Various ones described in (1st edition issued on November 7, 2010)), etc. are listed, and hindered phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, hydroxylamine-based antioxidants. Etc., and secondary antioxidants such as sulfur-based oxidants and phosphorus-based oxidants can be used.

As the hindered phenolic antioxidant, a phenolic antioxidant having a hindered phenol structure or a single hindered phenol structure in the molecule is preferable from the viewpoint of heat resistance and light resistance.

Specific examples of the hindered phenol-based antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or mono). Di or tri) (α-methylbenzyl) phenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di- tert-amylhydroquinone, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-) t-Butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Pentaerythrityl-tetrax [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-) Hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-) Di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-t-butyl-4-4) Hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α,) α-Dimethylbenzyl) phenyl] -2H-benzoto Riazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5-(2H-benzotriazole-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight approx. Condensate with 300), hydroxyphenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6) −Pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like.

In the product name, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all of the above are large). MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-80, MARK AO -15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by ADEKA), IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX 1010, IRGANOX 1024, IRGANOX 1035, IRGANOX 1076, IRGANOX , IRGANOX 1222, IRGANOX 1330, IRGANOX 1425WL (all manufactured by BASF Japan), Sumilizer GM, Sumitomo Chemical Co., Ltd. Examples thereof include SONGNOX1290, SONGNOX2590, SONGNOX1098, SONGNOX4150, SONGNOX4425, SONGNOX2246, SONGNOX2500, SONGNOX1330, SONGNOX1790, and SONGNOX1520 (manufactured by SONGWON).

The phosphorus-based oxidizing agent is not particularly limited, and conventionally known ones can be widely used, but from the viewpoint of heat resistance and light resistance, alkyl phosphite and aryl phos, which do not contain phosphoric acid and phosphoric acid ester in the molecule, can be widely used. Fight, alkylaryl phosphite compounds and the like are preferable.
Specific examples of such phosphorus-based antioxidants include tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, diphenyl, mono (2-ethylhexyl) phosphite, diphenyl, mono (tridecyl). Phenylphosphite, diphenyl, mono (isodecyl) phosphite, diphenyl, mono (isooctyl) phosphite, diphenyl, mono (nonylphenyl) phosphite, triphenylphosphite, tris (tridecyl) phosphite, triisodecylphosphite, tris (2-Ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, tris (2,4-gyt-butylphenyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (Tridecyl) pentaerythritol-tetraphosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-) 6-t-butyl-di-tridecylphosphite), 2,2'-methylenebis (4,6-di-t-butylphenol) octylphosphite, 4,4'-isopropylidene-diphenolalkyl (C12-C15) ) Phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenylphosphite), Cyclic neopentanetetraylbis (nonylphenylphosphite), bis (nonylphenyl) pentaerythritol diphosphite, distearyl, pentaerythritol, diphosphite, bis [2,4-bis (1,1'-dimethylethyl) -6 -Methylphenyl] Ethyl ester phosphite and the like.

In terms of product names, Adekastab 1178, Adekastab 329K, Adekastab 135A, Adekastab C, Adekastab TPP, Adekastab 3010, Adekastab 2112, Adekastab 522A, Adekastab 260, Adekastab HP-10, Adekastab 1500, Adekastab PEP-24-G, Adekastab , ADEKA STUB PEP-4C, ADEKASTA PEP-8 (all manufactured by ADEKA), JPM-308, JPM-313, JPM-333E, JPP-100, JPP-613M, JPP-31, JP-351, JP-308E , JP-310, JP-321L, JP-333E, JP-318O, JP-318E (all manufactured by Johoku Chemical Industry Co., Ltd.), GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.), IRGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ ((BASF Japan), SONGNOX1680, SONGNOX6260, SONGNOX6280, SONGNOX DHOP, SONGNOX DPDP, SONGNOX EHDPP, SONGNOX PQ, SONGNex TPP (SONG) It can, but is not limited to these.

Among phosphorus-based antioxidants, it is preferable that all of the substituents of the phosphorus atom have a hydrocarbon group having 8 or more carbon atoms because it is stable with respect to hydrolyzability and has good heat resistance. Specifically, tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite,
Tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, and tristearyl phosphite are preferred.

These antioxidants may be used alone or in combination of two or more. In particular, primary antioxidants such as hindered phenolic antioxidants, amine-based antioxidants, lactone-based antioxidants, and hydroxylamine-based antioxidants, and secondary antioxidants such as sulfur-based and phosphorus-based antioxidants. Heat resistance tends to be improved by combining agents.

When the antioxidant is contained, the content ratio thereof is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2 in the total solid content. It is usually 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the quantum yield tends to be improved.

[1-5-3] Thermal Crosslinking Agent The self-luminous photosensitive resin composition of the present invention may contain a thermal crosslinking agent. The heat resistance tends to be improved by containing the thermal cross-linking agent.
As the thermal cross-linking agent, a known one can be used as long as it undergoes a cross-linking reaction by hard baking after image formation by exposure / development. Specific examples thereof include compounds having an epoxy group in the molecule, and one type may be used alone or two or more types may be mixed and used.

Examples of the compound having an epoxy group in the molecule include a (poly) glycidyl ether compound obtained by reacting a monohydroxy compound or a polyhydroxy compound with epichlorohydrin, and a (poly) carboxylic acid compound obtained by reacting epichlorohydrin. Examples thereof include compounds ranging from low molecular weight to high molecular weight compounds such as the polyglycidyl ester compound obtained by reacting the (poly) amine compound with epichlorohydrin and the (poly) glycidyl amine compound.

When the thermal cross-linking agent is contained, the content ratio thereof is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more in the total solid content. Yes, it is usually 40% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, the developability tends to be improved.

[1-5-4] Solvent The self-luminous photosensitive resin composition of the present invention usually contains a solvent and is used in a state where each of the above-mentioned components is dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether , Glycol dialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate Glycolalkyl ether acetates such as triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol diacetate, 1 , 3-butylene glycol diacetate, glycol diacetates such as 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether , Ethylisobutyl ethers, ethers such as dihexyl ethers; acetone, methylethylketone, methylamylketone, methylisopropylketone, methylisoamylketone, diisopropylketone, diisobutylketone, methylisobutylketone, cyclohexanone, ethylamylketone, methylbutylketone, methyl Ketones such as hexyl ketone, methylnonyl ketone, methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxy Monovalent or polyhydric alcohols such as methylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amylformate, ethylformate, ethyl acetate, butyl acetate, Ppropyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprilate, butyl stearate, ethyl benzoate, 3-ethoxypropion Chain or cyclic esters such as methyl acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amilk loride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile. Una nitriles: tetrahydrofurans such as tetrahydrofuran, dimethyl tetrahydrofuran, dimethoxytetrahydrofuran and the like.

Commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2. Solbesso # 150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, jiglime (all trade names) and the like can be mentioned.

The solvent can dissolve or disperse each component in the self-luminous photosensitive resin composition of the present invention, and is selected according to the method of use thereof, but from the viewpoint of coatability, it is under atmospheric pressure. It is preferable to select one having a boiling point in the range of 60 to 280 ° C. at (1013.25 hPa). More preferably, it has a boiling point of 70 ° C. or higher and 260 ° C. or lower, and for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.
These solvents may be used alone or in admixture of two or more.

When the solvent is contained, the content ratio thereof is not particularly limited, but the content ratio of the total solid content in the self-luminous photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably. Is preferably used in an amount of 12% by mass or more, usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 20% by mass or less. When it is at least the above lower limit value, the film thickness at the time of forming the coating film tends to be stable, and when it is at least the above upper limit value, the storage stability tends to be improved.

[2] Method for Producing Self-luminous Photosensitive Resin Composition The method for producing the self-luminous photosensitive resin composition of the present invention is not particularly limited, and is prepared, for example, by mixing each of the above components with a stirrer. .. In addition, you may filter using a membrane filter or the like so that the prepared self-luminous photosensitive resin composition becomes uniform.

[3] Color conversion layer The self-luminous photosensitive resin composition of the present invention can be suitably used for forming a color conversion layer, particularly a color conversion layer for a color filter of an image display device. That is, the cured product obtained by curing the self-luminous photosensitive resin composition of the present invention can be used as the color conversion layer.

The color conversion layer can be formed as a pattern corresponding to red pixels and green pixels of a color filter by applying a self-luminous photosensitive resin composition and then patterning by a photolithography method. As the photolithography method, a conventionally known method can be adopted.

In the photolithography method, first, a self-luminous photosensitive resin composition is applied to the entire surface of a substrate to form a photosensitive resin composition layer. The formed photosensitive resin composition layer is exposed according to the pattern of a predetermined color conversion layer, and then the exposed photosensitive resin composition layer is developed to form a color conversion layer on the substrate.

In the coating process of coating on a substrate, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact coating device such as a spinner (rotary coating device) or a curtain flow coater is used to sensitize the substrate. The sex resin composition is applied, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

Next, in the exposure step, the photosensitive resin composition layer is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask, and the photosensitive resin composition layer is subjected to the pattern of the color conversion layer. Partially exposed. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, and a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to ^{400 mJ / cm 2, for example.}

Next, in the developing step, a partition wall is formed by developing the photosensitive resin composition layer exposed according to the pattern of the color conversion layer with a developing solution. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. Can be mentioned. Further, an antifoaming agent or a surfactant can be added to the developing solution.

Then, the photosensitive resin composition layer after development is post-baked and heat-cured. Post-baking is preferably at 150-250 ° C. for 15-60 minutes.

The substrate used for forming the color conversion layer is not particularly limited, and examples of suitable substrate materials include glass and various resin materials. Specific examples of the resin material include polyester such as polyethylene terephthalate; polyethylene and polyolefin such as polypropylene; polycarbonate; poly (meth) metaacrylic resin; polysulfone; polyimide. Among these substrate materials, glass and polyimide are preferable because they have excellent heat resistance.

The thickness of the color conversion layer is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, from the viewpoint of maintaining high brightness, ensuring excellent color conversion characteristics and high light efficiency.

[4] Color Filter The color filter of the present invention includes a color conversion layer formed by using the self-luminous photosensitive resin composition of the present invention.
The layer structure of the color filter of the present invention is not particularly limited, but those including a color layer including red pixels, green pixels, and blue pixels and the color conversion layer are preferable.
As the color layer, conventionally known ones can be adopted.

[5] Image Display Device The image display device of the present invention includes the color filter.
In the image display device of the present invention, it is preferable that the color conversion layer is arranged between the backlight unit (light source) and the color layer, and specifically, the structure in which the color conversion layer is in direct contact with the color layer. , A structure in which another layer or a substrate is interposed between the color conversion layer and the color layer can be mentioned.

The type of image display device is not particularly limited as long as it is of a type provided with a color filter, and examples thereof include a liquid crystal display device and an organic EL display device, and examples of the light source of the backlight unit include an LED, a cold cathode tube, and an organic device. An EL element and the like can be mentioned.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
<Synthesis of fluorescent compounds>

(Synthesis Example 1: Synthesis of Fluorescent Compound-I)

A mixture of Intermediate 1 (11.7 g), N-methyl-2-pyrrolidone (240 ml), potassium carbonate (11.6 g) and 4- (2-methoxyethyl) phenol (12.8 g) under a nitrogen atmosphere. The mixture was stirred at 90 to 100 ° C. for 14 hours. After cooling to room temperature, the mixture was poured into ice water, the obtained insoluble material was collected by filtration, and purified by silica gel column chromatography to obtain fluorescent compound-I (15 g).

<Synthesis of alkali-soluble resin>
(Synthesis Example 2: Synthesis of Alkali-Soluble Resin-I)
145 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 107 parts by mass of styrene, 42.6 parts by mass of glycidyl methacrylate and 22 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and 2.2'-azobis-2-methylbuty was added. 8.47 parts by mass of ronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 21.6 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 35 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained as measured by GPC was about 10,000, and the solid acid value was 68.8 mgKOH / g.

<Preparation of fluorescent compound solution>
The fluorescent compound-I and the fluorescent compound-II obtained in Synthesis Example 1 were dissolved in PGMEA so that their concentrations were 8 ppm by mass, respectively, to prepare fluorescent compound solutions-I and II, respectively. As the fluorescent compound-II, Lumogen F Red 305 (manufactured by BASF) was used.

<Preparation of self-luminous photosensitive resin composition>
Fluorescent compound-I, fluorescent compound-II, alkali-soluble resin-I and other components are mixed so that the content ratio of the solid content in the total solid content is the composition shown in Table 1, and the total solid content is further mixed. PGMEA was added and diluted so that the content of the component was 15% by mass to prepare self-luminous photosensitive resin compositions-I and II.
At the time of mixing, the mixture was stirred for 1 hour or more until each component was sufficiently mixed, and finally filtered through a 5 μm piece-shaped filter to remove foreign substances.

The details of each component in Table 1 are as follows.
Photopolymerizable Compound-I: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization Initiator-I: Irgacure907 (manufactured by BASF)
Photopolymerization Initiator-II: 2,4-Diethylthioxanthone Additive-I: Pentaerythritol Tetrakis (3-Mercaptopropionate)
Additive-II: Tetrahydro-1,3,4,6-tetrakis (2-oxylanylmethyl) -imidazole [4,5-d] imidazole-2,5- (1H, 3H) -dione (TG-G) , Made by Shikoku Kaseisha)
Additive-III: Irganox 1010 (manufactured by BASF)
Additive-IV: JPP-100 (manufactured by Johoku Chemical Industry Co., Ltd.)
Surfactant-I: Megafuck RS-72K (manufactured by DIC Corporation)

The performance evaluation method will be described below.
<Measurement of development time>
A self-luminous photosensitive resin composition was applied onto a glass substrate using a spinner so as to have a thickness of 2.0 μm after drying. Then, it was heated and dried on a hot plate at 100 ° C. for 3 minutes to obtain a coated substrate. Next, an aqueous solution prepared by dissolving 0.04% by mass of KOH and 0.07% by mass of Emargen A-60 (surfactant manufactured by Kao Co., Ltd.) without exposing the obtained coating film substrate to ultraviolet rays was used as a developing solution. The coating film was completely developed and removed by spray development at 23 ° C. (development time). The results are shown in Table 2.

<Measurement of quantum yield>
Next, in order to evaluate the luminescence characteristics of the fluorescent compounds contained in the self-luminous photosensitive resin compositions-I and II, respectively, the quantum yield of the fluorescent compound was measured using the fluorescent compound solution. ..

4 mL of each fluorescent compound solution was placed in a quartz cell, and the quantum yield at an excitation wavelength of 560 nm was measured using an absolute PL quantum yield measuring device (C9920, manufactured by Hamamatsu Photonics). The results are shown in Table 3.

From Tables 2 and 3, the fluorescent compound (1) of Example 1 shows a better quantum yield than the fluorescent compound of Comparative Example 1, and the self-luminous light of the present invention containing the fluorescent compound (1). The type photosensitive resin composition has a shorter development time than the self-luminous photosensitive resin composition of Comparative Example 1. That is, it was suggested that the self-luminous photosensitive resin composition of the present invention can shorten the time required to form a pattern while exhibiting excellent emission intensity.

The fluorescent compound (1) is considered to exhibit a high quantum yield by having a perylene bisimide in the mother skeleton, and is particularly a hydrophilic group by having two or more arbitrary monovalent groups including a hydrophilic group. It is considered that the affinity for PGMEA, which is a solvent having a certain ester group and ether group, is increased, the formation of aggregates between perylene bisimide skeletons is inhibited, and the anti-dimming action between molecules is prevented, thereby further improving the quantum yield. Be done. This suggests that the fluorescent compound (1) exhibits a high quantum yield even in a self-luminous photosensitive resin composition containing an alkali-soluble resin having a carboxyl group which is a hydrophilic group.
Further, it is considered that the hydrophilic group increased the solubility in the developing solution and shortened the developing time.

According to the present invention, it is possible to provide a self-luminous photosensitive resin composition showing a high quantum yield and a short dissolution time in a developing solution. Therefore, the present invention is useful in applications such as a color filter including a color conversion layer and an image display device.

Claims (8)

A self-luminous photosensitive resin composition containing (A) a fluorescent compound, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator.
A self-luminous photosensitive resin composition, wherein the fluorescent compound (A) contains a fluorescent compound represented by the following general formula (1).

(In the formula (1), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ³ represents any monovalent group, including hydrophilic groups.
n represents an integer of 2 to 6.
The benzene ring in the formula (1) may be further substituted with an arbitrary substituent. ) The self-luminous photosensitive resin composition according to claim 1, wherein the fluorescent compound represented by the general formula (1) is a fluorescent compound represented by the following general formula (2).

(In the formula (2), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^{4 to} R ⁷ each independently represent any monovalent group, including a hydrophilic group.
The benzene ring in the formula (2) may be further substituted with an arbitrary substituent. ) The self-luminous photosensitive resin composition according to claim 2, wherein in the formula (2), R ^{4 to} R ^{7 are all the same group.} The self-luminous photosensitive resin composition according to claim 2, wherein the fluorescent compound represented by the general formula (2) is a fluorescent compound represented by the following general formula (3).

(In the formula (3), R ¹ and R ² each independently represent an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ⁸ is a monovalent group represented by the following general formula (4), and all are the same. )

(In the formula (4), X ^{1 to} X ⁵ each independently represent an arbitrary monovalent group including a hydrogen atom, an alkyl group which may have a substituent, or a hydrophilic group, and X ^{At least one of 1 to} X ⁵ represents any monovalent group, including hydrophilic groups.) In the formula (4), the hydrophilic group is a hydroxyl group, an alkoxy group, an alkylthio group, a carboxyl group, an acyl group, an ester group, an amino group, an alkylamino group, an amide group, an imide group, a carbamate group, and a urea group. The self-luminous photosensitive resin composition according to claim 4, which is one or more selected from the group consisting of. The self-luminous photosensitive resin composition according to any one of claims 1 to 5, wherein the content ratio of the fluorescent compound (A) is 20% by mass or less in the total solid content. A color filter including a color conversion layer formed by using the self-luminous photosensitive resin composition according to any one of claims 1 to 6. An image display device including the color filter according to claim 7.