JP2017173765A - Colored photosensitive composition, colored cured product obtained therefrom, display element, and method of producing colored cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive composition excellent in solvent resistance, a colored cured product obtained therefrom, a display element, and a method of producing the colored cured product.SOLUTION: The colored photosensitive composition contains (P) a cationically and/or acid-catalytically polymerizable and/or crosslinkable compound, (A) at least one photosensitizer selected from the group consisting of photoinitiators and sulfonium salts represented by the general formula (a1) in the figure, and (B) a colorant.SELECTED DRAWING: None

Description

  The present invention relates to a colored photosensitive composition, a colored cured product obtained thereby, a display element, and a method for producing a colored cured product.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes facing each other is formed. A color filter having pixels of red (R), green (G), blue (B) and the like is formed inside one substrate. In this color filter, in order to prevent color mixing of different colors in each pixel or to conceal the electrode pattern, the color filter is usually arranged in a matrix so as to partition the pixels of R, G, and B colors. A black matrix is formed.
Generally, the color filter is formed by a photolithography method. Specifically, first, a black photosensitive composition is applied to a substrate, exposed, and developed to form a black matrix. Then, for each of the photosensitive compositions of red (R), green (G), and blue (B), coating, exposure, and development are repeated to form a pattern of each color at a predetermined position, thereby forming a color filter. Form.

  According to such a method, it is easy to form a colored film pattern having excellent dimensional accuracy and positional accuracy. As a method of forming a colored film such as a black matrix by a photolithography method, a method of forming a colored cured product (colored film) by a photolithography method using a photosensitive resin composition containing carbon black as a light shielding agent has been proposed. (See Patent Documents 1 and 2).

JP 2000-199967 A JP 2011-170075 A

However, in the formation of a color filter or the like, as described above, since the photosensitive composition is repeatedly applied, exposed, and developed, a colored cured product such as a colored film is often repeatedly exposed to an organic solvent. Nevertheless, a colored cured product formed by a conventionally known method often causes excessive dissolution due to repeated contact with an organic solvent.
When the post-baking temperature after exposure (particularly after development) is carried out in a lower temperature range (for example, in the case of low-temperature baking at about 80 to 160 ° C.), it is difficult to obtain sufficient film resistance to an organic solvent. there were.

  The present invention has been made in view of the above problems, and a colored photosensitive composition in which a colored cured product is excellent in solvent resistance even when the baking temperature range such as post-baking is low, It is an object of the present invention to provide a colored cured product, a display element, and a method for producing a colored cured product obtained by the above method.

The inventors of the present invention provide the colored photosensitive composition at least selected from the group consisting of a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound, a specific sulfonium salt and a photopolymerization initiator. It has been found that the above-mentioned problems can be solved by including one photosensitive agent and a colorant, and the present invention has been completed.
Specifically, the present invention is as follows.

（上記一般式中、Ｒ^１及びＲ^２は独立に、ハロゲン原子で置換されていてもよいアルキル基又は下記一般式（ａ２）で表される基を示し、Ｒ^１及びＲ^２は相互に結合して式中の硫黄原子と共に環を形成してもよく、Ｒ^３は下記一般式（ａ３）で表される基又は下記一般式（ａ４）で表される基を示し、Ａ^１はＳ、Ｏ、又はＳｅを示し、Ｘ⁻は１価のアニオンを示し、但し、Ｒ^１及びＲ^２は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

（上記一般式中、環Ｚ^１は芳香族炭化水素環を示し、Ｒ^４はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アルコキシカルボニル基、アシロキシ基、アルキルチオ基、チエニル基、チエニルカルボニル基、フラニル基、フラニルカルボニル基、セレノフェニル基、セレノフェニルカルボニル基、複素環式脂肪族炭化水素基、アルキルスルフィニル基、アルキルスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ１は０以上の整数を示す。）

（上記一般式中、Ｒ^５はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記一般式（ａ５）で表される基を示し、Ｒ^６はヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキル基又は下記一般式（ａ６）で表される基を示し、Ａ^２は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、ｎ１は０又は１を示す。）

（上記一般式中、Ｒ^７及びＲ^８は独立に、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、若しくはハロゲン原子で置換されていてもよいアルキレン基又は下記一般式（ａ５）で表される基を示し、Ｒ^９及びＲ^１０は独立に、ハロゲン原子で置換されていてもよいアルキル基又は上記一般式（ａ２）で表される基を示し、Ｒ^９及びＲ^１０は相互に結合して式中の硫黄原子と共に環を形成してもよく、Ａ^３は単結合、Ｓ、Ｏ、スルフィニル基、又はカルボニル基を示し、Ｘ⁻は前記の通りであり、ｎ２は０又は１を示し、但し、Ｒ^９及びＲ^１０は、同時に、ハロゲン原子で置換されていてもよいアルキル基ではない。）

（上記一般式中、環Ｚ^２は芳香族炭化水素環を示し、Ｒ^１１はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ２は０以上の整数を示す。）

（上記一般式中、環Ｚ^３は芳香族炭化水素環を示し、Ｒ^１２はハロゲン原子で置換されていてもよいアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシロキシ基、アリールチオ基、アルキルチオ基、チエニルカルボニル基、フラニルカルボニル基、セレノフェニルカルボニル基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ（ポリ）アルキレンオキシ基、置換されていてよいアミノ基、シアノ基、ニトロ基、又はハロゲン原子を示し、ｍ３は０以上の整数を示す。） The first aspect of the present invention is:
(P) a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound;
(A) at least one photosensitizer selected from the group consisting of a sulfonium salt represented by the following general formula (a1) and a photopolymerization initiator;
(B) A colored photosensitive composition containing a colorant.

(In the above general formula, R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following general formula (a2), and R ¹ and R ² are bonded to each other. A ring may be formed together with the sulfur atom in the formula, R ³ represents a group represented by the following general formula (a3) or a group represented by the following general formula (a4), A ¹ represents S, O or Se represents, and X ⁻ represents a monovalent anion, provided that R ¹ and R ² are not an alkyl group which may be substituted with a halogen atom at the same time.

(In the above general formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, acyloxy group optionally substituted with a halogen atom, Alkylthio group, thienyl group, thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy (poly) alkyleneoxy A group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)

(In the above general formula, R ⁵ represents a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a complex, Cyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen optionally substituted alkylene group or the following general formula atom a group represented by (a5), R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxy carbonitrile Group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly ) alkyleneoxy group, substituted amino group, a cyano group, a nitro group, or a group represented by optionally substituted alkyl group or the following general formula with a halogen atom (a6), a ² represents a single A bond, S, O, a sulfinyl group, or a carbonyl group, and n1 represents 0 or 1.)

(In the above general formula, R ⁷ and R ⁸ are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group. Group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, amino group which may be substituted, cyano group , A nitro group, or an alkylene group optionally substituted with a halogen atom or a group represented by the following general formula (a5), wherein R ⁹ and R ¹⁰ are independently alkyl optionally substituted with a halogen atom A group represented by the above general formula (a2) R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, and X ⁻ represents the above-mentioned And n2 represents 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group which may be substituted with a halogen atom.

(In the above general formula, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group optionally substituted with a halogen atom. , Aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, A hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more.)

(In the above general formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group optionally substituted with a halogen atom. , Aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl A group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more. .)

The second aspect of the present invention is:
It is a colored cured product obtained by curing the colored photosensitive composition of the first aspect.

The third aspect of the present invention is:
Forming a coating film by applying the colored photosensitive composition of the first aspect onto a substrate;
It is a manufacturing method of colored hardened | cured material including the process of exposing the said coating film, and the process of baking the said exposed coating film.

The fourth aspect of the present invention is:
It is a manufacturing method of colored hardened | cured material including the process of superposing | polymerizing and / or bridge | crosslinking the colored photosensitive composition of a 1st aspect.

The colored photosensitive composition of the present invention is formed even when baking such as post-baking is performed at a low temperature of, for example, less than 200 ° C, specifically about 80 to 160 ° C (more preferably 80 to 120 ° C). The colored cured product has excellent solvent resistance.
The method for producing a colored cured product of the present invention can provide a colored cured product having excellent solvent resistance.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. .
In the present specification, description such as “A and / or B”, “A and / or B”, “A and / or B”, and the like, for example, “cationically and / or acid-catalyzed” “At least one selected from the group consisting of A and B”. Here, A and B are arbitrary terms.

<Colored photosensitive composition>
First, the colored photosensitive composition according to the first aspect of the present invention will be described.
The colored photosensitive composition according to the first aspect of the present invention is:
(P) a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound;
(A) at least one photosensitive agent selected from the group consisting of the sulfonium salt represented by the general formula (a1) and a photopolymerization initiator;
(B) contains a colorant.
Hereinafter, selected from the group consisting of (P) a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound, and (A) a sulfonium salt represented by the above general formula (a1) and a photopolymerization initiator. The at least one photosensitive agent, the colorant (B), and other components will be described in order.

[(P) Cationic and / or acid-catalyzed polymerizable and / or crosslinkable compound]
A cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound (hereinafter also referred to as “compound (P)”) can be cationically polymerized, for example, by an alkyl group or aryl group-containing cation or by a proton. Contains compounds. Examples thereof include cyclic ethers, especially epoxy compounds and oxetane compounds, vinyl ether compounds and hydroxy-containing compounds. Lactone compounds and cyclic thioether compounds and vinyl thioether compounds can also be used.
In this specification, unless otherwise specified, “epoxy” generally includes not only oxiranyl but also oxetanyl and alicyclic epoxy.

  Further examples include amino plastics or phenolic resole resins. These are in particular melamine resins, urea resins, epoxy resins, phenol resins, acrylic resins, polyester resins and alkyd resins, but in particular mixtures of acrylic resins, polyester resins or alkyd resins with melamine resins. These include modified surface coating resins (for example, acrylic modified polyester resins and acrylic modified alkyd resins). The term surface coating resin preferably includes an amino resin. Examples thereof include etherified and non-etherified melamine resins, urea resins, guanidine resins, biuret resins. Acid catalysts for curing surface coatings comprising etherified amino resins (eg methylated melamine resins or butylated melamine resins (N-methoxymethyl-melamine or N-butoxymethyl-melamine) or methylated / butylated glycoluril) Of particular importance.

  When compound (P) is an epoxy compound, it is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, but is preferably a compound having at least two epoxy groups in the molecule. The epoxy compound can be selected from various compounds having an epoxy group that are conventionally blended in curable compositions. The epoxy compound may be a low molecular compound having an epoxy group which is a non-polymer, or may be a polymer having an epoxy group, but a non-polymer is preferred. As the non-polymer having an epoxy group, an aliphatic epoxy compound containing no aromatic group is preferable because a cured product formed using the colored photosensitive composition is excellent in thermogravimetric stability. Among the aliphatic epoxy compounds, an aliphatic epoxy compound having an alicyclic epoxy group is preferable in that sequential polymerization proceeds by ring-opening polymerization and polymerization is promoted.

（式（Ｐ−１）中、Ｚは単結合又は連結基（１以上の原子を有する二価の基）を示す。Ｒ^ａ１〜Ｒ^ａ１８は、水素原子、ハロゲン原子、又は酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。） Specific examples of the aliphatic epoxy compound having an alicyclic epoxy group include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ -Valerolactone modified 3,4-epoxy Xicyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxyl) Rate), epoxycyclohexahydrophthalate dioctyl, epoxycyclohexahydrophthalate di-2-ethylhexyl, epoxy resin having tricyclodecene oxide groups, and the following formulas (P-1) to (P-5) The compound which is made is mentioned. Among the specific examples of these aliphatic epoxy compounds, the alicyclic epoxy compounds represented by the following formulas (P-1) to (P-4) are represented in that sequential polymerization proceeds and polymerization is promoted. Preferably, alicyclic epoxy compounds represented by the following formulas (P-1) to (P-2) are more preferable. These alicyclic epoxy compounds may be used alone or in combination of two or more.

(In formula (P-1), Z represents a single bond or a linking group (a divalent group having one or more atoms). R ^{a1 to} R ^a18 are a hydrogen atom, a halogen atom, an oxygen atom, or a halogen atom. These may be the same or different from each other.)

Examples of the linking group Z include a divalent hydrocarbon group, —O—, —O—CO—, —S—, —SO—, —SO ₂ —, —CBr ₂ —, —C (CBr ₃ ) _2. And a divalent group selected from the group consisting of —, —C (CF ₃ ) ₂ —, and —R ^a19 —O—CO—, and a group in which a plurality of these groups are bonded.

  Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, and a divalent alicyclic hydrocarbon group. . Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, Examples include cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

R ^a19 is an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group or an ethylene group.

  As a compound represented by the formula (P-1), a compound that is difficult to take a conjugated structure (particularly, a π-electron conjugated structure) by dehydrogenation is a cured product having excellent transparency in addition to thermogravimetric stability. It is preferable in that it can be obtained, and in particular, an alicyclic epoxy compound, specifically, two alicyclic epoxy groups in one molecule are connected via a linking group containing a quaternary carbon and / or a hetero atom. Bound compounds are preferred.

Moreover, as a compound (P), the alicyclic epoxy compound represented by following formula (P-2)-(P-5) is mentioned.

(In Formula (P-2), R ^{a1 to} R ^a12 are a hydrogen atom, a halogen atom, or a hydrocarbon group that may contain an oxygen atom or a halogen atom, and may be the same or different. May be.)

（式（Ｐ−３）中、Ｒ^ａ１〜Ｒ^ａ１０は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ２及びＲ^ａ８は、互いに結合してもよい。）

(In Formula (P-3), R ^{a1 to} R ^a10 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a2 and R ^a8 are bonded to each other. May be.)

（式（Ｐ−４）中、Ｒ^ａ１〜Ｒ^ａ１２は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。Ｒ^ａ２及びＲ^ａ１０は、互いに結合してもよい。）

(In Formula (P-4), R ^{a1 to} R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R ^a2 and R ^a10 are bonded to each other. May be.)

（式（Ｐ−５）中、Ｒ^ａ１〜Ｒ^ａ１２は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。）

(In formula (P-5), R ^{a1 to} R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In formula (P-5), when R ^{a1 to} R ^a12 are organic groups, the organic group is not particularly limited as long as it does not impair the object of the present invention, and even if it is a hydrocarbon group, a carbon atom and a halogen atom Or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

  The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, a carbon atom and a hydrogen atom. And a group consisting of an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for the carbon atom number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Chain alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl, 2-n-butenyl, and 3-n-butenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl And a cycloalkyl group such as cycloheptyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl Group, biphenyl-2-yl group, anthryl group, phenanthryl group and other aryl groups; benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group And aralkyl groups such as

  Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And 4-bu Halogenated cycloalkyl group such as mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4- Halogenated aryl groups such as fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2 -Fluorophenylmethyl group, 3-fluorophenyl Methyl group, a halogenated aralkyl group such as 4-fluorophenyl methyl group.

  Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain groups such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group. Alkyl groups; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl groups; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3 -Hydroxyaryl groups such as dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group ; 2-hydroxyphenylmethyl group, 3-hydroxy A hydroxyaralkyl group such as an phenylmethyl group and a 4-hydroxyphenylmethyl group; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tri Decyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc. Chain alkoxy group; vinyloxy group, 1-propenylo Chain-like alkenyloxy groups such as 2- group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; phenoxy group, o-tolyloxy Group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, And aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group, etc. Aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-propoxymethyl group 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, Alkoxymethoxy groups such as 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2 -Methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4- Alkoxyalkoxy such as methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group Groups; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group and 4-methoxyphenyl group; alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group An aliphatic acyl group such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group; benzoyl group, α-naphthoyl group, and β-naphthoyl An aromatic acyl group such as a group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n -Octyloxy Chain alkyloxycarbonyl groups such as sulfonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl, α-naphthoxycarbonyl, and β-naphthoxycarbonyl Aliphatic groups such as formyloxy, acetyloxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy An acyloxy group; an aromatic acyloxy group such as a benzoyloxy group, an α-naphthoyloxy group, and a β-naphthoyloxy group;

R ^{a1 to} R ^a18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. It is more preferable that R ^{a1 to} R ^a18 are all hydrogen atoms because the cured product obtained using the photosensitive composition is excellent in mechanical properties.

Wherein (P-2) ~ (P -5), R a1 ~R a12 is the same as ^R a1 ^{to R a12} in Formula (P-1). In formula (P-2) and formula (P-4), examples of the divalent group formed when R ^a2 and R ^a10 are bonded to each other include, for example, —CH ₂ — and —C (CH ₃ ). _2- . In formula (P-3), examples of the divalent group formed when R ^a2 and R ^a8 are bonded to each other include —CH ₂ — and —C (CH ₃ ) ₂ —.

Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P-1) include alicyclic rings represented by the following formulas (P1-1a) (P1-1b) (P1-1c). An epoxy compound of the formula, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], and the like can be given.

Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P-2) include bicyclononadiene diepoxides or dicyclononadiene diepoxides represented by the following formula (P1-2a). Etc.

Among the alicyclic epoxy compounds represented by the formula (P-3), specific examples of suitable compounds include S spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6. , 2′-oxirane] and the like.

  Specific examples of suitable compounds among the alicyclic epoxy compounds represented by the formula (P-4) include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4- (3 -Methyloxiran-2-yl) -7-oxabicyclo [4.1.0] heptane and the like.

  Among the alicyclic epoxy compounds represented by the formula (P-5), specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane.

In addition to the aliphatic epoxy compounds having an alicyclic epoxy group described above, examples of non-polymers having an epoxy group that can be used as the compound (P) include glycidyl (meth) acrylate, 2-methylglycidyl (meta ) Epoxyalkyl (meth) acrylates such as acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n- Epoxyalkyloxyalkyl such as propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate (Meth) acrylate; bis Bifunctional epoxy resins such as enol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; phenol novolac type epoxy resin, brominated phenol Novolac epoxy resins such as novolac epoxy resins, orthocresol novolac epoxy resins, bisphenol A novolac epoxy resins, and bisphenol AD novolac epoxy resins; cycloaliphatic epoxy resins such as epoxidized products of dicyclopentadiene phenol resins; Aromatic epoxy resin such as epoxidized naphthalene type phenol resin; 9,9-bis [4- (glycidyloxy) phenyl] -9H-fluorene, 9,9-bis [4 [2- (Glycidyloxy) ethoxy] phenyl] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethyl] phenyl] -9H-fluorene, 9,9-bis [4- (glycidyl) Oxy) -3-methylphenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3,5-dimethylphenyl] -9H-fluorene, and 9,9-bis (6-glycidyloxynaphthalene) -2-yl) -9H-fluorene-containing fluorene compound such as dimer acid glycidyl ester and glycidyl ester-type epoxy resin such as triglycidyl ester; tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmeta Xylylenediamine and tetraglycidylbisua Glycidylamine type epoxy resins such as minomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3 -Bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl ] Trifunctional epoxy such as ethyl] phenoxy] -2-propanol Resin; tetrafunctional epoxy resin such as tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl, and 1,2-bis (hydroxymethyl) -1-butanol , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol is commercially available as EHPE-3150 (manufactured by Daicel Corporation).
Further, 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl oxetane, 3-ethyl-3-hydroxymethyl oxetanyl methacrylate, bis-1-ethyl-3-oxetanyl methyl ether, 1,4-bis-3-ethyl oxetane Monofunctional or bifunctional or higher functional oxetane compounds such as -3-ylmethoxymethylbenzene, 3-ethyl-3--2-ethylhexyloxymethyl oxetane, and 3-ethyl-3-phenoxymethyl oxetane are also preferably exemplified.

(Polymer having epoxy group)
The polymer having an epoxy group may be a polymer obtained by polymerizing a monomer mixture containing an epoxy group-containing monomer or an epoxy group-containing monomer, and includes a hydroxyl group, a carboxy group, and an amino group. For example, an epoxy group may be introduced into a polymer having a functional group having reactivity such as an epoxy group such as epichlorohydrin. A partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain such as 1,2-polybutadiene can also be suitably used as the polymer having an epoxy group. Such a partial oxide includes an epoxy group generated by oxidation of an unsaturated bond contained in the side chain.

  Since it is easy to obtain, prepare, adjust the amount of the epoxy group in the polymer, etc., the polymer having an epoxy group includes a monomer having an epoxy group or a monomer having an epoxy group A polymer obtained by polymerizing a body mixture and a partial oxide of a polymer having an unsaturated aliphatic hydrocarbon group in the side chain are preferred.

(Polymer of a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group)
Among polymers having an epoxy group, is it a homopolymer of (meth) acrylic acid ester having an epoxy group in terms of ease of preparation and coating properties of the colored photosensitive composition to the substrate? A copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is preferable.

  The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Moreover, the (meth) acrylic acid ester which has an epoxy group may contain the aromatic group. Among the (meth) acrylic acid ester having an epoxy group, an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group from the viewpoint of transparency of a cured product formed using the colored photosensitive composition Or, an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is preferable, and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group is more preferable.

  Examples of (meth) acrylic acid ester containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

  Examples of the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group include an ester group (—O—CO—, such as epoxy alkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate). (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in (). Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

  Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meta And epoxyalkyloxyalkyl (meth) acrylates such as acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate.

  Specific examples of the aliphatic (meth) acrylic acid ester having an alicyclic epoxy group include compounds represented by the following formulas (a2-1) to (a2-15). Among these, compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and compounds represented by the following formulas (a2-1) to (a2-3) are more preferable.

In the above general formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents a divalent group having 1 to 10 carbon atoms. And t represents an integer of 0 to 10. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a cyclohexylene group are preferable.

  As the polymer having an epoxy group, any of a homopolymer of (meth) acrylic acid ester having an epoxy group and a copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is used. However, the content of the unit derived from the (meth) acrylic acid ester having an epoxy group in the polymer having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % Or more is particularly preferable, and 100% by mass is most preferable.

  When the polymer having an epoxy group is a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer, the other monomer has an unsaturated carboxylic acid or an epoxy group. Examples thereof include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more. From the viewpoint of the storage stability of the colored photosensitive composition and the chemical resistance to the alkali or the like of the cured product formed using the colored photosensitive composition, (meth) acrylic acid ester having an epoxy group and other simple substances are used. The copolymer with the monomer preferably does not contain a unit derived from an unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

  Examples of (meth) acrylic acid esters having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like. Linear or branched alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (Meth) acrylate, furfuryl (meth) acrylate; (meth) acrylic acid ester having a group having an alicyclic skeleton. Among (meth) acrylic acid esters having no epoxy group, (meth) acrylic acid ester having a group having an alicyclic skeleton is used from the viewpoint of transparency of a cured product formed using a colored photosensitive composition. preferable.

  In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Examples of the (meth) acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a3-1) to (a3-8). Among these, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and compounds represented by the following formula (a3-3) or (a3-4) are more preferable.

In the above general formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or the number of carbon atoms. 1-5 alkyl groups are shown. R ^a24 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. R ^a25 is preferably a methyl group or an ethyl group.

  Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, and N, N-aryl (meth) acrylamide. N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of allyl compounds include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Etc.

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

  Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Examples include phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

  Examples of styrenes include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene. Alkyl styrene such as ethoxymethyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Methylstyrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

(Partial oxide of polymer having unsaturated aliphatic hydrocarbon group in side chain)
The polymer having an unsaturated aliphatic hydrocarbon in the side chain is not particularly limited, but 1,2-polybutadiene having a vinyl group in the side chain is preferred because it is easily available and synthesized. By partially oxidizing 1,2-polybutadiene, an epoxidized polybutadiene having an oxiranyl group and a vinyl group in the side chain is obtained. The ratio of the oxiranyl group in such epoxidized polybutadiene is preferably 10 to 70 mol%, more preferably 10 to 50 mol%, and more preferably 10 to 40 mol% with respect to the total number of moles of the oxiranyl group and the vinyl group. preferable. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Nippon Soda Co., Ltd. can be suitably used.

  The molecular weight of the polymer having an epoxy group described above is not particularly limited as long as the object of the present invention is not impaired, but the polystyrene-equivalent mass average molecular weight is preferably 3,000 to 30,000, preferably 5,000 to 5,000. 15,000 is more preferable.

  Moreover, as a compound (P), the compound represented by a following formula (P-6) is mentioned.

（式（Ｐ−６）中、Ｒ^Ｐ３１〜Ｒ^Ｐ３３は、直鎖状、分岐鎖状又は環状のアルキレン基、アリーレン基、−Ｏ−、−Ｃ（＝Ｏ）−、−ＮＨ−及びこれらの組み合わせからなる基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ^１〜Ｅ^３は、エポキシ基、オキセタニル基、エチレン性不飽和基、アルコキシシリル基、イソシアネート基、ブロックイソシアネート基、チオール基、カルボキシ基、水酸基及びコハク酸無水物基からなる群より選択される少なくとも１種の置換基又は水素原子である。但し、Ｅ^１〜Ｅ^３のうち少なくとも１つは、エポキシ基及びオキセタニル基からなる群より選択される少なくとも１種である。）

(In Formula (P-6), R ^{P31 to} R ^P33 represent a linear, branched or cyclic alkylene group, an arylene group, —O—, —C (═O) —, —NH—, and these E ^{1 to} E ³ are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate. And at least one substituent selected from the group consisting of a group, a thiol group, a carboxy group, a hydroxyl group and a succinic anhydride group, provided that at least one of E ^{1 to} E ³ is an epoxy group. And at least one selected from the group consisting of oxetanyl groups.)

In formula (P-6), at least one group represented by R ^P31 and E ¹ , R ^P32 and E ² , and R ^P33 and E ³ is a group represented by the following formula (P-6a), for example. It is preferable that at least two are groups each represented by the following formula (P-6a), and each is a group represented by the following formula (P-6a). More preferably it is. The groups represented by the formula (P-6a) bonded to one compound are preferably the same group.
-LC (P-6a)
(In the formula (P-6a), L is a group comprising a linear, branched or cyclic alkylene group, an arylene group, -O-, -C (= O)-, -NH-, and a combination thereof. And C is at least one selected from the group consisting of an epoxy group and an oxetanyl group, and in formula (P-6a), L and C may be combined to form a cyclic structure.

  In formula (P-6a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is a carbon atom. The arylene group of several 5-10 is preferable. In the formula (P-6a), L represents a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, —O—, —C (═O) —, —NH—, and a combination thereof. It is preferable that at least one of a linear alkylene group having 1 to 3 carbon atoms such as a methylene group and a phenylene group, or these, and -O-, -C (= O)-, and NH-. A group consisting of a combination with at least one of these is preferred.

（式（Ｐ−６ｂ）中、Ｒ^Ｐ３４は、水素原子又はメチル基である。）

In the formula (P-6a), when L and C are bonded to form a cyclic structure, for example, a branched alkylene group and an epoxy group are bonded to form a cyclic structure (alicyclic structure). When forming the structure which has an epoxy group, the organic group represented by the following formula (P-6b) or (P-6c) is mentioned.

(In formula (P-6b), R ^P34 represents a hydrogen atom or a methyl group.)

Hereinafter, examples of the epoxy compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, and an alicyclic epoxy group are shown as examples of the compound represented by the formula (P-6). The invention is not limited to these.

  Examples of the compound (P) include a siloxane compound having two or more glycidyl groups in the molecule (hereinafter also referred to as “siloxane compound (S)”).

  The siloxane compound (S) can impart yellowing prevention property (= heat resistant transparency) when exposed to a high temperature environment for a long time to the obtained cured product, and two or more glycidyl groups in the molecule. And a compound having a siloxane skeleton composed of siloxane bonds (Si—O—Si). Examples of the siloxane skeleton in the siloxane compound (S) include a cyclic siloxane skeleton and a polysiloxane skeleton (for example, a linear or branched silicone (linear or branched polysiloxane), a cage type or a ladder type). And polysilsesquioxane, etc.).

  As the siloxane compound (S), among them, a compound having a cyclic siloxane skeleton represented by the following formula (S-1) (hereinafter, referred to as the following formula (S-1) in that the cured product is excellent in heat-resistant transparency. (It may be referred to as “cyclic siloxane”).

式（Ｓ−１）中、Ｒ^Ｂ１、Ｒ^Ｂ２は、グリシジル基を含有する一価の基又はアルキル基を示す。但し、式（Ｓ−１）で表される化合物におけるｎ個のＲ^Ｂ１及びｎ個のＲ^Ｂ２のうち、少なくとも２個はグリシジル基を含有する一価の基である。また、式（Ｓ−１）中のｎは３以上の整数を示す。尚、式（Ｓ−１）で表される化合物におけるＲ^Ｂ１、Ｒ^Ｂ２は同一であってもよいし、異なっていてもよい。また、複数のＲ^Ｂ１は同一であってもよいし、異なっていてもよい。複数のＲ^Ｂ２も同一であってもよいし、異なっていてもよい。

In formula (S-1), R ^B1 and R ^B2 represent a monovalent group or an alkyl group containing a glycidyl group. However, at least two of n R ^B1 and n R ^{B2 in} the compound represented by Formula (S-1) are monovalent groups containing a glycidyl group. N in the formula (S-1) represents an integer of 3 or more. In addition, R ^B1 and R ^B2 in the compound represented by the formula (S-1) may be the same or different. Moreover, several R ^<B1> may be the same and may differ. The plurality of R ^B2 may be the same or different.

The monovalent group containing the glycidyl group is preferably a glycidyl ether group represented by -D-O-R ^B3 [D represents an alkylene group, and R ^B3 represents a glycidyl group]. Examples of D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. be able to.

  Examples of the alkyl group include linear chains having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. And a branched alkyl group.

  N in the formula (S-1) represents an integer of 3 or more, and among these, an integer of 3 to 6 is preferable from the viewpoint of excellent curability of the colored photosensitive composition and heat resistance and mechanical strength of the cured product.

  The number of glycidyl groups in the molecule of the siloxane compound (S) is 2 or more, and 2 to 6 are preferable from the viewpoint of curability of the colored photosensitive composition, heat resistance of the cured product, and mechanical strength, and particularly preferable. 2-4.

  The epoxy equivalent (based on JlS K7236) of the siloxane compound (S) is preferably from 100 to 350, particularly preferably from 150 to 300, most preferably from the viewpoint of excellent curability of the colored photosensitive composition and heat-resistant transparency of the cured product. Is 200-270.

  In addition to the siloxane compound (S), the colored photosensitive composition of the present embodiment includes other siloxane compounds (for example, alicyclic epoxy group-containing cyclic siloxane, and alicyclic epoxy groups described in JP-A-2008-248169). Containing silicone resin, organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422, and the like.

  More specific examples of the siloxane compound (S) include cyclic siloxanes having two or more glycidyl groups in the molecule represented by the following formula. Examples of the siloxane compound (S) include trade names “X-40-2701”, “X-40-2728”, “X-40-2738”, “X-40-2740” (hereinafter, Shin-Etsu Chemical). Commercial products such as Kogyo Co., Ltd. can be used.

  In the colored photosensitive composition of the first aspect, the content of the compound (P) is preferably 5 to 70% by mass with respect to the entire colored photosensitive composition (excluding the solvent), More preferably, it is 10-60 mass%, and it is still more preferable that it is 15-55 mass%. When the content of the compound (P) is within the above range, the solvent resistance of the colored cured product to be formed tends to be good even when baking is performed at a low temperature.

[Photosensitive agent (A)]
The colored photosensitive composition according to the first aspect includes (A) at least one photosensitive agent selected from the group consisting of a sulfonium salt represented by the general formula (a1) and a photopolymerization initiator (hereinafter referred to as “photosensitive agent”). (A) "))].
[Sulphonium salt represented by general formula (a1) above]
The sulfonium salt represented by the general formula (a1) (hereinafter, also referred to as “sulfonium salt (Q)”) is bonded to the carbon atom to which A ¹ is bonded in the benzene ring in the general formula (a1). A methyl group is bonded to an ortho-position carbon atom. Since the sulfonium salt (Q) has a methyl group at the above-mentioned position, it is more prone to generate protons and has higher sensitivity to active energy rays such as ultraviolet rays as compared with conventional sulfonium salts.

In the general formula (a1), it is preferable that both R ¹ and R ² are groups represented by the general formula (a2). R ¹ and R ² may be the same or different from each other.
In the general formula (a1), when R ¹ and R ² are bonded to each other to form a ring together with the sulfur atom in the formula, the formed ring is a 3 to 10-membered ring including the sulfur atom. Is preferable, and a 5- to 7-membered ring is more preferable. The ring formed may be polycyclic and is preferably a condensed 5- to 7-membered ring.
In the general formula (a1), R ³ is preferably a group represented by the general formula (a3).
In the general formula (a1), A ¹ is preferably S or O, and more preferably S.

In the general formula (a2), R ⁴ may be an alkyl group which may be substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophenylcarbonyl group or an optionally substituted group. An amino group or a nitro group is preferable, and an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group that may be substituted with a halogen atom is more preferable.
In the above general formula (a2), m1 is the ring ^Z can be selected according to the ^first type, for example, an integer of 0 to 4, preferably an integer of 0 to 3, even more preferably 0-2 integer Good.

In the general formula (a3), R ⁵ represents an alkylene group; a hydroxyl group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or a group represented by the general formula (a5). The group represented by the general formula (a5) is more preferable.
In the general formula (a3), R ⁶ represents an alkyl group; a hydroxy group, an optionally substituted amino group, or an alkyl group substituted with a nitro group; or a group represented by the general formula (a6). The group represented by the general formula (a6) is more preferable.
In the general formula (a3), A ² is preferably S or O, and more preferably S.
In the general formula (a3), n1 is preferably 0.

In the general formula (a4), R ⁷ and R ⁸ are independently an alkylene group; an alkylene group that is substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or the general formula (a5) It is preferable that it is group represented by the said general formula (a5). R ⁷ and R ⁸ may be the same or different from each other.
In the general formula (a4), both R ⁹ and R ¹⁰ are preferably groups represented by the general formula (a2). R ⁹ and R ¹⁰ may be the same as or different from each other.
In the general formula (a4), when R ⁹ and R ¹⁰ are bonded to each other to form a ring together with the sulfur atom in the formula, the formed ring is a 3 to 10-membered ring including the sulfur atom. Is preferable, and a 5- to 7-membered ring is more preferable. The ring formed may be polycyclic and is preferably a condensed 5- to 7-membered ring.
In the general formula (a4), A ³ is preferably S or O, and more preferably S.
In the general formula (a4), n2 is preferably 0.

In the general formula (a5), R ¹¹ is preferably an alkyl group that may be substituted with a halogen atom, a hydroxy group, an amino group that may be substituted, or a nitro group, and is substituted with a halogen atom. More preferably, it may be an alkyl group.
In the general formula (a5), m @ 2, the ring ^Z can be selected according to the type of ^2, for example, an integer of 0 to 4, preferably an integer of 0 to 3, even more preferably 0-2 integer Good.

In the general formula (a6), R ¹² may be an alkyl group, hydroxy group, alkylcarbonyl group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, or optionally substituted with a halogen atom. An amino group or a nitro group is preferable, and an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group that may be substituted with a halogen atom is more preferable.
In the general formula (a6), m3 is ring ^Z can be selected according to the ^three types, e.g., an integer of 0 to 4, preferably an integer of 0 to 3, even more preferably 0-2 integer Good.

In the general formula (a1), X ⁻ corresponds to an acid (HX) generated by irradiating the sulfonium salt (Q) with active energy (heat, visible light, ultraviolet light, electron beam, X-ray, etc.). It is a monovalent anion. When the sulfonium salt (Q) is used as an acid generator, preferred examples of X ⁻ include monovalent polyatomic anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY ₄₋ An anion represented by _c ⁻ , R ^x1 _c GaY _4-c ⁻ , R ^x2 SO ₃ ⁻ , (R ^x2 SO ₂ ) ₃ C ⁻ , or (R ^x2 SO ₂ ) ₂ N ⁻ is more preferable. X ⁻ may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.

M represents a phosphorus atom, a boron atom, or an antimony atom.
Y represents a halogen atom (a fluorine atom is preferred).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and cyclo And alkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like. The ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%. When the ratio of substitution by fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt (Q) is further improved. As particularly preferred Rf, CF ₃ −, CF ₃ CF ₂ ⁻ , (CF ₃ ) ₂ CF ⁻ , CF ₃ CF ₂ CF ₂ ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ ⁻ , (CF ₃ ) ₂ CFCF ₂ ⁻ _{, CF 3 CF 2 (CF 3} ) CF - and _{(CF 3) 3} C ^- and the like. The b Rf's are independent of each other, and therefore may be the same as or different from each other.

  P represents a phosphorus atom and F represents a fluorine atom.

R ^x1 represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group. Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom. Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable. The c R ^x1 are independent of each other, and therefore may be the same as or different from each other.

  B represents a boron atom, and Ga represents a gallium atom.

R ^x2 represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the fluoroalkyl group are linear or branched. The alkyl group, the fluoroalkyl group, or the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group, an optionally substituted amino group (for example, those exemplified in the following description of the general formulas (a2) to (a6)), a nitro group, and the like. Can be mentioned.
Further, the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. In particular, the carbon chain in the alkyl group or fluoroalkyl group represented by R ^x2 is a divalent functional group (eg, ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide). A bond, a sulfonylimide bond, a urethane bond, etc.).
When the alkyl group, fluoroalkyl group or aryl group represented by R ^x2 has the above substituent, heteroatom, or functional group, the number of the substituent, heteroatom, or functional group may be one. Two or more may be sufficient.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.
a represents an integer of 4 to 6.
b is preferably an integer of 1 to 5, more preferably an integer of 2 to 4, particularly preferably 2 or 3.
c is preferably an integer of 1 to 4, more preferably 4.

Examples of the anion represented by MY _a ⁻ include an anion represented by SbF ₆ ⁻ , PF ₆ ^— or BF ₄ ^— .

Examples of the anion represented by (Rf) _b PF _6-b ^— include (CF ₃ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ PF _4. ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ^— or (CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ^— Anions and the like. Among these, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ CF) ₂ An anion represented by PF ₄ ⁻ , ((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ^— or ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ^— is preferable.

The anion represented by R ^x1 _c BY _4-c ^— is preferably R ^x1 _c BY _4-c ^—.
(In the formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms are substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.)
For example, (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF _{^{2 -, C 6 F 5 BF}} 3 - or _{(C 6 H 3 F 2)} 4 B - anion, and the like represented. Of _{these, (C 6 F 5) 4} B - , or _{((CF 3) 2 C 6} H 3) 4 B - anion represented by are preferred.

Examples of the anion represented by R ^x1 _c GaY _4-c ^— include (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , and (CF ₃ C ₆ H ₄ ) _4. Examples include an anion represented by Ga ⁻ , (C ₆ F ₅ ) ₂ GaF ₂ ⁻ , C ₆ F ₅ GaF ₃ ^— or (C ₆ H ₃ F ₂ ) ₄ Ga ⁻ . Of _{these, (C 6 F 5) 4} Ga - or _{((CF 3) 2 C 6} H 3) 4 Ga - anion represented by are preferred.

^{Examples of the} anion represented by R ^x2 SO ₃ ^— include a trifluoromethanesulfonic acid anion, a pentafluoroethanesulfonic acid anion, a heptafluoropropanesulfonic acid anion, a nonafluorobutanesulfonic acid anion, a pentafluorophenylsulfonic acid anion, and p-toluene. Examples include a sulfonate anion, a benzenesulfonate anion, a camphorsulfonate anion, a methanesulfonate anion, an ethanesulfonate anion, a propanesulfonate anion, and a butanesulfonate anion. Of these, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion or p-toluenesulfonate anion are preferred.

The anion represented ^{_{by, (CF 3 SO 2) 3}} C - - (R x2 SO 2) 3 C, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C - or _{(C 4 F 9 SO 2)} 3 C - anion such as represented and the like.

The anion represented ^{_{by, (CF 3 SO 2) 2}} N - - (R x2 SO 2) 2 N, (C 2 F 5 SO 2) 2 N -, (C 3 F 7 SO 2) 2 N - or _{(C 4 F 9 SO 2)} 2 N - anion, and the like represented.

As monovalent polyatomic anions, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ , R ^x2 SO ₃ ⁻ , (R ^x2 SO _{2) 3} C ^- or ^{_{(R x2 SO 2) 2 N}} - besides the anion represented by the perhalogenated acid ion _{^(ClO 4} ^-, BrO 4 -, etc.), halogenated sulfonic acid ion ^_(FSO 3 -, ClSO ₃ ^- and the like), sulfate ion ^{_{(CH 3 SO 4 -, CF}} 3 SO 4 -, HSO 4 - , etc.), carbonate ions ^_(HCO 3 -, _CH 3 CO ₃ ^-, etc.), aluminate ions (AlCl ₄ ^-, AlF ₄ ^-, etc.), hexafluoro bismuthate ions (BiF ₆ ^-), carboxylate ion ^{_{(CH 3 COO -, CF 3}} COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 ^{_{F 5 COO -, CF 3 C}} 6 H 4 COO - , etc.), an aryl boronic acid ions ^{_{(B (C 6 H 5)}} 4 -, CH 3 CH 2 CH 2 CH 2 B (C 6 H 5) 3 - , etc.), Thiocyanate ion (SCN ⁻ ), nitrate ion (NO ₃ ⁻ ) and the like can be used.

Among these X ⁻ , in terms of cationic polymerization performance, MY _a ⁻ , (Rf) _b PF _6-b ⁻ , R ^x1 _c BY _4-c ⁻ , R ^x1 _c GaY _4-c ⁻ and (R ^x2 SO _{2) 3} C ^- anion is preferably represented _{^{by, SbF 6 -, PF 6 -}} , (CF 3 CF 2) 3 PF 3 -, (C 6 F 5) 4 B -, ((CF 3) 2 C 6 H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ are more preferable, and R ^x1 _c BY _{4 -c} ^- it is more preferable.

In the general formulas (a2), (a5), and (a6), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C _8-20 condensed bicyclic hydrocarbon ring such as naphthalene ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (for example, anthracene ring, phenanthrene ring, etc.) Condensed 2- to 4-cyclic aromatic hydrocarbon rings] and the like. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

  In the general formulas (a1) to (a6), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formulas (a1) to (a6), as the alkyl group, a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n -Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, isooctadecyl and the like), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl and the like) and the like. In particular, in the general formulas (a1), (a2), and (a4) to (a6), the alkyl group which may be substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. To do. Examples of the alkyl group substituted with a halogen atom include groups in which at least one hydrogen atom in the above linear alkyl group, branched alkyl group, or cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, trimethyl). Fluoromethyl and the like). Of the alkyl groups that may be substituted with a halogen atom, R ¹ , R ² , R ⁹ , or R ¹⁰ is particularly preferably a trifluoromethyl group, and R ⁴ , R ⁶ , R ¹¹ , or R ¹² Is particularly preferably a methyl group.

  In the general formulas (a2) to (a6), as the alkoxy group, a linear or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert -Butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy and the like).

  In the general formulas (a2) to (a6), as the alkyl group in the alkylcarbonyl group, the above-described linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or the number of carbon atoms Examples of the alkylcarbonyl group include linear, branched or cyclic alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl). 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, cyclopentanoyl group, cyclohexanoyl group and the like.

  In the general formulas (a3) to (a6), examples of the arylcarbonyl group include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

  In the above general formulas (a2) to (a6), as the alkoxycarbonyl group, a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, Isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.).

  In the general formulas (a3) to (a6), examples of the aryloxycarbonyl group include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

  In the general formulas (a3) to (a6), examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthoxythiocarbonyl).

  In the general formulas (a2) to (a6), as the acyloxy group, a linear or branched acyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, Isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy and the like).

  In the general formulas (a3) to (a6), as the arylthio group, an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenyl) Thio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2- Hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) Phenoxy] phenylthio, 4- [4- ( Phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl 2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p -Isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like.

  In the general formulas (a2) to (a6), as the alkylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio).

  In the general formulas (a3) to (a6), examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, and naphthyl).

  In the above general formula (a2), the heterocyclic aliphatic hydrocarbon group is a heterocyclic hydrocarbon group having 2 to 20 carbon atoms (preferably 4 to 20) (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl, Tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.).

  In the general formulas (a3) to (a6), as the heterocyclic hydrocarbon group, a heterocyclic hydrocarbon group having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, Pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromyl Thioxanthonyl, dibenzofuranyl and the like).

  In the general formulas (a3) to (a6), examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

  In the general formulas (a2) to (a6), as the alkylsulfinyl group, a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl) Sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, isooctadecylsulfinyl and the like.

  In the general formulas (a3) to (a6), examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

  In the general formulas (a2) to (a6), as the alkylsulfonyl group, a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutyl) Sulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, octadecylsulfonyl, etc.).

  In the general formulas (a3) to (a6), examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl).

In the above general formulas (a2) to (a6), as the hydroxy (poly) alkyleneoxy group, HO (AO) _q- (wherein AO independently represents an ethyleneoxy group and / or a propyleneoxy group, And a hydroxy (poly) alkyleneoxy group represented by 1 to 5).

In the above general formulas (a2) to (a6), the amino group which may be substituted includes an amino group (—NH ₂ ) and a substituted amino group having 1 to 15 carbon atoms (methylamino, dimethylamino, ethylamino, Methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, Methylphenylamino, ethylphenylamino, n-propylphenylamino, isopropylphenylamino, etc.).

  In the general formulas (a3) and (a4), the alkylene group may be a linear or branched alkylene group having 1 to 18 carbon atoms (methylene group, 1,2-ethylene group, 1,1-ethylene group, propane). -1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3- Diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane- 1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 2-ethylhexane-1,6-diyl group, nonane-1, 9-diyl group, decane-1,10-diyl group, un Can-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, and hexadecane-1, 16-diyl group, etc.).

The sulfonium salt (Q) can be synthesized, for example, according to the following scheme. Specifically, 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) is reacted with a compound represented by the following formula (b2) in the presence of a base such as potassium hydroxide. Thus, a nitro compound represented by the following formula (b3) is obtained, and then reduction is performed in the presence of reduced iron to obtain an amine compound represented by the following formula (b4). A diazo compound is obtained by reacting this amine compound with MaNO ₂ (wherein Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom) represented by a nitrite (for example, sodium nitrite). Next, a cuprous halide represented by this diazo compound and CuX ′ (wherein X ′ represents a halogen atom such as a bromine atom, the same shall apply hereinafter) and a hydrogen halide represented by HX ′. Mixing is allowed to proceed to obtain a halide represented by the following formula (b5). A Grignard reagent is prepared from this halide and magnesium, and then this Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane to represent the following formula (b7). Can be obtained. Further, this sulfonium salt is converted into Mb ⁺ X ″ ⁻ (wherein Mb ⁺ represents a metal cation, for example, an alkali metal cation such as potassium ion, and X ″ ⁻ represents a monovalent anion represented by X ⁻ (wherein The sulfonium salt represented by the following formula (b8) can be obtained by performing salt exchange by reacting with the salt represented by the formula (b8). In the following formulas (b2) to (b8), R ^{1 to} R ³ and A ¹ are the same as those in the general formula (a1).

<Scheme>

Specific examples of the cation moiety of the sulfonium salt (Q) represented by the general formula (a1) include the following. Specific examples of the anion moiety of the sulfonium salt (Q) represented by the above general formula (a1) is the X ^- like those described for, it can be mentioned those known in the art. The sulfonium salt (Q) represented by the above general formula (a1) can be synthesized according to the above scheme, and the cation moiety can be combined with the desired anion moiety by further salt exchange if necessary. R ^x1 _c BY _4-c ⁻ (wherein R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents 1 to 4) The combination with the anion represented by this is preferable.
The

  The sulfonium salt (Q) may be previously dissolved in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in the cationic polymerizable compound.

Such solvents include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ- Butyrolactone, δ-valerolactone, ε-caprolactone, etc.); ether (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.); and Ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether) Acetic acid ester and diethylene glycol monobutyl ether acetic acid ester), and the like.
In addition, a conventionally known ketone solvent, alcohol solvent, amide solvent, or hydrocarbon solvent may be used. Further, a solvent known as a protic solvent and / or a basic solvent may be used.
Examples of protic solvents include alcohols such as monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, diethylene glycol monomethyl ether, and polyhydric alcohols such as ethylene glycol and glycerin; acetic acid, formic acid, (meth) Carboxylic acids such as acrylic acid; Amines such as ethylenediamine and diethylamine; Amides such as formamide and N, N-dimethylformamide; Phenols such as phenol and p-butylphenol; Acetylacetone and diethyl malonate Examples include active methylene compounds.
Examples of the basic solvent include, in addition to the examples of the above amines and the above nitrogen-containing amides, pyridine, triethylamine, N, N-dimethylacetamide, hexamethylphosphoric triamide, 1,3-dimethyl-2- Examples include imidazolidinone, N, N, N ′, N′-tetramethylurea, N, N, 2-trimethylpropionamide and the like.

(Combination onium salt)
The colored photosensitive composition according to the first aspect includes at least one photosensitive agent (A) selected from the group consisting of the sulfonium salt (Q) and a photopolymerization initiator described later, and other than the sulfonium salt (Q). A conventional onium salt (also referred to as a combined onium salt) may be contained.
Examples of the onium salt include an onium salt composed of a monovalent anion represented by X ⁻ in the formula (a1) and an onium ion different from a cation other than X ⁻ in the formula (a1). And a sulfonium salt (also referred to herein as “sulfonium salt (Q ′)”) is preferable. As the monovalent anion represented by X ⁻ , the above-described R ^x1 _c BY _4-c ^— is preferable.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ａ^１、Ｒ^ｘ１、Ｙ及びｃは上述のとおり。） Examples of the sulfonium salt (Q ′) having a monovalent anion represented by R ^x1 _c BY _4-c ^— include a sulfonium salt represented by the following formula (a1 ′).

(Wherein R ¹ , R ² , R ³ , A ¹ , R ^x1 , Y and c are as described above.)

Specific examples of the cation moiety of the sulfonium salt (Q ′) represented by the above formula (a1 ′) include the following.

The sulfonium salt (Q ′) is also represented by the above formula (a1) (wherein R ¹ and R ² independently represent a group represented by the following formula (a2 ′)). A sulfonium salt is mentioned.

（式中、環Ｚ^１及びｍ１は上述のとおりであり、Ｒ^４’はアリール基を示す。）

(In the formula, rings Z ¹ and m 1 are as described above, and R ^{4 ′} represents an aryl group.)

Specific examples of the cation moiety of the sulfonium salt (Q ′) include the following.

Specific examples of the cation moiety of the sulfonium salt (Q ′) include the following.

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

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbazol-3-yl ) [4- (2-Methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamido Benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2 -Ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoy Dazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p ′ -Bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopro Offenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) ) Pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis ( Lichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

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

（Ｒ^ｄ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ｎ１は０〜４の整数であり、ｎ２は０又は１であり、Ｒ^ｄ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、Ｒ^ｄ３は、水素原子又は炭素原子数１〜６のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (d1).

(R ^d1 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, n1 is an integer of 0 to 4, and n2 is 0 or 1. R ^d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ^d3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (d1), R ^d1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ^d1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Examples include an amino group substituted with an mino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 to 4, R ^d1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^d1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^d1 is an alkyl group, it may be linear or branched. Specific examples when R ^d1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When Rd1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^d1 is an alkoxy group, it may be linear or branched. Specific examples when R ^d1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^d1 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^d1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples in the case where R ^d1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^d1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like.

When R ^d1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples in the case where R ^d1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^d1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^d1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples in the case where R ^d1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group , Isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group and the like.

When R ^d1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Further, when R ^d1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples when Rd1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ^d1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^d1 is a phenylalkyl group or a naphthylalkyl group, R ^d1 may further have a substituent on the phenyl group or naphthyl group.

When R ^d1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles are fused with each other or with such a monocycle and a benzene ring. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^d1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^d1 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. A saturated aliphatic acyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ^d1 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl. Amino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples thereof include a noylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d1 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^d1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^d1 , an alkyl group having 1 to 6 carbon atoms, 1 to 1 carbon atoms, because it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound. A group selected from the group consisting of 6 alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferred, alkyls having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.

Position R ^d1 is bonded to the phenyl group, the phenyl group R ^d1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R ^d2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^d2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms. -10 cycloalkyl group, C3-C10 cycloalkoxy group, C2-C20 saturated aliphatic acyl group, C2-C20 alkoxycarbonyl group, C2-C20 saturated Aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Naphthyl A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have a group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1 or 2 organic groups Examples include an amino group substituted with a group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^d2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a substituent. A phenoxycarbonyl group which may have, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent; Heterogeneity And a krylcarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. With respect to an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups, The same as R ^d1 .

Examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or the carbazolyl group in R ^d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; Benzoyl group; benzoyl group; benzoyl substituted by a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Examples include a holin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^d2 , a group represented by the following formula (d2) or (d3) is preferable, and a group represented by the following formula (d2) is more preferable, from the viewpoint of easily obtaining a photopolymerization initiator having excellent sensitivity. A group represented by the following formula (d2) in which A is S is particularly preferable.

（Ｒ^ｄ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０〜４の整数である。）

(R ^d4 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A is S or O, and n3 is an integer of 0 to 4. is there.)

（Ｒ^ｄ５及びＲ^ｄ６は、それぞれ、１価の有機基である。）

(R ^d5 and R ^d6 are each a monovalent organic group.)

When R ^d4 in the formula (d2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. In the formula (d2), when R ^d4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic group having 2 to 7 carbon atoms. An acyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms; A benzoyl group substituted by a group selected from the group consisting of a -1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having 1 to 6 alkyl groups; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group.

In R ^d4 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In formula (d2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^d4, relative bond which the phenyl group R ^d4 are attached is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

R ^d5 in formula (d3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferred examples of R ^d5 include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkoxycarbonyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, carbon atoms which may have a substituent 7 ~ 20 phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^d5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^d6 in formula (d3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R ^d6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. The heterocyclyl group which may be sufficient is mentioned. Among these groups, R ^d6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. 6 alkoxy groups, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl having 1 to 6 carbon atoms And a monoalkylamino group having a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 further have a substituent, the number of substituents is not limited as long as the object of the present invention is not impaired, 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in the formula (d1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^d3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

When p is 0, the oxime ester compound represented by the formula (d1) can be synthesized according to the following scheme 1, for example. Specifically, an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (d1-2), and the following formula: A ketone compound represented by (d1-3) is obtained, and the resulting ketone compound (d1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (d1-4), and then the formula The hydroxy group in the oxime compound of (d1-4) can be acylated to obtain an oxime ester compound represented by the following formula (d1-7). Examples of the acylating agent include acid anhydrides ((R ^d3 CO) ₂ O) represented by the following formula (d1-5), or acid halides (R ^d3 COHal, Hal represented by the following formula (d1-6) Is preferably halogen.). In the following formula (d1-2), Hal is halogen, and in the following formulas (d1-1), (d1-2), (d1-3), (d1-4), and (d1-7) , R ^d1 , R ^d2 , R ^d3 , and n1 are the same as those in the formula (d1).

<Scheme 1>

When n2 is 1, the oxime ester compound represented by the formula (d1) can be synthesized according to the following scheme 2, for example. Specifically, a ketone compound represented by the following formula (d2-1) is added to a nitrite ester (RONO, R is represented by 1 to 6 carbon atoms) represented by the following formula (d2-2) in the presence of hydrochloric acid. To obtain a ketoxime compound represented by the following formula (d2-3), and then acylate the hydroxy group in the ketoxime compound represented by the following formula (d2-3). An oxime ester compound represented by the following formula (d2-6) can be obtained. As an acylating agent, an acid anhydride (R ^d3 COHal, Hal represented by the following formula (d2-5) or an acid anhydride (R ^d3 CO) ₂ O represented by the following formula (d2-4) Is preferably halogen.). In the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and (d2-6), R ^d1 , R ^d2 , R ^d3 , and n1 are formulas Same as (d1).

<Scheme 2>

Further, the oxime ester compound represented by the formula (d1) may, n2 is ^1, and ^{R d1} is a methyl ^group, with respect to methyl groups attached to the benzene ring ^{to which R d1} are ^{attached, R d1} para In the case of bonding to a position, for example, a compound represented by the following formula (d2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1. In the following formula (d2-7), R ^d2 is the same as in formula (d1).

Among the oxime ester compounds represented by the formula (d1), the following PI-1 to PI-42 are particularly preferable compounds.

  Moreover, the oxime ester compound represented by a following formula (d4) is also preferable as a photoinitiator.

（Ｒ^ｄ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｄ８及びＲ^ｄ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｄ８とＲ^ｄ９とは相互に結合して環を形成してもよく、Ｒ^ｄ１０は１価の有機基であり、Ｒ^ｄ１１は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０〜４の整数であり、ｎ５は０又は１である。）

(R ^d7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^d8 and R ^d9 are each a chain alkyl group which may have a substituent, or a cyclic organic which may have a substituent. R ^d8 and R ^d9 may be bonded to each other to form a ring, R ^d10 is a monovalent organic group, R ^d11 has a hydrogen atom and a substituent. An alkyl group having 1 to 11 carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1.)

  For this reason, the compound represented by the following formula (d5) is suitable as the oxime compound for producing the oxime ester compound of the formula (d4).

（Ｒ^ｄ７、Ｒ^ｄ８、Ｒ^ｄ９、Ｒ^ｄ１０、ｎ４、及びｎ５は、式（ｄ４）と同様である。）

(R ^d7 , R ^d8 , R ^d9 , R ^d10 , n4, and n5 are the same as in formula (d4).)

In formulas (d4) and (d5), R ^d7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^d7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _n5 — on the fluorene ring in the formula (d4). In formula (d4), the bonding position of R ^{d7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (d4) has one or more Rd7, from such that the synthesis of compounds of formula (d4) is easy, one or more one is in the fluorene ring of R ^d7 It is preferable to bond to the 2-position. If R ^d7 is a plurality, the plurality of R ^d7 may be different even in the same.

When R ^d7 is an organic group, R ^d7 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferred examples when R ^d7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, Examples include a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^d7 is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ^d7 is an alkyl group, it may be linear or branched. Specific examples when R ^d7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^d7 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, and more preferably 1-6. Further, when R ^d7 is an alkoxy group, it may be linear or branched. Specific examples when R ^d7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^d7 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^d7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples in the case where Rd7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^d7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^d7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ^d7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^d7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^d7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ^d7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^d7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, and more preferably 7-10. Further, when R ^d7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11-20, and more preferably 11-14. Specific examples when R ^d7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ^d7 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^d7 is a phenylalkyl group or a naphthylalkyl group, R ^d7 may further have a substituent on the phenyl group or naphthyl group.

When R ^d7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, or O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ^d7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^d7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^d7 is a heterocyclyl group.

When R ^d7 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ^d7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d7 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^d7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^d7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^d7 is preferably a nitro group or a group represented by R ^d12 —CO— because the sensitivity tends to be improved. R ^d12 is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Examples of a group suitable as R ^d12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R ^d12 is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.
Further, it is preferable that R ^d7 is a hydrogen atom because transparency tends to be good. When R ^d7 is a hydrogen atom and R ^d10 is a group represented by the following formula (d4b), the transparency tends to be better.

In formula (d4), R ^d8 and R ^d9 each represent a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ^d8 and R ^d9 may be bonded to each other to form a ring. Among these groups, R ^d8 and R ^d9 are preferably chain alkyl groups which may have a substituent. When R ^d8 and R ^d9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^d8 and R ^d9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Specific examples when R ^d8 and R ^d9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Group, isononyl group, n-decyl group, isodecyl group and the like. When R ^d8 and R ^d9 are alkyl groups, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d8 and R ^d9 are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples in the case where R ^d7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples in the case where R ^d7 is a heterocyclyl group. When R ^d7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

When R ^d8 and R ^d9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^d8 and R ^d9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^d8 and R ^d9 are chain alkyl groups.

When R ^d8 and R ^d9 are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? A group formed by condensation of a plurality of benzene rings is preferred. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^d8 and R ^d9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^d8 and R ^d9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done.

R ^d8 and R ^d9 may be bonded to each other to form a ring. The group formed by the ring formed by R ^d8 and R ^d9 is preferably a cycloalkylidene group. When R ^d8 and R ^d9 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, and more preferably a 5-membered ring.

When the group formed by combining R ^d8 and R ^d9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

Examples of the preferable group among R ^d8 and R ^d9 described above include a group represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of an alkoxy group, 1-6 are more preferable. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^d8 and R ^d9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that R ^d8 and R ^d9 have as a substituent.

Preferred examples of R ^d8 and R ^d9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n − Cyanoalkyl groups such as an nyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopent Cycloalkylalkyl groups such as ru-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n -Pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxy Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ^d8 and R ^d9 , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta A fluoro-n-pentyl group;

Examples of suitable organic groups for R ^d10 are the same as R ^d7 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, substituent a good heterocyclylcarbonyl group optionally having 1 or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^d7 . R ^d10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ^d7 may have.

Among organic groups, as R ^d10 , an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthio which may have a substituent on an aromatic ring Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

Further, as R ^d10 , a group represented by —A ³ —CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

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

Preferable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferred examples of the group represented by —A ³ —CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｄ４ａ）及び（ｄ４ｂ）中、Ｒ^ｄ１３及びＲ^ｄ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｄ１３及びＲ^ｄ１４がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｄ１３とＲ^ｄ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｄ１５は有機基である。） ^Having described ^{R d10,} as the ^{R d10,} preferably a group represented by the following formula (d4a) or (D4B).

(In the formulas (d4a) and (d4b), R ^d13 and R ^d14 are each an organic group, n6 is an integer of 0 to 4, and R ^d13 and R ^d14 are present at adjacent positions on the benzene ring. , R ^d13 and R ^d14 may be bonded to each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, and n9 is an integer of 0 to (n8 + 3). And R ^d15 is an organic group.)

Examples of the organic group for R ^d13 and R ^{d14 in} formula (d4a) are the same as those for R ^d7 . R ^d13 is preferably an alkyl group or a phenyl group. When R ^d13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^d13 is most preferably a methyl group. When R ^d13 and R ^d14 are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (d4a) in which R ^d13 and R ^d14 form a ring include a naphthalen-1-yl group, 1,2,3,4- And tetrahydronaphthalen-5-yl group. In the above general formula (d4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the general formula (d4b), R ^d15 represents an organic group. ^Examples of the organic group include the same groups as those described for R ^d7 . Of the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. R ^d15 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and among these, a methyl group is more preferable.

  In said general formula (d4b), n8 is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said general formula (d4b), n9 is 0- (n8 + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said general formula (d4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In formula (d4), R ^d11 represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be contained when R ^d11 is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that R ^d7 may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (d4), R ^d11 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, or the like. Among these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (d4) represents an oxime group (> C═N—OH) contained in the compound represented by the above formula (d5) by> C═N—O—COR ^d11. It is produced by a method including a step of converting to an oxime ester group. R ^d11 is the same as ^{R d11} in formula (d4).

The conversion of the oxime group (> C═N—OH) to the oxime ester group represented by> C═N—O—COR ^d11 involves the conversion of the compound represented by the above formula (d5), It is performed by reacting.
The acylating agent to give the acyl group represented by -COR ^{d11, (R d11} _CO) or an acid anhydride represented by ₂ ^O, R d11 COHal (Hal is a halogen atom) include acid halide represented by It is done.

When n5 is 0, the compound represented by the general formula (d4) can be synthesized according to the following scheme 3, for example. In Scheme 3, a fluorene derivative represented by the following formula (d3-1) is used as a raw material. When R ^d7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (d3-1) is converted into a fluorene derivative substituted at the 9-position with R ^d8 and R ^d9 by a known method, It can be obtained by introducing a substituent R ^d7 . The fluorene derivative substituted at the 9-position with R ^d8 and R ^d9 is, for example, an alkali metal hydroxide when R ^d8 and R ^d9 are alkyl groups, as described in JP-A-06-234668. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

An acyl group represented by -CO-R ^d10 is introduced into the fluorene derivative represented by the formula (d3-1) by Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (d3-3) can get. The acylating agent for introducing an acyl group represented by —CO—R ^d10 may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by the formula (d3-2) is preferable. In formula (d3-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by changing the Friedel-Crafts reaction conditions as appropriate, or by performing protection and deprotection at other positions where acylation is performed. it can.

Next, the group represented by —CO—R ^d10 in the fluorene derivative represented by the formula (d3-3) to be obtained is converted into a group represented by —C (═N—OH) —R ^d10 , An oxime compound represented by the formula (d3-4) is obtained. The method for converting the group represented by —CO—R ^d10 to the group represented by —C (═N—OH) —R ^d10 is not particularly limited, but oximation with hydroxylamine is preferred. An oxime compound of the formula (d3-4) and an acid anhydride ((R ^d11 CO) ₂ O) represented by the following formula (d3-5) or an acid halide represented by the following formula (d3-6) ( A compound represented by the following formula (d3-7) can be obtained by reacting R ^d11 COHal, Hal is a halogen atom.

In formulas (d3-1), (d3-2), (d3-3), (d3-4), (d3-5), (d3-6), and (d3-7), R ^d7 , R ^d8 , R ^d9 , R ^d10 , and R ^d11 are the same as those in formula (d4).

In scheme 3, R ^d10 contained in each of formula (d3-2), formula (d3-3), and formula (d3-4) may be the same or different. That is, R ^d10 in formula (d3-2), formula (d3-3), and formula (d3-4) may be chemically modified in the synthesis process represented as Scheme 3. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^d10 may undergo is not limited thereto.

<Scheme 3>

When n5 is 1, the compound represented by the formula (d4) can be synthesized according to the following scheme 4, for example. In Scheme 4, a fluorene derivative represented by the following formula (d4-1) is used as a raw material. The fluorene derivative represented by the formula (d4-1) is converted into a compound represented by the formula (d3-1) by the same method as in the scheme 3 and represented by —CO—CH ₂ —R ^d10 by Friedel-Crafts reaction. It is obtained by introducing an acyl group. The acylating agent of formula (d3-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R d10}} . Subsequently, the methylene group present between R ^d10 and the carbonyl group in the compound represented by the formula (d4-1) is oximed to obtain a ketoxime compound represented by the following formula (d4-3). The method for oximation of the methylene group is not particularly limited, but a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (d4-2) in the presence of hydrochloric acid. A reaction method is preferred. Next, a ketoxime compound represented by the following formula (d4-3) and an acid anhydride ((R ^d11 CO) ₂ O) represented by the following formula (d4-4) or the following formula (d4-5) A compound represented by the following formula (d4-6) can be obtained by reacting with an acid halide (R ^d11 COHal, Hal is a halogen atom). In the following formulas (d4-1), (d4-3), (d4-4), (d4-5), and (d4-6), R ^d7 , R ^d8 , R ^d9 , R ^d10 , and R ^d11 is the same as that of Formula (d4).
When n5 is 1, there exists a tendency which can reduce more the generation | occurrence | production of the foreign material in the pattern formed using the photosensitive resin composition containing the compound represented by Formula (d4).

In scheme 4, Rd10 contained in each of formula (d3-8), formula (d4-1), and formula (d4-3) may be the same or different. That is, Rd10 in formula (d3-8), formula (d4-1), and formula (d4-3) may undergo chemical modification in the synthesis process represented as Scheme 4. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^d10 may undergo is not limited thereto.

<Scheme 4>

Preferable specific examples of the compound represented by the formula (d4) include the following PI-43 to PI-82.

  The content of at least one photosensitizer (A) selected from the group consisting of the sulfonium salt represented by the general formula (a1) and the photopolymerization initiator is the entire colored photosensitive composition (excluding the solvent). ) It is preferable that it is 0.001-30 mass% with respect to mass, and it is more preferable that it is 0.01-20 mass%. By making content of a photoinitiator into said range, there exists a tendency for the solvent tolerance of the colored hardened | cured material obtained by low-temperature baking to become favorable.

  Moreover, you may combine a photoinitiator with a photoinitiator. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

[Colorant (B)]
The colored photosensitive composition of the first aspect contains a colorant (B).
Moreover, it can be set as the coloring photosensitive composition for color filter formation by making a coloring agent (B) into a chromatic coloring agent.
When the colorant (B) is a chromatic colorant, it is possible to obtain a display element capable of displaying a color image by configuring a color filter by combining several different hues selected from chromatic colors. .
When the colored photosensitive composition contains the aforementioned compound (P), the photosensitive agent (A), and the coloring agent (B) in combination, discoloration of the colored cured product during the formation of the colored cured product is suppressed, A colored cured product having a desired hue can be formed.

  Conventionally, examples of widely used color filters include RGB (red, green, blue) primary color filters and CMYG (cyan, magenta, yellow, green) complementary color filters.

The colorant (B) is preferably an organic pigment from the viewpoint of the light resistance and weather resistance of the color filter when a colored cured product is used as a color filter. The organic pigment is not particularly limited. For example, the organic pigment is a compound classified as “Pigment” in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color It is preferable to use an index (CI) number.
The colorant (B) may contain a small amount of an achromatic colorant such as black or white for the purpose of adjusting the hue.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37, Pigment Green 58, Pigment Green 59, Pigment Green 60;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  A dye may be used as the colorant (B). When a dye is used, it can be used alone, but is more preferably combined with a pigment. Examples of usable dyes include brilliant green, alizarin green, methyl green, fast green, brilliant blue, brilliant cresyl blue, patent blue, phenol blue, tetrabromophenol blue, bromophenol blue, methylene blue, and solvent blue 35. However, this is not a limitation.

  The colorant (B) may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Moreover, it can be set as the coloring photosensitive composition for black matrix formation by using a coloring agent (B) as a light-shielding agent.
When the colorant (B) is used as a light shielding agent, it is preferable to use a black pigment or a purple pigment as the light shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides and composite oxides. In addition, various pigments may be mentioned regardless of organic matter or inorganic matter such as metal sulfide, metal sulfate or metal carbonate. Among these, it is preferable to use carbon black having high light shielding properties.

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

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

  Among the carbon blacks that have been treated to introduce acidic groups as described above, the light-blocking cured film formed using the colored photosensitive composition has a low relative dielectric constant, so that the carboxylic acid group and the carboxylic acid group. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid group is preferable.

  The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods. 1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using sulfite, bisulfite, or the like. 2) A method of diazo coupling an organic compound having an amino group and an acidic group with carbon black. 3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method. 4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group. 5) A method of performing deprotection after performing a Friedel-Crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

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

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

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

  A perylene pigment is also preferable as the light-shielding agent. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (e-1), the perylene pigment represented by the following formula (e-2), and the following formula (e-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

式（ｅ−１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｅ３及びＲ^ｅ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^e3 and R ^e4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or Represents an acetyl group.

式（ｅ−２）中、Ｒ^ｅ５及びＲ^ｅ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In formula (e-2), R ^e5 and R ^e6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｅ−３）中、Ｒ^ｅ７及びＲ^ｅ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｅ７及びＲ^ｅ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. Good. When R ^e7 and R ^e8 are alkyl groups, the alkyl group may be linear or branched.

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

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

  The light-shielding agent may contain a dye having a hue such as red, blue, green, and yellow together with the black pigment and the purple pigment for the purpose of adjusting the color tone. The pigment of other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as the coloring matter of other hues of black pigments and purple pigments. The amount of the dye having a hue other than the black pigment or the purple pigment is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total mass of the light shielding agent.

  In order to uniformly disperse the colorant in the composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

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

  The amount of the colorant (B) used in the composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically based on the mass of the entire colored photosensitive composition (excluding the solvent). 5 to 70 mass% is preferable, 20 to 60 mass% is more preferable, and 25 to 50 mass% is still more preferable.

  In addition, it is preferable to add a coloring agent (B) to the photosensitive composition, after making it into the dispersion liquid disperse | distributed by the appropriate density | concentration using the dispersing agent. As the known dispersant, a polymer dispersant is preferable, and examples thereof include an acrylic copolymer dispersant, a polyurethane dispersant, a polyester dispersant, a polyethyleneimine dispersant, and a polyallylamine dispersant. Of these, polyurethane dispersants are preferred. When these polymer dispersants are used, the dispersibility and dispersion stability of the colorant (B) can be improved, and the hue, contrast ratio, and heat resistance can be improved.

[Other ingredients]
The colored photosensitive composition of the first aspect may further contain an alkali-soluble resin, or may further contain an alkali-soluble resin and a polyfunctional monomer.

[Alkali-soluble resin]
Examples of the alkali-soluble resin include conventionally known resins having an alkali-soluble group such as a carboxy group, a phenol hydroxyl group, or a sulfo group (—SO ₃ H). The skeleton of the resin having an alkali-soluble group is not particularly limited. For example, a resin having a cardo structure, a polyimide resin, an epoxy resin, a (meth) acrylic resin, a (hydroxy) styrene resin, or silicon such as polysiloxane or polysilane Containing resin and the like. The alkali-soluble resin preferably contains a resin selected from the group consisting of a resin having a cardo structure, a resin having a phenolic hydroxyl group, a polyimide resin, and an epoxy resin.

The alkali-soluble resin in the colored photosensitive composition of the first aspect is not particularly limited, and conventionally known alkali-soluble resins can be used. This alkali-soluble resin may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.
In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 2.38% by mass. When immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more.

  As the alkali-soluble resin having an ethylenically unsaturated group, for example, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

  Among these, a resin represented by the following formula (f-1) is preferable. The resin represented by the formula (f-1) itself is preferable in terms of high photocurability.

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

In the general formula (f-2), R ^f1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^f2 independently represents a hydrogen atom or a methyl group. , W ^f represents a single bond or a group represented by the following formula (f-3).

In the general formula (f-1), Y ^f represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

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

Moreover, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or a polybasic acid. (Meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine Epoxy resins, and epoxy resins such as dihydroxybenzene type epoxy resin, can also be used (meth) epoxy obtained by reacting acrylic acid (meth) acrylate resin.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate.

  On the other hand, as an alkali-soluble resin having no ethylenically unsaturated group, an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound are at least copolymerized. It is possible to use a resin obtained by the above process.

  Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylic acid epoxy alkyl esters such as (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 4-oxatetracyclo- [6.2.1.02,703,5] undecanyl (meth) acrylate Α-alkyl acrylate epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl; o-Vinylbenzylglycidyl ether, m-vinylbenzyl Glycidyl ether, glycidyl ethers such as p- vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulae.

In the above general formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or 1 to carbon atoms. 5 represents an alkyl group. R ^a4 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R ^a5 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, and more preferably 5 to 25% by mass. Moreover, it is preferable that the ratio of the structural unit derived from the said epoxy-group-containing unsaturated compound is 71-95 mass%, and it is more preferable that it is 75-90 mass%. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound is 1-25 mass%, It is more preferable that it is 3-20 mass%, It is 5-15 mass%. More preferably. By setting it as said range, the adhesiveness to the board | substrate of a coloring photosensitive composition and the intensity | strength after hardening of a coloring photosensitive composition can be improved, making alkali solubility of resin obtained moderate.

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

  When the alkali-soluble resin is contained, the content of the alkali-soluble resin is preferably 5 to 80% by mass with respect to the entire colored photosensitive composition of the first aspect (excluding the solvent), and 15 More preferably, it is -50 mass%, and it is still more preferable that it is 25-40 mass%. By setting it as said range, there exists a tendency for the developability balance to be easy to be taken, and there exists a tendency for the solvent tolerance of the colored hardened | cured material formed even if baking is low-temperature baking to become favorable.

[Polyfunctional monomer]
On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate), methylenebis (meth) acrylamide, (meth) acrylamide Examples thereof include polyfunctional monomers such as methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  Among these polyfunctional monomers, a trifunctional or higher polyfunctional monomer is preferable, and a hexafunctional or higher polyfunctional monomer is more preferable from the viewpoint of increasing the strength after curing of the colored photosensitive composition.

When the polyfunctional monomer is contained, the content of the polyfunctional monomer in the colored photosensitive composition is preferably 1 to 40% by mass with respect to the mass of the entire colored photosensitive composition (excluding the solvent), 3-20 mass% is more preferable, and 5-10 mass% is still more preferable. By setting the above range, the sensitivity, developability, and resolution tend to be easily balanced, and the solvent resistance of the colored cured product that is formed even when baking is performed at low temperature tends to be good. is there.
The colored photosensitive composition of the first aspect may or may not contain an alkali-soluble resin and a polyfunctional monomer, but when it is contained, the total content of the alkali-soluble resin and the polyfunctional monomer is: 1-50 mass% is preferable with respect to the whole coloring photosensitive composition (however, except a solvent), 3-40 mass% is more preferable, and 5-30 mass% is still more preferable. By setting the above range, the above tendency can be easily achieved.

[Organic solvent]
The colored photosensitive composition of the first aspect preferably contains an organic solvent for improving coatability and adjusting the viscosity.

  Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate (MA), 3-methyl-3-methoxybutyl acetate, 3-methyl Ru-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, butyric acid Other esters such as ethyl, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N, N-diethylacetamide, N , N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidino , Pyridine, and N, N, N ', N'- tetramethylurea (TMU), etc. The nitrogen-containing polar organic solvent; and the like. In addition, sulfonium salt (Q) may be mentioned the solvents mentioned for solubility in the cationically polymerizable compound.

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

  The content of the organic solvent is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. The viscosity of the colored photosensitive composition is preferably 0.005 to 0.5 Pa · s (5 to 500 cp), more preferably 0.01 to 0.05 Pa · s (10 to 50 cp), and 0 More preferably, it is 0.02 to 0.03 Pa · s (20 to 30 cp). Moreover, it is preferable that solid content concentration is 5-80 mass%, and it is more preferable that it is 10-40 mass%.

  The colored photosensitive composition according to the present invention may contain known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow regulators, light stabilizers, if necessary. Agents, antioxidants, adhesion-imparting agents, ion scavengers, anti-coloring agents, non-reactive resins and radical polymerizable compounds).

  The colored photosensitive composition according to the present invention is prepared by mixing all the above components with a stirrer. In addition, you may filter using a filter so that the prepared colored photosensitive composition may become uniform.

<Colored cured product>
The colored cured product according to the second aspect of the present invention is a colored cured product obtained by curing the colored photosensitive composition according to the first aspect described above. The colored cured product is preferably a colored cured film. The colored cured product according to the present invention is excellent in solvent resistance as described above.
Although there is no restriction | limiting in particular as a film thickness of the colored hardened | cured material which concerns on this invention, 0.5-10 micrometers is mentioned.
The colored cured product is suitable as, for example, a color filter or a black matrix.

<Method for producing colored cured product>
The method for producing a colored cured product according to the third aspect of the present invention includes:
Forming a coating film by applying the colored photosensitive composition of the first aspect described above onto a substrate;
A step of exposing the coating film, and a step of baking the exposed coating film.
Specifically, the colored photosensitive composition of the first aspect described above is applied to a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), slit coater, curtain flow coater. It coats on a substrate using a non-contact type coating device such as. Examples of the material for the substrate include glass, polyethylene terephthalate, acrylic resin, and polycarbonate.
Next, the coating film of the colored photosensitive resin composition is dried. Although a drying method is not specifically limited, For example, it vacuum-drys at room temperature using a vacuum dryer (VCD), Then, 50-110 degreeC with a hotplate, Preferably it is 60-180 degreeC at the temperature of 60-90 degreeC. The method (prebaking) which dries for 2 seconds is mentioned.

Subsequently, this coating film is exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask as necessary. Although the energy dose to be irradiated varies depending on the composition of the colored photosensitive composition, it is preferably, for example, 30 to 2000 mJ / cm ² .

  Next, the exposed coating film may be patterned into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Next, the pattern after development can be used for a range of less than 200 ° C., specifically about 80 to 160 ° C., a display element having low heat resistance, a substrate (a substrate of a colored cured product), and the like. 80-150 degreeC is preferable, More preferably, it is about 80-120 degreeC, More preferably, post-baking is performed at about 80-110 degreeC. At this time, it is preferable to expose the entire surface of the formed pattern.
The post-bake time is preferably 40 to 120 minutes.
As described above, a color filter or a black matrix having a predetermined pattern shape can be formed as necessary.

The method for producing a colored cured product according to the fourth aspect of the present invention includes a step of polymerizing and / or cross-linking the colored photosensitive composition according to the first aspect described above.
The colored photosensitive composition according to the first aspect described above can be cured by polymerization and / or crosslinking by heating or exposure. Examples of the heating or exposure include heat, visible light, ultraviolet rays, electron beams, and X-rays.

<Display element>
A display element according to the present invention includes the above-described color filter or black matrix. In order to manufacture this display element, first, the color filter or the black matrix is formed on one substrate, and then electrodes, spacers, and the like are sequentially formed. Then, an electrode or the like is formed on the other substrate, and both are bonded together to inject and seal a predetermined amount of liquid crystal.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
Using the following components, colored photosensitive compositions of Examples and Comparative Examples shown in Table 1 below were prepared. The unit of the numbers in Table 1 is mass%.

[Alkali-soluble resin]
Resin having a cardo structure (solid content 55%, solvent: 3-methoxybutyl acetate)

[Polyfunctional monomer]
Dipentaerythritol hexaacrylate (DPHA)

[Compound (P)]
The following compound (P1-1a) was used as the compound (P).

[Photoinitiator (A)]
The following compound (A1) was used as the photopolymerization initiator (A).

[Sulphonium salt (A)]
The following compound (Q1) was used as the sulfonium salt (A).

[Pigment dispersion]
As the colorant (B), a carbon dispersion containing carbon black (“CF black” (trade name: 25% solid content, solvent: 3-methoxybutyl acetate, manufactured by Mikuni Dye Co., Ltd.)) was used.

<Synthesis of the alkali-soluble resin>
A method for synthesizing the resin having the cardo structure is as follows.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (f-4) of colorless and transparent solid.

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

<Preparation of colored photosensitive composition>
Using each component and organic solvent (3-methoxybutyl acetate (MA), N, N, N ′, N′-tetramethylurea (TMU) and propylene glycol monomethyl ether acetate (PGMEA)) shown in Table 1 below. The colored photosensitive compositions of Examples and Comparative Examples shown in Table 1 below were prepared so that the solvent composition ratio of the final composition was MA / TMU / PGMEA = 5/25/70 (mass ratio). In addition, the solvent ratio is 80 mass% in the whole colored photosensitive composition.

<Solvent resistance test against PGMEA>
The colored photosensitive composition of each Example and Comparative Example is applied on a glass substrate (100 mm × 100 mm) using a spin coater and prebaked at 80 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. did. Next, the coating film was irradiated with ultraviolet rays (broadband light) using an ultraviolet irradiation device (manufactured by ORC). The exposure amount was 30 mJ / cm ² . The exposed coating film was post-baked at 100 ° C. for 60 minutes to form a solvent resistance test substrate.
The substrate for solvent resistance test was measured using a stylus type surface shape measuring instrument (product name: Dektak-3ST, manufactured by Veeco), and the substrate was measured for propylene glycol monomethyl ether acetate (at 25 ° C. for 100 seconds) The film was dipped in PGMEA and spin-dried. Further, dipping and spin-drying were repeated twice, and the film thickness of the substrate was measured again. (Film thickness after immersion in PGMEA / film thickness before immersion in PGMEA × 100) was evaluated as the remaining film ratio. The results are shown in Table 1 below.

As shown in Table 1 above, it can be seen that Comparative Example 1 containing no compound (P) has a residual film ratio of less than 5% and poor solvent resistance in the case of low temperature post-bake treatment.
On the other hand, it can be seen that Examples 1-5 all have a residual film ratio of 70% or more and excellent solvent resistance.
Moreover, from the results of Examples 3 to 5, it can be seen that it is more excellent in solvent resistance to reduce the total content of the alkali-soluble resin and the polyfunctional monomer and increase the content of the compound (P).

Claims (12)

(P) a cationically and / or acid-catalyzed polymerizable and / or crosslinkable compound;
(A) at least one photosensitizer selected from the group consisting of a sulfonium salt represented by the following general formula (a1) and a photopolymerization initiator;
(B) A colored photosensitive composition containing a colorant.

(In the above general formula, R ¹ and R ² independently represent an alkyl group optionally substituted with a halogen atom or a group represented by the following general formula (a2), and R ¹ and R ² are bonded to each other. A ring may be formed together with the sulfur atom in the formula, R ³ represents a group represented by the following general formula (a3) or a group represented by the following general formula (a4), A ¹ represents S, O or Se represents, and X ⁻ represents a monovalent anion, provided that R ¹ and R ² are not an alkyl group which may be substituted with a halogen atom at the same time.

(In the above general formula, ring Z ¹ represents an aromatic hydrocarbon ring, and R ⁴ represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, acyloxy group optionally substituted with a halogen atom, Alkylthio group, thienyl group, thienylcarbonyl group, furanyl group, furanylcarbonyl group, selenophenyl group, selenophenylcarbonyl group, heterocyclic aliphatic hydrocarbon group, alkylsulfinyl group, alkylsulfonyl group, hydroxy (poly) alkyleneoxy A group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m1 represents an integer of 0 or more.)

(In the above general formula, R ⁵ represents a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a complex, Cyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen optionally substituted alkylene group or the following general formula atom a group represented by (a5), R ⁶ is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxy carbonitrile Group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly ) alkyleneoxy group, substituted amino group, a cyano group, a nitro group, or a group represented by optionally substituted alkyl group or the following general formula with a halogen atom (a6), a ² represents a single A bond, S, O, a sulfinyl group, or a carbonyl group, and n1 represents 0 or 1.)

(In the above general formula, R ⁷ and R ⁸ are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group. Group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, amino group which may be substituted, cyano group , A nitro group, or an alkylene group optionally substituted with a halogen atom or a group represented by the following general formula (a5), wherein R ⁹ and R ¹⁰ are independently alkyl optionally substituted with a halogen atom A group represented by the above general formula (a2) R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with the sulfur atom in the formula, A ³ represents a single bond, S, O, a sulfinyl group, or a carbonyl group, and X ⁻ represents the above-mentioned And n2 represents 0 or 1, provided that R ⁹ and R ¹⁰ are not simultaneously an alkyl group which may be substituted with a halogen atom.

(In the above general formula, ring Z ² represents an aromatic hydrocarbon ring, and R ¹¹ is an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group optionally substituted with a halogen atom. , Aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, A hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m2 represents an integer of 0 or more.)

(In the above general formula, ring Z ³ represents an aromatic hydrocarbon ring, and R ¹² represents an alkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group optionally substituted with a halogen atom. , Aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, thienylcarbonyl group, furanylcarbonyl group, selenophenylcarbonyl group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl A group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy (poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, and m3 represents an integer of 0 or more. .)   The colored photosensitive composition of Claim 1 whose said compound (P) is an alicyclic epoxy compound. The sulfonium salt, wherein X ^- the monovalent anion represented by is a boron-containing anion represented by the following general formula, colored photosensitive composition according to claim 1 or 2.
R ^x1 _c BY _4-c ⁻
(In the above general formula, R ^x1 represents a phenyl group in which at least a part of hydrogen atoms is substituted with a halogen atom or an electron withdrawing group, Y represents a halogen atom, and c represents an integer of 1 to 4.)   The colored photosensitive composition of any one of Claims 1-3 whose said photoinitiator is an oxime ester compound. The colored photosensitive composition of Claim 4 whose said oxime ester compound is an oxime ester compound represented by the following general formula (d4).

(R ^d7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^d8 and R ^d9 are each a chain alkyl group which may have a substituent, or a cyclic organic which may have a substituent. R ^d8 and R ^d9 may be bonded to each other to form a ring, R ^d10 is a monovalent organic group, R ^d11 has a hydrogen atom and a substituent. An alkyl group having 1 to 11 carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1.)   The colored photosensitive composition of any one of Claims 1-5 which further contains alkali-soluble resin or further contains alkali-soluble resin and a polyfunctional monomer.   The colored photosensitive composition according to any one of claims 1 to 6, which is used for forming a color filter or a black matrix.   A colored cured product obtained by curing the colored photosensitive composition according to claim 1.   A display device comprising a color filter or a black matrix, wherein the color filter or black matrix is the colored cured product according to claim 8. Forming a coating film by applying the colored photosensitive composition according to any one of claims 1 to 7 on a substrate;
The manufacturing method of colored hardened | cured material including the process of exposing the said coating film, and the process of baking the said exposed coating film.   The manufacturing method of the colored hardened | cured material of Claim 10 with which the said baking is performed at 80-160 degreeC.   The manufacturing method of colored hardened | cured material including the process of superposing | polymerizing and / or bridge | crosslinking the colored photosensitive composition of any one of Claims 1-7.