JP6968633B2 - Photosensitive composition and photopolymerization initiator used therein - Google Patents

Description

The present invention relates to a photosensitive composition having good curability, a photosensitive composition suitable as a photosensitive adhesive, a compound used therein, and a photopolymerization initiator.

In a panel for a display device such as a liquid crystal display device, an insulating film or a material such as a spacer needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, in order to form an insulating film or a spacer pattern, a photosensitive composition that gives a transparent cured film by exposure is used. By selectively exposing such a photosensitive composition, a transparent cured film pattern can be formed.

Further, in a panel for a display device, a patterned light-shielding film such as a black matrix or a black column spacer is often formed. Various photosensitive compositions containing a light-shielding agent and a photopolymerization initiator, which are used to form a light-shielding film in such applications, have also been proposed.
Since the photosensitive composition used for forming the light-shielding film contains a light-shielding agent, the photopolymerization initiator is required to have higher sensitivity.

For example, as a photosensitive composition containing a photopolymerization initiator having excellent sensitivity, a photosensitive composition containing an oxime ester compound containing a fluorene ring substituted at the 9-position as a main skeleton as a photopolymerization initiator has been proposed. (See Patent Document 1.).

Japanese Unexamined Patent Publication No. 2016-218353

However, there is a problem that the photopolymerization initiator contained in the photosensitive composition is inactivated by oxygen in the air.
On the other hand, LEDs are being used as light sources for exposure from the viewpoint of energy saving and reduction of environmental load.
There is a demand for a photosensitive composition having excellent curability even under various exposure conditions including LED exposure (for example, various exposure wavelengths).
The present invention has been made in view of the above-mentioned problems of the prior art, and provides a photosensitive composition in which tack (stickiness) after curing is suppressed and excellent in curability, a compound used therein, and a photopolymerization initiator are provided. The purpose.

The present inventors have a photosensitive composition by having an oxime ester-based photopolymerization initiator having a specific structure _{having a substituent containing a group represented by HX 2} C- or H ₂ XC- (X is a halogen atom). It has been found that the curability (particularly, surface curability) of the ester can be improved, and the present invention has been completed. That is, the present invention is as follows.

（上記式（１）中、Ｒ^ａ１は、各々独立に、水素原子、ニトロ基、又は１価の有機基であり、Ｒ^ａ２及びＲ^ａ３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鎖状アルコキシ基、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^ａ２とＲ^ａ３とは相互に結合して環を形成してもよく、Ｒ^ａ４は１価の有機基であり、Ｒ^ａ５は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、ｎ１は０以上４以下の整数であり、ｎ２は０又は１である。）
で表される化合物を含み、
前記式（１）で表される化合物が、下記１）〜３）：
１）ｎ１は１以上４以下の整数であり、Ｒ^ａ１の少なくとも１つがＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
２）Ｒ^ａ４がＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
３）Ｒ^ａ５がＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
のうちの少なくとも１つを満たす（ただし、Ｘは、各々独立に、ハロゲン原子である）、感光性組成物である。 The first aspect of the present invention is
A photosensitive composition containing (A) a photopolymerization initiator and (B) a photopolymerizable compound, wherein the (A) photopolymerization initiator is the following formula (1):.

(In the above formula (1), R ^a1 is an independently hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 and R ^a3 are chain-like groups which may have a substituent, respectively. It is an alkyl group, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and Ra ² and Ra ³ are bonded to each other to form a ring. R ^a4 may be a monovalent organic group, and R ^a5 may have a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or a substituent. It may be an aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.)
Including compounds represented by
The compounds represented by the formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
3) R ^a5 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
A photosensitive composition that satisfies at least one of the above (where X is an independent halogen atom).

（上記式（１）中、Ｒ^ａ１は、各々独立に、水素原子、ニトロ基、又は１価の有機基であり、Ｒ^ａ２及びＲ^ａ３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鎖状アルコキシ基、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^ａ２とＲ^ａ３とは相互に結合して環を形成してもよく、Ｒ^ａ４は１価の有機基であり、Ｒ^ａ５は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、ｎ１は０以上４以下の整数であり、ｎ２は０又は１である。）
で表され、上記式（１）で表される化合物が、下記１）〜３）：
１）ｎ１は１以上４以下の整数であり、Ｒ^ａ１の少なくとも１つがＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
２）Ｒ^ａ４がＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
３）Ｒ^ａ５がＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である。
のうちの少なくとも１つを満たす（ただし、Ｘは、各々独立に、ハロゲン原子である）化合物である。 The second aspect of the present invention is
The following formula (1):

(In the above formula (1), R ^a1 is an independently hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 and R ^a3 are chain-like groups which may have a substituent, respectively. It is an alkyl group, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and Ra ² and Ra ³ are bonded to each other to form a ring. R ^a4 may be a monovalent organic group, and R ^a5 may have a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or a substituent. It may be an aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.)
The compounds represented by the above formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
3) R ^a5 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
A compound that satisfies at least one of the above (where X is an independent halogen atom).

A third aspect of the present invention is a photopolymerization initiator comprising the compound according to the second aspect.

The photosensitive composition of the present invention is excellent in curability because tack (stickiness) after curing is suppressed even under various exposure conditions including LED exposure (for example, various exposure wavelengths). The photosensitive composition of the present invention is suitable as, for example, a photosensitive adhesive.
According to the present invention, it is possible to provide a compound suitable for the photosensitive composition and a photopolymerization initiator.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. ..
Further, in the present specification, "~" means the following from the above unless otherwise specified.

<< Photosensitive composition >>
The photosensitive composition according to the first aspect is a photosensitive composition containing (A) a photopolymerization initiator and (B) a photopolymerizable compound, and the above-mentioned (A) photopolymerization initiator is the above-mentioned formula (1). ), And the compound represented by the above formula (1) satisfies at least one of the following 1) to 3) (where X is independently a halogen atom). ..
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
3) R ^a5 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
Hereinafter, the components contained in the photosensitive composition will be described in order.

<(A) Photopolymerization initiator>
The photosensitive composition contains (A) a photopolymerization initiator (hereinafter, also referred to as a component (A)) containing a compound represented by the above formula (1).
When the compound represented by the above formula (1) satisfies at least one of the above 1) to 3), the curability (particularly, surface curability) of the photosensitive composition can be improved. As a result, the tack (stickiness) on the surface of the formed cured product can be reduced.

Above 1) when at least one ^{of R a1} is a monovalent organic group, at least one of the group represented by _HX 2 C-or _H 2 XC of the monovalent organic group described above Can correspond to a containing substituent.
In the case of 2) above, ^Ra4 is a monovalent organic group, and the monovalent organic group may correspond to a substituent containing a group represented by _{HX 2} C- or H _{2 XC-.}
In the case of 3) above, ^Ra5 is an aliphatic hydrocarbon group having a substituent and having 1 to 20 carbon atoms or an aryl group having a substituent, and the aliphatic hydrocarbon group having the substituent or the substituent. The aryl group having the above may correspond to a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom is preferable.
As the substituent containing a HX ₂ C-or a group represented by _H 2 XC, halogenated alkoxy group containing a group represented by _HX 2 C-or _H 2 XC-, _HX 2 C- or _H 2 XC - a group having a halogenated alkoxy group containing a group represented, a halogenated alkyl group containing a group represented by _HX 2 C-or _H 2 XC, represented by _HX 2 C-or _H 2 XC Examples thereof include a group having an alkyl halide group including a group, and an alkoxy halide group containing a group represented by _{HX 2} C- or H _{2 XC-, or a group represented by HX 2} C- or H ₂ XC-. It is more preferable that the group has a halogenated alkoxy group including a group.

Examples of the group having a halogenated alkyl group containing HX ₂ C-or a group represented by _H 2 XC, substituted with a halogenated alkyl group containing a group represented by _HX 2 C-or _H 2 XC A cycloalkyl group substituted with an alkyl halide group (eg, cyclopentyl group, cyclohexyl) including an aromatic group (eg, phenyl group, naphthyl group, etc.), _{a group represented by HX 2} C- or H _{2 XC-.} Groups and the like) are mentioned, and it is preferable that it is an aromatic group substituted with an alkyl halide group containing a group represented by _{HX 2} C- or H _{2 XC-.}

Specific Examples of Halogenated Alkyl Groups Containing Groups Represented by HX ₂ C- or H ₂ XC-, and Specific Examples of Groups Having Halogenated Alkyl Groups Containing Groups Represented by _{HX 2} C- or H _{2 XC-} As an example, the following structure can be exemplified.

Examples of the group having a halogenated alkoxy group containing HX ₂ C-or a group represented by _H 2 XC, substituted by halogenated alkoxy group containing a group represented by _HX 2 C-or _H 2 XC Alkyl groups (eg, methyl groups, ethyl groups, etc.) substituted with halogenated alkoxy groups, including aromatic groups (eg, phenyl groups, naphthyl groups, etc.), _{groups represented by HX 2} C- or H _{2 XC-.} , n- propyl, i- propyl group), a cycloalkyl group substituted with a halogenated alkoxy group containing _HX 2 C-or _H 2 XC group represented by (e.g., a cyclopentyl group, a cyclohexyl group ) And the like, and it is preferable that it is an aromatic group substituted with a halogenated alkoxy group containing a group represented by _{HX 2} C- or H _{2 XC-.}

（上記式（１−ａ）中、Ｒ^ａ６はＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含むハロゲン化アルキル基であり、Ｒ^ａ７は、１価の置換基であり、＊は結合手であり、ｎ３は１又は２であり、ｎ３＋ｎ４は１以上５以下の整数である。）
Ｒ^ａ７の１価の置換基としては、ハロゲン原子、ニトロ基、炭素原子数１以上６以下のアルキル基、又は炭素原子数１以上６以下のアルコキシ基等が挙げられ、炭素原子数１以上６以下のアルキル基又は炭素原子数１以上６以下のアルコキシ基が好ましく、炭素原子数１以上６以下のアルキル基がより好ましく、メチル基又はエチル基がさらに好ましく、メチル基が特に好ましい。
ｎ４は０以上２以下であることが好ましく、１であることがより好ましい。 The _{aromatic group substituted with a halogenated alkoxy group containing a group represented by HX 2} C- or H ₂ XC- is preferably a group represented by the following formula (1-a).

(In the formula ^{(1-a), R a6} is a halogenated alkyl group containing a group represented by _HX 2 C-or _H 2 ^{XC, R a7} is a monovalent substituent, and * It is a combiner, n3 is 1 or 2, and n3 + n4 is an integer of 1 or more and 5 or less.)
Examples of the monovalent substituent of R ^a7 include a halogen atom, a nitro group, an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, and 6 or more carbon atoms. The following alkyl groups or alkoxy groups having 1 or more and 6 or less carbon atoms are preferable, alkyl groups having 1 or more and 6 or less carbon atoms are more preferable, methyl groups or ethyl groups are further preferable, and methyl groups are particularly preferable.
n4 is preferably 0 or more and 2 or less, and more preferably 1.

Specific examples of the group having a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ XC- can exemplify, for example, the following structure, but the present invention is limited thereto. It's not a thing.

Above 1) When, halogenated containing the ^{R a1} is _HX 2 C-or _H 2 halogenated alkoxy group containing a group represented by the XC, or _HX 2 C-or _H 2 group represented by XC It is preferably a group having an alkoxy group.
Above 2) or 3) when, it is preferable that the ^{R a4} or ^{R a5} is a group having a halogenated alkoxy group containing a group represented by _HX 2 C-or _H 2 XC.

In formula (1), ^Ra1 is a hydrogen atom, a nitro group or a monovalent organic group. R ^a1 is attached to a 6-membered aromatic ring on the fluorene ring in the formula (1), which is different from the 6-membered aromatic ring attached to the group represented by _{− (CO) n2-.} In the formula (1), the binding position relative to the fluorene ring of R ^a1 is not particularly limited. When the compound represented by the formula (1) has 1 or more Ra ^{1 , one of the 1 or more Ra 1} is a fluorene ring because the compound represented by the formula (1) can be easily synthesized. It is preferable to bind to the 2-position of the inside. If R ^a1 is plural, the plurality of R ^a1 may be the same or different.

When R ^a1 is a monovalent organic group, R ^a1 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. when, at least one of R ^a1 is a monovalent organic radical, substituents containing at least one group represented by HX 2 _C-or H ₂ XC of the monovalent organic group described above Is. Suitable examples where R ^a1 is a monovalent organic group is a substituted group containing a group represented by XC- the HX 2 _C-or H _2, alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy Group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, phenyl group which may have a substituent, phenoxy group which may have a substituent, benzoyl group which may have a substituent. , Phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, and a substituent. It has 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, and a substituent. May have a naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, morpholin-1-yl. Examples include a group and a piperazine-1-yl group.
Specific substituents containing at least one of _HX 2 C-or _H 2 XC group represented by where a substituent containing a group represented by _HX 2 C-or _H 2 XC of the R ^a1 Examples and preferred examples are as described above.

When R ^a1 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When ^Ra1 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^a1 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, Examples thereof include an n-decyl group and an isodecyl group. Further, when ^Ra1 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, a methoxypropyl group and the like.

When R ^a1 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. When ^Ra1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^a1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octioxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, an isodecyloxy group and the like. When ^Ra1 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 methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When ^Ra1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where R ^a1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. ^{Specific examples of the case where Ra1} 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 ^a1 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 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^a1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanol group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and 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-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^a1 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, and 2, 2-Dimethylpropanoloxy 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 can be mentioned.

When R ^a1 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^a1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octioxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^a1 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When ^Ra1 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where R ^a1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^a1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When R ^a1 is a phenylalkyl group or a naphthylalkyl group, R ^a1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^a1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indolidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done. When R ^a1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^a1 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^a1 is a heterocyclyl group.

When R ^a1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and the like. Saturated aliphatic acyl group having 2 or more and 21 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more and 20 carbon atoms which may have a substituent. The following phenylalkyl group, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, and heterocyclyl. The group etc. can be mentioned. Specific examples of these suitable organic groups are the same as for ^Ra1. Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group and an 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, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoyylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When the phenyl group, the naphthyl group, and the heterocyclyl group contained in ^{R a1} _{further have a substituent, the substituent includes a substituent represented by HX 2} C- or H ₂ X C- (for example, HX). ₂ C- or halogenated alkoxy group containing a group represented by _H 2 XC, _HX halogenated alkyl group containing 2 C- or _H 2 XC group represented by), the 1 to 6 carbon atoms Alkyl group, alkoxy group with 1 to 6 carbon atoms, saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated fat with 2 to 7 carbon atoms Group acyloxy group, monoalkylamino group having an alkyl group with 1 to 6 carbon atoms, dialkylamino group having an alkyl group with 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group , Halogen, nitro group, cyano group and the like. Included in R ^a1, when having a phenyl group, a naphthyl group and heterocyclyl group is further substituted, the number of the substituent is not limited within a range not inhibiting the object of the present invention, 1 to 4 are preferred. Included in R ^a1, a phenyl group, a naphthyl group, and the heterocyclyl group, when having a plurality of substituents, the plurality of substituents may be different and the same.

Halogen Among the groups described ^above, the ^{R a1,} containing _HX 2 C-or _H halogenated alkoxy group containing a group represented by 2 XC, _HX 2 C-or _H 2 XC group represented by A group represented by an alkylated group, a nitro group, or ^Ra11- CO- tends to improve sensitivity and is preferable. ^Ra11 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R ^a11 _{include a substituent containing a group represented by HX 2} C- or H ₂ XC-, an alkyl group having 1 to 20 carbon atoms, and a phenyl which may have a substituent. Examples thereof include a group, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^a11, Among these groups, a phenyl group, _HX 2 C-or _H 2 XC group represented by having a halogenated alkoxy group containing a group represented by _HX 2 C-or _H 2 XC A phenyl group having an alkyl halide group containing the above, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.
Further, when ^Ra1 is a hydrogen atom, the transparency tends to be good, which is preferable. When R ^a1 is a hydrogen atom and R ^a4 is a group represented by the formula (R4-2) described later, the transparency tends to be better.

Preferred specific examples of the group represented by R ^a11 −CO− can be exemplified below, but the present invention is not limited thereto. In the following formula, m3 is 0 or 1.

In the formula (1), Ra ² and Ra ³ are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^a2 and R ^a3 may be coupled to each other to form a ring. Among these groups, ^{as Ra2} and ^Ra3 , a chain alkyl group which may have a substituent is preferable. When R ^a2 and R ^a3 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.

When R ^a2 and Ra ³ are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. preferable. Specific examples of cases where R ^a2 and R ^a3 are chain alkyl groups 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, and a 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 Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when Ra ² and Ra ³ are alkyl groups, the alkyl group may contain an ether bond (—O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^a2 and Ra ³ are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. .. In this case, the number of carbon atoms 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 it does not impair the object of the present invention. 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. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when ^{Ra1 is a cycloalkyl group.} Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when ^{Ra1 is a heterocyclyl group.} When ^Ra1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched chain, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

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

When R ^a2 and R ^a3 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 ^a2 and R ^a3 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ^a2 and R ^a3 are chain alkyl groups.

When R ^a2 and R ^a3 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? , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring 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. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

When R ^a2 and R ^a3 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^a2 and R ^a3 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or such monocycles, or such monocycles and benzene rings. It is a heterocyclyl group condensed with. When the heterocyclyl group is a fused ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indolidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Be done.

R ^a2 and R ^a3 may be coupled to each other to form a ring. The group consisting of the ring formed by ^{R a2} and R ^{a3 is preferably a cycloalkylidene group.} When R ^a2 and R ^a3 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

When ^{the group formed by binding R a2} and R ^a3 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

Examples of suitable groups among ^{R a2} and ^{R a3} which has been described above is exemplified group of 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, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkylene group of A 1} is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. 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 an alkyl halide group, the halogen atom contained in the alkyl halide 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 alkyl halide group may be linear or branched, preferably linear. When A ² is a cyclic organic group, the example of the cyclic organic group is the same as that of the cyclic organic group that Ra ² and Ra ³ have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that Ra ² and Ra ³ have as substituents.

Suitable specific examples of R ^a2 and R ^a3 are 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- Alkyl alkyl 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 pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Phenyl such as group, 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. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarboni-n-hexyl group, 7-methoxycarboni-n-heptyl group, 8-methoxycarboni-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonin-n-hexyl group, 7- Ethylcarbo An alkoxycarbonylalkyl group such as a ni-n-heptyl group and an 8-ethoxycarbonin-n-octyl group; 2-chlorethyl group, 3-chlor-n-propyl group, 4-chlor-n-butyl group, 5- Chlor-n-pentyl group, 6-chlor-n-hexyl group, 7-chlor-n-heptyl group, 8-chlor-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-tri Examples thereof include a fluoropropyl group and an alkyl halide group such as a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

As R ^a2 and R ^a3 , the preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 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-hepta It is a fluoro-n-pentyl group.

As described above, when ^Ra4 is a monovalent organic group, in the case of 2) above, the monovalent organic group is a substituent containing a group represented by _{HX 2} C- or H _{2 XC-.} ..
Examples of suitable organic groups for R ^a4 include substituents including the groups represented by HX ₂ C- or H ₂ XC-, alkyl groups, alkoxy groups, cycloalkyl groups and cycloalkoxys ^{, as in R a1.} Group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, phenyl group which may have a substituent, phenoxy group which may have a substituent, benzoyl group which may have a substituent. , Phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, and a substituent. It has 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, and a substituent. May have a naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, morpholin-1-yl. Examples include a group and a piperazine-1-yl group. Specific examples of these groups are the same as those described for ^Ra1. Further, ^{as Ra4} , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in ^{Ra1 may have.}

Among the organic group, the R ^a4, the HX 2 _C-or a substituent containing a group represented by H ₂ XC, alkyl group, cycloalkyl group, phenyl group which may have a substituent group, or Cycloalkylalkyl groups and phenylthioalkyl groups which may have a substituent on the aromatic ring are preferable. 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 the most preferable. 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 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferable. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

^As the ^{R a4,} a group represented by -A 3 ^{-CO-O-A 4} are also preferred. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group is preferably a monovalent hydrocarbon group.

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

Preferred examples of A ^4, the number 1 to 10 alkyl group carbon atoms, having 7 or more carbon atoms and 20 or less aralkyl group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific preferable examples of A ⁴ is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

Specific preferable examples of the group represented by ^{-A 3 -CO-O-A 4} , 2- methoxycarbonylethyl group, 2-ethoxycarbonylethyl, 2-n-propyl-oxycarbonyl ethyl, 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, 3-phenoxycarbonyl-n-propyl group and the like.

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^ａ８及びＲ^ａ９はそれぞれ有機基であり、ｐは０以上４以下の整数であり、Ｒ^ａ８及びＲ^ａ９がベンゼン環上の隣接する位置に存在する場合、Ｒ^ａ８とＲ^ａ９とが互いに結合して環を形成してもよく、ｑは１以上８以下の整数であり、ｒは１以上５以下の整数であり、ｓは０以上（ｒ＋３）以下の整数であり、Ｒ^ａ１０は有機基である。） ^Having described ^{R a4,} as the ^{R a4,} preferably a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ^a8 and R ^a9 are organic groups, respectively, p is an integer of 0 or more and 4 or less, and R ^a8 and R ^a9 are adjacent to each other on the benzene ring. When present at the position, R ^a8 and R ^a9 may be combined with each other to form a ring, q is an integer of 1 or more and 8 or less, r is an integer of 1 or more and 5 or less, and s is 0. It is an integer equal to or less than (r + 3), and ^Ra10 is an organic group.)

Examples of the organic group for ^{R a8} and R ^a9 in the formula (R4-1) include a halogenated alkoxy group containing a group represented by _{HX 2} C- or H _{2 X C-, HX 2} C- or H _2. It has an alkyl halide group including a group represented by XC-, 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. 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 benzoyloxy group which may have a substituent. , 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, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.
HX ₂ C-or halogenated alkoxy group containing a group represented by _H 2 XC, above specific examples and preferred examples of the halogenated alkyl group containing a group represented by _HX 2 C-or _H 2 XC It is a street.
The R ^a8, a halogenated alkyl group containing _HX 2 C-or _H 2 XC halogenated alkoxy group containing a group represented by, _HX 2 C-or _H 2 XC, a group represented by the alkyl group or Phenyl groups are preferred. Halogenated alkyl groups include groups wherein R ⁷ is a halogenated alkoxy group containing a group represented by _HX 2 C-or _H 2 XC, represented by _HX 2 C-or _H 2 XC, or an alkyl group In this case, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.
When R ^a8 and R ^a9 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 (R4-1) in which R ^a8 and R ^a9 form a ring include a naphthalene-1-yl group and 1,2,3. Examples thereof include 4-tetrahydronaphthalene-5-yl group. In the above formula (R4-1), p is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula ^{(R4-2), R a10} represents an organic group. ^{Examples of the} organic group include groups similar to the organic groups described for Ra8 and ^Ra9. Among the organic group, halogenated alkyl group containing _HX 2 C-or _H halogenated alkoxy group containing a group represented by 2 XC, _HX 2 C-or _H 2 XC, a group represented by or alkyl Groups are preferred. HX ₂ C-or _H halogenated alkoxy group containing a group represented by 2 XC-, _HX 2 C- or a halogenated alkyl group containing a group represented by _H 2 XC, or alkyl group may be linear It may be in the form of a branched chain. HX ₂ C-or halogenated alkoxy group containing a group represented by _H 2 XC-, _HX 2 C- or a halogenated alkyl group containing a group represented by _H 2 XC and number of carbon atoms in the alkyl group, the 1 or more and 10 or less are preferable, 1 or more and 5 or less are more preferable, and 1 or more and 3 or less are particularly preferable. The R ^a10, a halogenated alkyl group containing _HX 2 C-or _H 2 XC halogenated alkoxy group containing a group represented by, _HX 2 C-or _H 2 XC, a group represented by a methyl group, Ethyl group, propyl group, isopropyl group, butyl group and the like are preferably exemplified, and among these, a halogenated alkoxy group including a group represented by _{HX 2} C- or H _{2 XC-, HX 2} C- or H ₂ XC. It is more preferably an alkyl halide group containing a group represented by − or a methyl group.

In the above formula (R4-2), r is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (R4-2), s is 0 or more (r + 3) or less, an integer of 0 or more and 3 or less is preferable, an integer of 0 or more and 2 or less is more preferable, and 0 is particularly preferable. In the above formula (R4-2), q is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

In the formula (1), ^Ra5 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
However, as described above, in the case of 3) above, ^Ra5 is an aliphatic hydrocarbon group having a substituent and having 1 to 20 carbon atoms or an aryl group having a substituent, and is an aliphatic group having the above substituent. The hydrocarbon group or the aryl group having the above-mentioned substituent is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
Specific examples and preferred examples of the substituent containing a group R ^a5 is represented by _HX 2 C-or _H 2 XC when a substituent containing a group represented by _HX 2 C-or _H 2 XC Is as described above.
When R ^a5 is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed. Further, ^{as the substituent which may be possessed when Ra1} is an aryl group, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In formula (1), R ^a5 is a _{substituent containing a group represented by HX 2} C- or H ₂ XC-, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-butyl. A group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, _{a substituent including a group represented by HX 2} C- or H ₂ XC-, a methyl group or a phenyl group is more preferable. preferable.

Specific examples of the compound represented by the formula (1) include the following compounds, but the present invention is not limited thereto.

The content of the photopolymerization initiator as the component (A) is preferably 0.001 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass in total of the mass of the components other than the solvent in the photosensitive composition. , 0.1 part by mass or more and 20 parts by mass or less is more preferable, 0.5 part by mass or more and 10 parts by mass or less is further preferable, and 1 part by mass or more and 5 parts by mass or less is particularly preferable.
The content of the photopolymerization initiator as the component (A) is preferably 0.05% by mass or more and 50% by mass or less with respect to the total of the components (A) and (B). It is more preferably 1% by mass or more and 30% by mass or less, and further preferably 0.5% by mass or more and 20% by mass or less.
The compound represented by the formula (1) in the component (A) may be used alone or in combination of two or more.

（Ｒ^ａ１、Ｒ^ａ２、Ｒ^ａ３、Ｒ^ａ４、ｎ１、及びｎ２は、式（１）と同様である。）
ただし、Ｒ^ａ４がＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含む置換基である上記２）の場合、Ｒ^ａ４はハロゲン化アリール基であることが好ましい。
上記２）の場合、オキシム基（＝Ｎ−ＯＨ）を、＝Ｎ−Ｏ−ＣＯＲ^ａ５で表されるオキシムエステル基に変換した後に、Ｒ^ａ４の上記ハロゲン化アリール基のハロゲン原子と、ＨＸ_２Ｃ−又はＨ_２ＸＣ−で表される基を含むアルコールとを任意の芳香族求核置換反応を行うことにより上記式（１）で表される化合物を製造することが好ましい。
上記芳香族求核置換反応の条件としては、例えば、極性溶媒（例えば、ＤＭＳＯ、ＤＭＦ等）中、塩基若しくはアルカリ触媒下（例えば、炭酸カリウム（Ｋ_２ＣＯ_３）、水素化ナトリウム等）、室温ないし昇温下（例えば、５０℃以上２００℃以下、より好ましくは５５以上１８０℃以下）等が挙げられる。 <Method for producing the compound represented by the formula (1)>
The method for producing the compound represented by the formula (1) is not particularly limited. The compound represented by the formula (1) preferably contains an oxime group (= N—OH) contained in the compound represented by the formula (2) below, and is an oxime ester represented by ^{= NO—COR a5.} It can be manufactured by a method including a step of converting into a group. R ^a5 are the same as ^{R a5} in formula (1).

(R ^a1 , R ^a2 , R ^a3 , R ^a4 , n1, and n2 are the same as in the equation (1).)
However, when R ^a4 is a substituent containing a group represented by _{HX 2} C- or H ₂ ^{X C- above 2), it is preferable that R a4} is an aryl halide group.
For the 2), an oxime group (= N-OH), after converting to the oxime ester group represented by = ^{N-O-COR a5,} and halogen atoms of the halogenated aryl group ^{R a4,} _{HX 2} it is preferred to produce a compound represented by the above formula (1) by performing any aromatic nucleophilic substitution reaction of an alcohol containing C- or a group represented by H ₂ XC.
The conditions for the above aromatic nucleophilic substitution reaction are, for example, in a polar solvent (for example, DMSO, DMF, etc.), under a base or alkali catalyst (for example, potassium carbonate (K ₂ CO ₃ ), sodium hydride, etc.), at room temperature. Or under a temperature rise (for example, 50 ° C. or higher and 200 ° C. or lower, more preferably 55 or higher and 180 ° C. or lower) and the like.

The method for converting an oxime group (= N-OH) to an oxime ester group represented by ^{= NO-COR a5 is not particularly limited.} Typically, there is a method of reacting a hydroxyl group in an oxime group with an acylating agent that gives an acyl group represented by ^{−COR a5.} The acylating ^agent, (R a5 _CO) acid anhydride represented by ₂ O ^and, R a5 COHal (Hal is a halogen atom) include acid halide represented by.

If R ^a5 are the 3) is a substituent containing a group represented by _HX 2 C-or _H 2 XC, a method of introducing a substituent containing a group represented by _HX 2 C-or _H 2 XC Is, for example, an oxime ester by an arbitrary esterification reaction between an acid anhydride or an acid halide having a substituent containing a group represented by _{HX 2} C- or H _{2 XC- and an oxime compound (= N-OH).} This can be done by converting to a compound.

When n2 is 0, the compound represented by the general formula (1) can be synthesized, for example, according to the following scheme 1. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ^a1 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (1-1) is a fluorene derivative in which the 9-position is ^{substituted with Ra 2} and Ra ³ by a well-known method. It can be obtained by introducing a substituent R ^a1.

In ^particular, substitutions comprising group ^{R a1} is the case of the above 1) is a substituent containing a group represented by _HX 2 C-or _H 2 XC, for example, represented by _HX 2 C-or _H 2 XC By reacting an alkyl halide or acid halide having a group with a fluorene derivative in which the ^{9-position is substituted with Ra2} and ^Ra3 by a Friedel-Crafts reaction in the presence _{of an arbitrary Lewis acid (eg, AlCl 3) catalyst.} , ^{R a1} , which is a substituent containing a group represented by _{HX 2} C- or H ₂ XC-, can be introduced into the compound represented by the formula (1).

Fluorene derivatives 9-position is substituted with ^{R a2} and ^{R a3} may be, for ^example, when ^{R a2} and ^{R a3} is an alkyl group, as described in JP-A-06-234668, alkali metal hydroxides It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotonic polar organic solvent. Further, 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 carrying out an alkylation reaction, a 9,9-alkyl substituted fluorene can be obtained.

^{An acyl group represented by -CO-R a4} is introduced into the fluorene derivative represented by the formula (1-1) by a Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (1-3) is obtained. can get.
Incidentally, as described ^above, when ^{R a4} is the above 2) is a substituent containing a group represented by _HX 2 C-or _H 2 ^{XC, R a4} is preferably a halogenated aryl group, fluorine More preferably, it is an arylated group.
The acylating agent for introducing the acyl group represented by -CO-R ^{a4 may be a halocarbonyl compound or an acid anhydride.} As the acylating agent, a halocarbonyl compound represented by the formula (1-2) is preferable. In formula (1-2), H is a halogen atom. The position where the acyl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or by applying protection and deprotection to other positions of the acylated position. can.

^{Next, the group represented by -CO-R a4} in the obtained fluorene derivative represented by the formula (1-3) is converted into the group represented by -C (= N-OH) -R ^a4. The oxime compound represented by the formula (1-4) is obtained. The method for converting the group represented by -CO-R ^a4 to the group represented by -C (= N-OH) -R ^a4 is not particularly limited, but oxime formation with hydroxylamine is preferable. The oxime compound of the formula (1-4) and the acid anhydride (( ^Ra5 CO) ₂ O) represented by the following formula (1-5), or the acid halide represented by the following general formula (1-6). ^(R a5 COHal, Hal is a halogen atom.) can be reacted and to obtain a compound represented by the following formula (1-7).

In the equations (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), ^Ra1 and R ^a2 , R ^a3 , R ^a4 , and R ^a5 are the same as those in the equation (1).
However, as described above, when R ^a4 is a substituent containing a group represented by _{HX 2} C- or H ₂ ^{X C- above 2), it is preferable that R a4} is an aryl halide group.
For the 2), as described above, an oxime group (= N-OH), = N-O-COR after converting the oxime ester group represented by ^a5, halogen atoms of the halogenated aryl group ^{R a4} And an _{alcohol containing a group represented by HX 2} C- or H ₂ XC- is preferably subjected to an arbitrary aromatic nucleophilic substitution reaction to produce the compound represented by the above formula (1).

^{Further, in Scheme 1, R a1} , R ^a4, and R ^a5 contained in Eqs. (1-2), Eqs. (1-3), and Eqs. (1-4) may be the same or different. May be good. ^{That is, even if R a1} , R ^a4 and R ^a5 in the formula (1-2), the formula (1-3), and the formula (1-4) are chemically modified in the synthetic process shown as the scheme 1. good. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, etc., among R ^a1 , R ^a4 , and R ^a5 . Acylation in which a halogenated alkoxy group containing a group represented by _{HX 2} C- or H ₂ XC- is introduced into at least one is preferable. The ^{chemical modifications that R a1} , R ^a4 and R ^a5 may undergo are not limited to these.

[Scheme 1]

When n2 is 1, the compound represented by the formula (1) can be synthesized, for example, according to the following scheme 2. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. _{The fluorene derivative represented by the formula (2-1) is represented by -CO-CH 2-} R ^a4 by the Friedel-Crafts reaction to the compound represented by the formula (1-1) by the same method as in Scheme 1. It is obtained by introducing the acyl group to be added.
As described above, when R ^a4 is a substituent containing a group represented by _{HX 2} C- or H ₂ ^{X C- above 2), it is preferable that R a4} is an aryl halide group.
The acylating agent of the formula (1-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R a4}} . ^{Next, the methylene group existing between the Ra4} and the carbonyl group in the compound represented by the formula (2-1) is oxime-ized to obtain the keto-oxime compound represented by the following formula (2-3). The method for oxime-forming the methylene group is not particularly limited, but a nitrite ester represented by the following general formula (2-2) (RONO and R are alkyl groups having 1 or more and 6 or less carbon atoms) represented by the following general formula (2-2) is used in the presence of hydrochloric acid. The method of reacting is preferable. Next, the ketooxime compound represented by the following formula (2-3), the acid anhydride represented by the following formula (2-4) (( ^Ra5 CO) ₂ O), or the following general formula (2-5). in represented by acid halide ^(R a5 COHal, Hal is a halogen atom.) can be reacted and to obtain a compound represented by the following formula (2-6). In the following equations (2-1), (2-3), (2-4), (2-5), and (2-6), R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 is the same as the general formula (1).
However, as described above, when R ^a4 is a substituent containing a group represented by _{HX 2} C- or H ₂ ^{X C- above 2), it is preferable that R a4} is an aryl halide group.
For the 2), as described above, an oxime group (= N-OH), = N-O-COR after converting the oxime ester group represented by ^a5, halogen atoms of the halogenated aryl group ^{R a4} And an _{alcohol containing a group represented by HX 2} C- or H ₂ XC- is preferably subjected to an arbitrary aromatic nucleophilic substitution reaction to produce the compound represented by the above formula (1).

When n2 is 1, there is a tendency that the generation of foreign substances in the pattern formed by using the photosensitive composition containing the compound represented by the formula (1) can be further reduced.
^{Further, in Scheme 2, Ra 4} contained in each of the formulas (1-8), the formula (2-1), and the formula (2-3) may be the same or different. ^{That is, R a4} in the formulas (1-8), formula (2-1), and formula (2-3) may undergo chemical modification in the synthetic process shown as Scheme 2. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. The ^{chemical modifications that R a4} may undergo are not limited to these.

[Scheme 2]

<Compounds and photopolymerization initiators>
The present invention also relates to a compound represented by the above-described formula (1) and a photopolymerization initiator containing the above compound.
That is, the compound according to the second aspect is the compound represented by the formula (1) described above.
The photopolymerization initiator according to the third aspect contains the compound represented by the above-described formula (1).

<Other photopolymerization initiators>
The (A) photopolymerization initiator may contain other photopolymerization initiators (hereinafter, also referred to as (A') component) other than the compound represented by the above formula (1). (A) The content of the compound represented by the above formula (1) in the photopolymerization initiator is, for example, 1% by mass or more and 99% by mass or less, preferably 10% by mass or more and 80% by mass or less, and 20% by mass or more. 60% by mass or less is more preferable, and 30% by mass or more and 50% by mass or less is further preferable.
(A) When the photopolymerization initiator contains other photopolymerization initiators other than the compound represented by the above formula (1), the photopolymerization initiator contains two or more other photopolymerization initiators in combination. You may be.

（上記式（３）中、Ｒ^１１及びＲ^１２は、各々独立に、アルキル基、シクロアルキル基、アリール基、炭素数１以上２０以下の脂肪族アシル基又は芳香族アシル基（但し、Ｒ^１１及びＲ^１２の双方が脂肪族アシル基又は芳香族アシル基である場合を除く。）であり、＊は結合手である。）
で表される構造部分を含むアシルホスフィンオキサイド系光重合開始剤、
Ｏ−アセチル−１−［６−（２−メチルベンゾイル）−９−エチル−９Ｈ−カルバゾール−３−イル］エタノンオキシム、エタノン，１−［９−エチル−６−（ピロール−２−イルカルボニル）−９Ｈ−カルバゾル−３−イル］，１−（Ｏ−アセチルオキシム）、及び１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］等のオキシムエステル化合物、 As the photopolymerization initiator other than the compound represented by the above formula (1), any conventionally known photopolymerization initiator can be used.
Specific examples of any photopolymerization initiator other than the compound represented by the above formula (1) include
The following formula (3):

(In the above formula (3), R ¹¹ and R ¹² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 1 or more and 20 or less carbon atoms, or an aromatic acyl group (however, R ^11). And R ¹² are both aliphatic acyl groups or aromatic acyl groups.), And * is a bond.)
Acylphosphine oxide-based photopolymerization initiator containing the structural portion represented by
O-Acetyl-1- [6- (2-Methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] Ethanone Oxime, Etanone, 1- [9-Ethyl-6- (Pyrol-2-ylcarbonyl) ) -9H-Carbazole-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and other oximes. Ester compound,

1-Hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-on, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 2, 2-Dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoate methyl , 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate butyl, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal , O-Methyl benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl Thioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumenhydro Peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 -Di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 -(P-Phenylphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bis Dimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethyl Michler's ketone), 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-dimethylaminopropiophenone, dichloroacetophenone, Trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-Isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridin, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1, 3-Bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-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 are mentioned, and since the composition is excellent in internal curability, the acylphosphine oxide-based light containing the structural portion represented by (3) above. It is preferably a polymerization initiator.

In the above formula (3), ^{the alkyl group for R 11} and R ¹² is an alkyl having 1 or more and 12 or less carbon atoms (preferably 1 or more and 8 or less carbon atoms, more preferably 1 or more and 4 or less carbon atoms). The group is mentioned.
Examples of the cycloalkyl group for R ¹¹ and R ¹² include a cycloalkyl group having 5 or more and 12 or less carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group for R ¹¹ and R ¹² may have a substituent such as a halogen atom, an alkyl group or an alkoxy group, and examples thereof include an aryl group having 6 to 12 carbon atoms, a phenyl group and a naphthyl. The group etc. can be mentioned.
The aliphatic acyl group for R ¹¹ and R ¹² may have a substituent such as a halogen atom or an alkoxy group, and the number of carbon atoms is 2 or more and 12 or less (preferably, the number of carbon atoms is 2 or more and 8 or less, and more. Preferred are aliphatic acyl groups having 2 or more and 6 or less carbon atoms), and examples thereof include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyle group, an octanoyl group, a nonanoyl group and a decanoyle group.
Examples of the aromatic acyl group for R ¹¹ and R ¹² may have a substituent such as a halogen atom, an alkyl group or an alkoxy group, and examples thereof include an aromatic acyl group having 6 or more and 12 or less carbon atoms. Examples thereof include a benzoyl group, an α-naphthoyl group, a β-naphthoyl group and the like.

Examples of the acylphosphine oxide-based photopolymerization initiator containing the structural portion represented by the above formula (3) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphos. Examples thereof include fin oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide.

The content of the photopolymerization initiator (A) in the photosensitive composition is not particularly limited as long as it does not impair the object of the present invention. The content of the photopolymerization initiator (A) is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.3% by mass or more and 15% by mass or less with respect to the mass of the solid content of the photosensitive composition. , 0.5% by mass or more and 10% by mass or less is more preferable, and 0.8% by mass or more and 5% by mass or less is particularly preferable. By using an amount of the photopolymerization initiator (A) within such a range, it is easy to obtain the desired effect by using the photopolymerization initiator (A).

<(B) Photopolymerizable compound>
The (B) photopolymerizable compound (hereinafter, also referred to as (B) component) contained in the photosensitive composition according to the first aspect is not particularly limited, and a conventionally known photopolymerizable compound is used. Can be done. Among them, a resin or a monomer having an ethylenically unsaturated group is preferable, and these may be combined. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, the curability of the photosensitive composition can be improved and pattern formation can be facilitated. In the first aspect, a monomer having an ethylenically unsaturated group is more preferable.

[Resin having an ethylenically unsaturated group]
Resins having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and ethylene. Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene Glycoldi (meth) acrylate, trimethylol propanetri (meth) acrylate, tetramethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Oligomers polymerized with dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxydiacrylate, etc .; obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid. Polyester (meth) acrylate obtained by reacting the polyester prepolymer to be obtained with (meth) acrylic acid; obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid. Polyurethane (meth) acrylate; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester , Polypolyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin and other epoxy resins, and epoxy (meth) acrylate resin obtained by reacting (meth) acrylic acid with (meth) acrylic acid, etc. Can be mentioned. Further, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be preferably used. In addition, in this specification, "(meth) acrylic" means "acrylic or methacryl".

Further, as the resin having an ethylenically unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound with an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be preferably used. ..

Among them, the compound represented by the following general formula (b1) is preferable. The compound represented by the general formula (b1) is preferable in that it has high photocurability.

In the above general formula (b1), X represents a group represented by the following general formula (b2).

In the above general formula (b2), R ^1b independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a halogen atom, and R ^2b independently represents a hydrogen atom or a methyl group, respectively. Represented, W represents a single bond or a group represented by the following structural formula (b3). In the general formula (b2) and the structural formula (b3), "*" means the end of the bond of the divalent group.

In the above general formula (b1), Y represents a residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides are phthalic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydro. Phthalic anhydride, glutaric anhydride and the like can be mentioned.

Further, in the above general formula (b1), Z represents a residue obtained by removing two acid anhydride groups from the tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride and the like. Further, in the above general formula (b1), b represents an integer of 0 or more and 20 or less.

The acid value of the resin having an ethylenically unsaturated group is preferably 10 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 70 mgKOH / g or more and 110 mgKOH / g or less in terms of resin solid content. It is preferable to set the acid value to 10 mgKOH / g or more because sufficient solubility in a developing solution can be obtained. Further, it is preferable to set the acid value to 150 mgKOH / g or less because sufficient curability can be obtained and surface properties can be improved.

The mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1000 or more and 40,000 or less, and more preferably 2000 or more and 30,000 or less. By setting the mass average molecular weight to 1000 or more, good heat resistance and film strength can be obtained, which is preferable. Further, it is preferable to set the mass average molecular weight to 40,000 or less because good developability can be obtained.

[Monomer having an ethylenically unsaturated group]
Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers. Hereinafter, the monofunctional monomer and the polyfunctional monomer will be described in order.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybuty (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivative and the like can be mentioned. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include 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, and butylene glycol di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, alkylene oxide-modified neopentyl glycol diacrylate with 1 to 5 carbon atoms (among others, propylene oxide-modified neopentyl glycol diacrylate) 1,6-hexane glycol di (meth) Acrylate, Trimethylol Propanetri (meth) Acrylate, Glycerindi (Meta) Acrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Pentaacrylate, Dipentaerythritol Hexaacrylate, Pentaerythritol di (meth) Acrylate, Pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane , 2,2-Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol di Glycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate. And polyfunctional such as a reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, and a condensate of polyhydric alcohol and N-methylol (meth) acrylamide. Examples thereof include monomers and triacrylic formal. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable compound as the component (B) is preferably 10 parts by mass or more and 99.9 parts by mass or less with respect to 100 parts by mass in total of the components excluding the solvent described later in the photosensitive composition. It is more preferably 80 parts by mass or more and 99.5 parts by mass or less, and more preferably 90 parts by mass or more and 99 parts by mass or less. (B) By setting the content of the component to 10 parts by mass or more with respect to 100 parts by mass in total of the components excluding the solvent described later, a photosensitive composition is used to form a film having good curability and no stickiness. Can be done.
In the first aspect, the component (B) is preferably composed of a polyfunctional monomer, and the polyfunctional monomer is more preferably a bifunctional or trifunctional monomer, and further preferably a bifunctional monomer. The proportion of the polyfunctional monomer in the component (B) is preferably 50% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more and 100% by mass or less.

<(C) Sensitizer>
The photosensitive composition may or may not contain (C) a sensitizer, but it preferably contains (C) a sensitizer.
By containing (C) a sensitizer together with (A) a photopolymerization initiator containing the compound represented by the above formula (1), the photosensitive composition can be satisfactorily subjected to LED exposure. Can be cured.
It is considered that this is because the compound represented by the formula (1) is particularly easily sensitized by the sensitizer.

As the (C) sensitizer, a compound conventionally used for the purpose of sensitizing a photopolymerization initiator in a photosensitive composition can be used without particular limitation.

(C) As the sensitizer, a compound having at least one selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O) as a substituent is preferable. As the compound having the substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferable.
The fused polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O). Examples of substituents are an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Examples thereof include an aliphatic acyl group of the above, an aromatic acyl group (aroyl group) having 7 to 11 carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and a mercapto group.

The alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 6 or less.
Preferable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy, n-butyloxy, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n. -Heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group and the like can be mentioned.

The substituted carbonyloxy group is a group represented by —O—CO—A. A is not particularly limited as long as the (C) sensitizer has a desired sensitizing effect, and may be various organic groups. As A, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms are preferable. ..

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as the object of the present invention is not impaired. When an aryl group or an aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different.
Preferable examples of the substituent are an alkoxy group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, an aryloxy group having 6 or more and 10 or less carbon atoms, and 6 or more and 10 or less carbon atoms. Aryloxy group, an aliphatic acyl group having 2 or more and 7 or less carbon atoms, an aromatic acyl group (aloyl group) having 7 or more and 11 or less carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and Examples include a mercapto group.

When A is an alkyl group or an alkoxy group, these groups may be linear or branched.
Preferable examples of the alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. , N-octyl group, 2-ethylhexyl group and the like.
Preferable examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an α-naphthyl group, a β-naphthyl group and the like.
Preferable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group and n-hexyloxy group. , N-Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group and the like.

In a fused polycyclic aromatic hydrocarbon compound substituted with one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O), or a condensed polycyclic aromatic heterocyclic compound. The number of rings constituting the fused ring is not particularly limited as long as the desired sensitizing effect can be obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 or more and 6 or less, and most preferably 3 or 4.
As long as the fused polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocycle forming the fused polycycle does not necessarily have to be an aromatic ring.

Preferable examples of the fused polycyclic aromatic hydrocarbon compound or the condensed polycyclic compound contained in the condensed polycyclic aromatic heterocyclic compound include an acenaphtylene ring, a phenanthrene ring, an anthracene ring, a naphthalene ring, a xanthene ring, and a thio. Examples include the xanthene ring. Among these rings, anthracene ring, naphthacene ring, and thioxanthene ring are preferable.

Specific examples of the compound containing an anthracene ring and preferably used as the (C) sensitizer include 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, and 9. , 10-bis (n-propylcarbonyloxy) anthracene, 9,10-bis (isopropylcarbonyloxy) anthracene, 9,10-bis (n-butylcarbonyloxy) anthracene, 9,10-bis (isobutylcarbonyloxy) anthracene , 9,10-bis (n-pentylcarbonyloxy) anthracene, 9,10-bis (n-hexylcarbonyloxy) anthracene, 9,10-bis (n-heptylcarbonyloxy) anthracene, 9,10-bis (n-heptylcarbonyloxy) anthracene 2-Ethlhexanoyloxy) anthracene, 9,10-bis (n-octylcarbonyloxy) anthracene, 9,10-bis (n-nonylcarbonyloxy) anthracene, 9,10-bis (n-decylcarbonyloxy) anthracene , 9,10-bis (benzoyloxy) anthracene, 9,10-bis (4-methylbenzoyloxy) anthracene, 9,10-bis (2-naphthoyloxy) anthracene, 2-methyl-9,10-bis ( Acetyloxy) anthracene, 2-methyl-9,10-bis (propionyloxy) anthracene, 2-methyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-methyl-9,10-bis (isopropylcarbonyl) Oxy) anthracene, 2-methyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-methyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-methyl-9,10-bis (n-) Pentylcarbonyloxy) anthracene, 2-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-methyl-9,10-bis (benzoyloxy) anthracene, 2-methyl-9,10-bis (4) -Methylbenzoyloxy) anthracene, 2-methyl-9,10-bis (2-naphthoyloxy) anthracene, 1-methyl-9,10-bis (acetyloxy) anthracene, 1-methyl-9,10-bis ( Propionyloxy) anthracene, 1-methyl-9,10-bis (n-propylcarbonyloxy) anthracene, 1-methyl-9,10-bis (isopropylcarbonyloxy) anthracene 1-Methyl-9,10-bis (n-butylcarbonyloxy) anthracene, 1-methyl-9,10-bis (isobutylcarbonyloxy) anthracene, 1-methyl-9,10-bis (n-pentylcarbonyl) Oxy) anthracene, 1-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-methyl-9,10-bis (benzoyloxy) anthracene, 1-methyl-9,10-bis (4-methyl) Benzoyloxy) anthracene, 1-methyl-9,10-bis (2-naphthoyloxy) anthracene, 2-ethyl-9,10-bis (acetyloxy) anthracene, 2-ethyl-9,10-bis (propionyloxy) ) Anthracene, 2-ethyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-butyl) Carbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n) -Hexylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (benzoyloxy) anthracene, 2-ethyl-9,10-bis (4-ethyl-benzoyloxy) anthracene, 2-ethyl-9,10-bis (2-naphthyloxy) anthracene, 1-ethyl-9,10-bis (acetyloxy) anthracene, 1-ethyl-9,10-bis (propionyloxy) anthracene, 1-ethyl-9,10-bis (n) -Propylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (isopropylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-butylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (Isobutylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-ethyl-9,10 -Bis (benzoyloxy) anthracene, 1-ethyl-9,10-bis (4-ethyl-benzoyloxy) anthracene, 1-ethyl-9,10-bis (2-naphthoyloxy) anthracene, 1- (t-) Butyl) -9,10-bi Su (n-propylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (isopropylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-butylcarbonyloxy) Anthracene, 1- (t-butyl) -9,10-bis (isobutylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-pentylcarbonyloxy) anthracene, 1- (t-butyl) ) -9,10-Bis (n-hexylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (benzoyloxy) anthracene, 1- (t-butyl) -9,10-bis (4) -(T-Butyl) -benzoyloxy) anthracene, 1- (t-butyl) -9,10-bis (2-naphthyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-) Propylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (isopropylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-butylcarbonyloxy) anthracene, 2- (T-Butyl) -9,10-bis (isobutylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (n-pentylcarbonyloxy) anthracene, 2- (t-butyl) -9, 10-bis (n-hexylcarbonyloxy) anthracene, 2- (t-butyl) -9,10-bis (benzoyloxy) anthracene, 2- (t-butyl) -9,10-bis (4- (t-t-) Butyl) -benzoyloxy) anthracene, 2- (t-butyl) -9,10-bis (2-naphthoyloxy) anthracene, 2-pentyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2- Pentyl-9,10-bis (isopropylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2- Pentyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (benzoyloxy) anthracene, 2 -Pentyl-9,10-bis (4- (t-butyl) -benzoyloxy) anthracene, and 2-pentyl-9,10-bis (2-na) Futoyloxy) Anthracene and the like can be mentioned.

An anthracene compound substituted with a halogen atom is also preferable as the (C) sensitizer. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the anthracene compound substituted with a halogen atom and preferable as the (C) sensitizer include 2-chloro-9,10-bis (acetyloxy) anthracene and 2-chloro-9,10-. Bis (propionyloxy) anthracene, 2-chloro-9,10-bis (n-propylcarbonyloxy) anthracene, 2-chloro-9,10-bis (isopropylcarbonyloxy) anthracene, 2-chloro-9,10-bis (N-butylcarbonyloxy) anthracene, 2-chloro-9,10-bis (isobutylcarbonyloxy) anthracene, 2-chloro-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-chloro-9,10 -Bis (n-hexylcarbonyloxy) anthracene, 2-chloro-9,10-bis (benzoyloxy) anthracene, 2-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 2-chloro-9, 10-bis (2-naphthoyloxy) anthracene, 1-chloro-9,10-bis (acetyloxy) anthracene, 1-chloro-9,10-bis (propionyloxy) anthracene, 1-chloro-9,10- Bis (n-propylcarbonyloxy) anthracene, 1-chloro-9,10-bis (isopropylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-butylcarbonyloxy) anthracene, 1-chloro-9, 10-bis (isobutylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-chloro- 9,10-bis (benzoyloxy) anthracene, 1-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 1-chloro-9,10-bis (2-naphthoyloxy) anthracene, 2-fluoro -9,10-bis (acetyloxy) anthracene, 2-fluoro-9,10-bis (propionyloxy) anthracene, 2-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 2-fluoro-9 , 10-bis (isopropylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (n-butylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene , 2-Fluoro-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (benzoyloxy) Anthracene, 2-fluoro-9,10-bis (4-methylbenzoyloxy) anthracene, 2-fluoro-9,10-bis (2-naphthoyloxy) anthracene, 1-fluoro-9,10-bis (acetyloxy) ) Anthracene, 1-fluoro-9,10-bis (propionyloxy) anthracene, 1-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isopropylcarbonyloxy) Anthracene, 1-fluoro-9,10-bis (n-butylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (n-pentylcarbonyl) Oxy) anthracene, 1-fluoro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (benzoyloxy) anthracene, 1-fluoro-9,10-bis (4-methyl) Benzoyloxy) anthracene, 1-fluoro-9,10-bis (2-naphthoyloxy) anthracene, 2-bromo-9,10-bis (acetyloxy) anthracene, 2-bromo-9,10-bis (propionyloxy) ) Anthracene, 2-bromo-9,10-bis (n-propylcarbonyloxy) anthracene, 2-bromo-9,10-bis (isopropylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-butyl) Carbonyloxy) anthracene, 2-bromo-9,10-bis (isobutylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n) -Hexylcarbonyloxy) anthracene, 2-bromo-9,10-bis (benzoyloxy) anthracene, 2-bromo-9,10-bis (4-methylbenzoyloxy) anthracene, 2-bromo-9,10-bis ( 2-naphthoyloxy) anthracene, 1-bromo-9,10-bis (acetyloxy) anthracene, 1-bromo-9,10-bis (propionyloxy) anthracene, 1-bromo-9,10-bi Su (n-propylcarbonyloxy) anthracene, 1-bromo-9,10-bis (isopropylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-butylcarbonyloxy) anthracene, 1-bromo-9, 10-Bis (isobutylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-bromo- 9,10-bis (benzoyloxy) anthracene, 1-bromo-9,10-bis (4-methylbenzoyloxy) anthracene, 1-bromo-9,10-bis (2-naphthoyloxy) anthracene and the like. Will be.

Further, an anthracene compound substituted with an alkoxy group is also preferable as the (C) sensitizer.
Specific examples of the anthracene compound substituted with an alkoxy group, which is preferable as the (C) sensitizer, include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-bis (n-). Propyloxy) anthracene, 9,10-bis (n-butyloxy) anthracene, 9,10-bis (n-pentyloxy) anthracene, 9,10-bis (isopentyloxyoxy) anthracene, 9,10-bis (n) -Hexyloxy) anthracene, 9,10-bis (n-heptyloxy) anthracene, 9,10-bis (n-octyloxy) anthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9- (n-propyloxy) anthracene, 9- (n-butyloxy) anthracene, 9- (n-pentyloxy) anthracene, 9- (isopentyloxyoxy) anthracene, 9- (n-hexyl). Oxy) anthracene, 9- (n-heptyloxy) anthracene, 9- (n-octyloxy) anthracene, 9- (2-ethylhexyloxy) anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9 , 10-Diethoxyanthracene, 2-methyl-9,10-bis (n-propyloxy) anthracene, 2-methyl-9,10-bis (n-butyloxy) anthracene, 2-methyl-9,10-bis ( n-pentyloxy) anthracene, 2-methyl-9,10-bis (isopentyloxyoxy) anthracene, 2-methyl-9,10-bis (n-hexyloxy) anthracene, 2-methyl-9,10-bis (N-Heptyloxy) anthracene, 2-methyl-9,10-bis (n-octyloxy) anthracene, 2-methyl-9,10-bis (2-ethylhexyloxy) anthracene, 2-ethyl-9,10- Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis (n-propyloxy) anthracene, 2-ethyl-9,10-bis (n-butyloxy) anthracene, 2- Ethyl-9,10-bis (n-pentyloxy) anthracene, 2-ethyl-9,10-bis (isopentyloxyoxy) anthracene, 2-ethyl-9,10-bis (n-hexyloxy) anthracene, 2 -Ethrace-9,10-bis (n-he) Petiloxy) anthracene, 2-ethyl-9,10-bis (n-octyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexyloxy) anthracene, 2-methyl-9-methoxyanthracene, 2-methyl -9-ethoxyanthracene, 2-methyl-9- (n-propyloxy) anthracene, 2-methyl-9- (n-butyloxy) anthracene, 2-methyl-9- (n-pentyloxy) anthracene, 2-methyl -9- (Isopentyloxyoxy) anthracene, 2-methyl-9- (n-hexyloxy) anthracene, 2-methyl-9- (n-heptyloxy) anthracene, 2-methyl-9- (n-octyloxy) ) Anthracene, 2-methyl-9- (2-ethylhexyloxy) anthracene, 2-ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9- (n-propyloxy) anthracene, 2 -Ethl-9- (n-butyloxy) anthracene, 2-ethyl-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-ethyl-9- (n-hexyl) Oxy) anthracene, 2-ethyl-9- (n-heptyloxy) anthracene, 2-ethyl-9- (n-octyloxy) anthracene, 2-ethyl-9- (2-ethylhexyloxy) anthracene, 2-chloro- 9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis (n-propyloxy) anthracene, 2-chloro-9,10-bis (n-butyloxy) Anthracene, 2-chloro-9,10-bis (n-pentyloxy) anthracene, 2-chloro-9,10-bis (isopentyloxyoxy) anthracene, 2-chloro-9,10-bis (n-hexyloxy) ) Anthracene, 2-chloro-9,10-bis (n-heptyloxy) anthracene, 2-chloro-9,10-bis (n-octyloxy) anthracene, 2-chloro-9,10-bis (2-ethylhexyl) Oxy) anthracene, 2-bromo-9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9,10-bis (n-propyloxy) anthracene, 2-bromo-9, 10-bis (n-butyloxy) anthracene, 2-bromo-9,10-bis (N-Pentyloxy) anthracene, 2-bromo-9,10-bis (isopentyloxyoxy) anthracene, 2-bromo-9,10-bis (n-hexyloxy) anthracene, 2-bromo-9,10- Bis (n-heptyloxy) anthracene, 2-bromo-9,10-bis (n-octyloxy) anthracene, 2-bromo-9,10-bis (2-ethylhexyloxy) anthracene, 2-chloro-9-methoxy Anthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9- (n-propyloxy) anthracene, 2-chloro-9- (n-butyloxy) anthracene, 2-chloro-9- (n-pentyloxy) Anthracene, 2-chloro-9- (isopentyloxyoxy) anthracene, 2-chloro-9- (n-hexyloxy) anthracene, 2-chloro-9- (n-heptyloxy) anthracene, 2-chloro-9- (N-octyloxy) anthracene, 2-chloro-9- (2-ethylhexyloxy) anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9- (n-propyl) Oxy) anthracene, 2-bromo-9- (n-butyloxy) anthracene, 2-bromo-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-bromo-9 -(N-Hexyloxy) anthracene, 2-bromo-9- (n-heptyloxy) anthracene, 2-bromo-9- (n-octyloxy) anthracene, and 2-bromo-9- (2-ethylhexyloxy). Anthracene and the like can be mentioned.

Among the anthracene compounds described above, 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, 9 from the viewpoint of ease of production and (C) performance as a sensitizer. , 10-bis (n-propylcarbonyloxy) anthracene, 9,10-bis (isopropylcarbonyloxy) anthracene, 9,10-bis (n-butylcarbonyloxy) anthracene, 9,10-bis (isobutylcarbonyloxy) anthracene , 9,10-bis (n-hexanoyloxy) anthracene, 9,10-bis (n-heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2) -Ethlhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene are preferred.

Specific examples of the compound containing a naphthacene ring and preferably used as the (C) sensitizer include
2-Methyl-5,11-dioxo-6,12-bis (acetyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2-methyl-5,11- Dioxo-6,12-bis (n-propylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6, 12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis ( n-Pentylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-hexylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-) Heptylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (acetyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2- Ethyl-5,11-dioxo-6,12-bis (n-propylcarbonyloxy) naphthalene, 2-ethyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis (n-pentylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-hexylcarbonyloxy) naphthacene, and 2-ethyl-5,11-dioxo-6. , 12-Bis (n-heptylbonyloxy) alkylcarbonyloxy group substituted naphthacene compounds such as naphthacene;
2-Methyl-5,11-dioxo-6,12-bis (benzoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (o-toluoleoxy) naphthacene, 2-methyl-5 , 11-dioxo-6,12-bis (m-toluoiloxy) naphthalene, 2-methyl-5,11-dioxo-6,12-bis (p-toluoiloxy) naphthalene, 2-methyl-5,11 -Dioxo-6,12-bis (α-naphthoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-naphthoyloxy) naphthacene, 2-ethyl-5,11-dioxo -6,12-bis (benzoyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (o-toluoiloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12- Bis (m-toluoleoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (p-toluoleoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis ( Aloyloxy group-substituted naphthacene compounds such as α-naphthoyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naphthoyloxy) naphthacene;
2-Methyl-5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphthacene, 2-methyl-5, 11-dioxo-6,12-bis (n-propyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 2-methyl-5,11- Dioxo-6,12-bis (n-butyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo- 6,12-bis (n-pentyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-hexyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo- 6,12-bis (n-heptyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-octyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis (methoxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis ( n-propyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-) Butyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-pentyloxy) Carbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-hexyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-heptyloxy) An alkoxycarbonyloxy group-substituted naphthacene compound such as carbonyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (n-octyloxycarbonyloxy) naphthacene;
2-Methyl-5,11-dioxo-6,12-bis (phenoxycarbonyloxy) naphthalene, 2-methyl-5,11-dioxo-6,12-bis (o-tolyloxycarbonyloxy) naphthalene, 2-methyl -5,11-dioxo-6,12-bis (m-tolyloxycarbonyloxy) naphthalene, 2-methyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthalene, 2-methyl -5,11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphthacene, 2-ethyl -5,11-dioxo-6,12-bis (phenoxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (o-tolyloxycarbonyloxy) naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis (m-tolyloxycarbonyloxy) naphthalene, 2-ethyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthalene, 2-ethyl-5, Aloyloxycarbonyl such as 11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphthacene. Examples thereof include oxy group-substituted naphthacene compounds.

Among the above compounds containing a naphthacene ring, 5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphthacene, 5,11- Dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (n-butylcarbonyl) Oxy) naphthacene, 5,11-dioxo-6,12-bis (n-pentylcarbonyloxy) naphthacene, and 5,11-dioxo-6,12-bis (n-heptanoyloxy) naphthacene are preferred.
(B) In terms of compatibility with the photopolymerizable compound, 5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene and 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) ) Naphthase, 5,11-dioxo-6,12-bis (n-butyryloxy) naphthacene, 5,11-dioxo-6,12-bis (n-valeryloxy) naphthacene, 5,11-dioxo-6,12-bis (Heptanoyloxy) Naphthalcene is preferred.

Specific examples of the compound containing a thioxanthene ring and preferably used as a (C) sensitizer include thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, and 2-one. Examples thereof include isopropyl-9H-thioxanthene-9-one, 1,4-dimethylthioxanthene-9-one, 3-methyl-9-oxo-9H-thioxanthene-2-ylacetate and the like.

The content of the sensitizer as the component (C) is, for example, 0.01 part by mass or more and 2000 parts by mass or less with respect to 100 parts by mass in total of the component (A) in the photosensitive composition, 0.01. It is preferably 1 part by mass or more and 1000 parts by mass or less, more preferably 0.1 part by mass or more and 150 parts by mass or less, and further preferably 0.3 parts by mass or more and 100 parts by mass or less.
When the total amount of the component (B) is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass, coloring due to absorption of the component (C) can be reduced, so that a cured product having good transparency or brightness can be obtained. Obtainable.

<(D) Colorant>
The photosensitive composition may or may not further contain the (D) colorant. By containing the colorant which is the component (D), the photosensitive composition is preferably used, for example, as a color filter forming application for a liquid crystal display. Further, the photosensitive composition according to the first aspect is preferably used for forming a black matrix in a color filter of a display device, for example, by containing a light-shielding agent as a colorant.

The (D) colorant contained in the photosensitive composition is not particularly limited, but is classified as Pigment in, for example, a color index (CI; The Society of Dyers and Colorists). It is preferable to use a compound having a color index (CI) number as described below.

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

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

Examples of suitably usable purple pigments include C.I. 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, and 50. Can be mentioned.

Examples of preferably usable red pigments include C.I. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is described.) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

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

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

Further, when imparting a light-shielding property to the photosensitive composition, it is preferable that the photosensitive composition contains a black pigment as the (D) colorant. The photosensitive composition containing a black pigment is suitably used for forming a black matrix or a black column spacer in a liquid crystal display panel, and forming a bank for partitioning a light emitting layer in an organic EL device.

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

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light-shielding properties. Further, resin-coated carbon black may be used.

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, it has less current leakage when used as a black matrix for liquid crystal display elements such as liquid crystal display displays, and is highly reliable. Can manufacture power consumption displays.

As the carbon black, carbon black that has been treated to introduce an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity as defined by Bronsted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group introduced into the carbon black may form a salt. The cation forming the salt with the acidic group is not particularly limited as long as it does not impair the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ions are preferable.

Among the carbon blacks that have been treated to introduce the acidic groups described above, carboxylic acid groups and carboxylic acid bases are used from the viewpoint of achieving high resistance of the light-shielding cured film formed by using the photosensitive composition. , A carbon black having one or more functional groups selected from the group consisting of a sulfonic acid group and a sulfonic acid base 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, etc., or an indirect substitution method using sulfite, hydrogen sulfite, etc.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method in which an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group are reacted 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 deprotecting carbon black after conducting a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

Among these methods, method 2) is preferable because the process of introducing an acidic group 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 aminobenzenesulfonic acid such as sulfanilic acid and aminobenzoic acid such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as it does not impair the object of the present invention. The number of moles of the acidic group introduced into the carbon black is preferably 1 mmol or more and 200 mmol or less, and more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

The carbon black into which an acidic group has been introduced may be coated with a resin.
When a 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 and insulating properties and low surface reflectance. It should be noted that the coating treatment with the resin does not cause any adverse effect on the dielectric constant of the light-shielding cured film formed by using the photosensitive composition. Examples of resins that can be used for coating carbon black include thermocurable resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, and polystyrene, polycarbonate, polyethylene terephthalate, and poly. Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulphon, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1% by mass or more and 30% by mass or less with respect to the total of the mass of the carbon black and the mass of the resin.

Further, as the black pigment, a perylene-based pigment can also be preferably used. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and a perylene-based pigment represented by the following formula (d-3). Examples include perylene-based pigments. As commercial products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene-based pigments.

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

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

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

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

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

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

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) are, for example, Japanese Patent Application Laid-Open No. 62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

In order to satisfactorily disperse the perylene-based pigment in the photosensitive composition, the average particle size of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less.

Further, the light-shielding agent may contain a lactam pigment. Examples of the lactam pigment include compounds represented by the following formula (d-4).

In formula (d-4), X ^d represents a double bond and is an E-form or a Z-form independently as geometric isomers, and R ^d9 is independently a hydrogen atom, a methyl group, a nitro group, and a methoxy. A group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, R ^d10 independently indicates a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 independently indicates a hydrogen atom. , Methyl group, or chlorine atom.
The compound represented by the formula (d-4) can be used alone or in combination of two or more.
R ^d9 is preferably bonded to the 6-position of the dihydroindron ring because the compound represented by the formula (d-4) can be easily produced, and R ^d11 is bonded to the 4-position of the dihydroindron ring. It is preferable to do. From the same viewpoint, R ^d9 , R ^d10 , and R ^d11 are preferably hydrogen atoms.
The compound represented by the formula (d-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but may be a single compound of any one of these, or these geometric isomers may be used. May be a mixture of.
The compound represented by the formula (d-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/0816224.

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

Further, fine particles containing silver-tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") are also preferably used as the black pigment. The AgSn alloy fine particles may contain AgSn alloy as a main component, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle size of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x in which a chemically stable AgSn alloy can be obtained is 1 ≦ x ≦ 10, and the range of x in which chemical stability and blackness can be obtained at the same time is. 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x above,
When x = 1, Ag / AgSn = 0.4762
When x = 3, 3.Ag / Ag3Sn = 0.7317
When x = 4, 4. Ag / Ag4Sn = 0.7843
When x = 10, 10 · Ag / Ag10Sn = 0.9008
Will be.
Therefore, this AgSn alloy becomes chemically stable when Ag is contained in an amount of 47.6% by mass or more and 90% by mass or less, and when Ag is contained in an amount of 73.17% by mass or more and 78.43% by mass or less. Chemical stability and blackness can be effectively obtained with respect to the amount.

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

The AgSn alloy fine particles have high insulating properties, but depending on the use of the photosensitive composition, the surface may be covered with an insulating film in order to further improve the insulating properties. As the material of such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, for example, silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (itria), titanium oxide (titania) and the like having insulating properties are preferably used. Be done.
Further, as the organic polymer compound, a resin having an insulating property, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound or the like is preferably used.

The thickness of the insulating film is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less in order to sufficiently enhance the insulating property of the surface of the AgSn alloy fine particles.
The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, it is preferable to use an alkoxide such as tetraethoxysilane or aluminum triethoxyde because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

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

Further dispersants may be used to uniformly disperse the colorants in the photosensitive composition. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the (D) colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.
In addition, corrosive gas due to the dispersant may be generated from the cured film. Therefore, it is also an example of a preferable embodiment that the pigment is dispersed without using a dispersant.

In the photosensitive composition, the pigment and the dye may be used in combination. This dye may be appropriately selected from known materials.
Examples of dyes applicable to the photosensitive composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like. be able to.
Further, these dyes can be raked (chlorinated) to be dispersed in an organic solvent or the like, and this can be used as the (D) colorant.
In addition to these dyes, for example, Japanese Patent Laid-Open Nos. 2013-225132, 2014-178477, 2013-137543, 2011-38085, 2014-197206, etc. The dyes and the like described can also be preferably used.

The amount of the colorant (D) used in the photosensitive composition can be appropriately selected as long as it does not impair the object of the present invention, and is typically 2% by mass with respect to the total mass of the solid content of the photosensitive composition. More than 75% by mass is preferable, and 3% by mass or more and 70% by mass or less is more preferable.

In particular, when a black matrix is formed using a photosensitive composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive composition so that the OD value per 1 μm of the black matrix film is 4 or more. .. When the OD value per 1 μm of the coating film in the black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display.

(D) When a pigment is used as the colorant, it is preferable to add the pigment to the photosensitive composition after preparing a dispersion liquid in which the pigment is dispersed at an appropriate concentration in the presence or absence of the dispersant.
In this specification, the amount of the above-mentioned pigment used can be defined as a value including the present dispersant.

<(E) Alkali-soluble resin>
The photosensitive composition according to the first aspect may contain a resin other than the resin used as the (B) photopolymerizable compound. Examples of the other resin include (E) an alkali-soluble resin, a resin whose solubility in a developing solution changes due to the action of an acid, and the like, and (E) an alkali-soluble resin is preferable. By blending (E) an alkali-soluble resin with the photosensitive composition, alkali developability can be imparted to the photosensitive composition.

In the present specification, the alkali-soluble resin means a resin film having a thickness of 1 μm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and KOH having a concentration of 0.05% by mass. A solvent that dissolves in a film thickness of 0.01 μm or more when immersed in an aqueous solution for 1 minute.

(E) Among the alkali-soluble resins, a polymer of a monomer having an ethylenically unsaturated double bond because of its excellent film-forming property and easy adjustment of the resin characteristics by selecting a monomer. Is preferable. Examples of the monomer having an ethylenically unsaturated double bond include (meth) allylic acid; (meth) allylic acid ester; (meth) allylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, and mesaconic acid. Itaconic acid, an anhydride of these dicarboxylic acids; such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol. Allyl compounds; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, And vinyl ethers such as vinyl allyl ether; vinyl butylate, vinylisobutyrate, vinyltrimethylacetate, vinyldiethylacetate, vinylvalate, vinylcaproate, vinylchloroacetate, vinyldichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, Vinyl esters such as vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene, Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyle , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethyl. Styrene or styrene derivatives such as styrene; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The (E) alkali-soluble resin, which is a polymer of a monomer having an ethylenically unsaturated double bond, usually contains a unit derived from an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids 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. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. .. The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5% by mass or more and 25% by mass or less, and 8% by mass or more and 16% by mass or less with respect to the mass of the resin. More preferred.

Among the polymers of monomers having an ethylenically unsaturated double bond, which are polymers of one or more types of monomers selected from the monomers exemplified above, (meth) acrylic acid and (meth) acrylic acid and (meth) ) A polymer of one or more monomers selected from acrylic acid esters is preferable. Hereinafter, a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester will be described.

The (meth) acrylic acid ester used in the preparation of a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is particularly suitable as long as it does not impair the object of the present invention. It is not limited, and is appropriately selected from known (meth) acrylic acid esters.

Preferable examples of the (meth) acrylic acid ester are linear or linear such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like. Branched chain alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) Examples thereof include acrylates, furfuryl (meth) acrylates; (meth) acrylic acid esters having a group having an epoxy group; and (meth) acrylic acid esters having a group having an alicyclic skeleton. Details of the (meth) acrylic acid ester having a group having an epoxy group and the (meth) acrylic acid ester having a group having an alicyclic skeleton will be described later.

Among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, the adhesion of the transparent insulating film formed by using the photosensitive composition to the substrate. A resin containing a unit derived from a (meth) acrylic acid ester having a group having an epoxy group is preferable because of its excellent mechanical strength.

The (meth) acrylic acid ester having a group having an epoxy group is a group having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group. It may be a (meth) acrylic acid ester having.

The (meth) acrylic acid ester having a group having an epoxy group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of (meth) acrylic acid esters having an aromatic group and having a group having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxy. Examples thereof include phenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

When the film formed by using the photosensitive composition is required to be transparent, the (meth) acrylic acid having a group having an epoxy group is preferably one containing no aromatic group.

Examples of (meth) acrylic acid esters having a group having a chain aliphatic epoxy group include ester groups (-O-CO) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. Examples thereof include a (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (−O−) in −). The chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more 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 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.

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

Epoxy groups in polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, including units derived from (meth) acrylic acid esters having groups with epoxy groups. The content of the unit derived from the (meth) acrylic acid ester having a group having a group is preferably 1% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 80% by mass or less with respect to the weight of the resin.

Further, among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, it is easy to form a transparent insulating film having excellent transparency by using a photosensitive composition. Therefore, a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable.

In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton is a group having an alicyclic epoxy group even if it is a group having an alicyclic hydrocarbon group. You may. 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, a tetracyclododecyl group and the like.

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, the (meth) acrylic acid ester having a group having an alicyclic hydrocarbon group is, for example, the following formulas (d1-1) to (d1-). Examples thereof include the compound represented by 8). Among these, the compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and the compounds represented by the following formulas (d1-3) or (d1-4) are more preferable.

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and R ^d3 represents a hydrogen atom or a carbon atom number. Indicates an alkyl group of 1 or more and 5 or less. As R ^d2 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^d3 , a methyl group and an ethyl group are preferable.

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, specific examples of the (meth) acrylic acid ester having a group having an alicyclic epoxy group include the following formulas (d2-1) to ( Examples thereof include the compound represented by d2-16). Among these, in order to make the developability of the photosensitive composition appropriate, the compounds represented by the following formulas (d2-1) to (d2-6) are preferable, and the following formulas (d2-1) to 2-6 are preferable. The compound represented by (d2-4) is more preferable.

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less ^{carbon atoms, and R d6} represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 10 or less carbon atoms. It indicates a hydrocarbon group, and n indicates an integer of 0 or more and 10 or less. As R ^d5 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. Examples of R ^d6 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, -CH ₂ -Ph-CH _2- (Ph is (Indicating a phenylene group) is preferable.

A resin containing a unit derived from a (meth) acrylic acid ester in which a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester has a group having an alicyclic skeleton. In the above case, the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5% by mass or more and 95% by mass or less, and 10% by mass or more and 90% by mass or less. More preferably, it is more preferably 30% by mass or more and 70% by mass or less.

In addition, a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, which comprises a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton. Among them, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group is preferable. The film formed by using the photosensitive composition containing the (E) alkali-soluble resin has excellent adhesion to the substrate. Further, when such a resin is used, it is possible to cause a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, a film formed by causing a self-reaction between a carboxyl group and an alicyclic epoxy group by using a method of heating the film or the like. Mechanical properties such as hardness can be improved.

In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth) acrylic acid in the resin. The amount of is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a group having an alicyclic epoxy group in the resin is used. The amount of the unit derived from the (meth) acrylic acid ester contained is preferably 1% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.

Selected from (meth) acrylic acid and (meth) acrylic acid esters, including units derived from (meth) acrylic acid and units derived from (meth) acrylic acid esters having a group having an alicyclic epoxy group. Among the polymers of one or more types of monomers, a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having an alicyclic hydrocarbon group, and an alicyclic epoxy. A resin containing a unit derived from a (meth) acrylic acid ester having a group having a group is preferable.

It is derived from a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a (meth) acrylic acid ester having a group having an alicyclic epoxy group. In the resin containing the unit, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1% by mass or more and 95% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. It is derived from a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a (meth) acrylic acid ester having a group having an alicyclic epoxy group. In the resin containing the unit, the amount of the unit derived from the (meth) acrylic acid ester having an alicyclic hydrocarbon group in the resin is preferably 1% by mass or more and 95% by mass or less, preferably 10% by mass or more and 70% by mass. % Or less is more preferable. It is derived from a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a (meth) acrylic acid ester having a group having an alicyclic epoxy group. In the resin containing the unit, the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic epoxy group in the resin is preferably 1% by mass or more and 95% by mass or less, preferably 30% by mass or more. More preferably, it is 80% by mass or less.

(E) The mass average molecular weight of the alkali-soluble resin (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene. The same applies in the present specification) is preferably 2000 or more and 200,000 or less, preferably 2000 or more and 18,000 or less. Is more preferable. Within the above range, it tends to be easy to balance the film forming ability of the photosensitive composition and the developability after exposure.

When the photosensitive composition contains a resin such as (E) alkali-soluble resin, the content of the resin such as (E) alkali-soluble resin in the photosensitive composition is the mass of components other than the solvent in the photosensitive composition. 15% by mass or more and 95% by mass or less are preferable, 35% by mass or more and 85% by mass or less are more preferable, and 50% by mass or more and 70% by mass or less are particularly preferable.

<Other ingredients>
The photosensitive composition according to the first aspect may contain various additives, if necessary. Specifically, solvents, sensitizers, curing accelerators, photocrosslinkers, dispersion aids, fillers, fillers, adhesion promoters, silane coupling agents, antistatic agents, antioxidants, UV absorbers, agglomerates. Examples thereof include an inhibitor, a thermal polymerization inhibitor, a plasticizer, a flame retardant, a defoaming agent, a leveling agent, a filler, a thickener, a thixophilic imparting agent, and a surfactant.

The photosensitive composition according to the first aspect may be prepared by dispersing and dissolving each component in a solvent, but if the component (B) is liquid, the solvent may not be used. When a solvent is contained, examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- Propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri. (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono (Poly) alkylene glycol monoalkyl ether acetates such as ethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone. Classes: Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybuty Lupropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide and other amides and the like. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (MEDG), cyclohexanone, 3-methoxybutyl acetate. (MBA) is preferable because it exhibits excellent solubility in the above-mentioned components (A) and (B) and can improve the dispersibility of the above-mentioned component (D), and is preferably propylene glycol monomethyl ether. It is particularly preferable to use acetate, 3-methoxybutyl acetate. The solvent may be appropriately determined depending on the intended use of the photosensitive composition, but as an example, 50 parts by mass or more and 900 parts by mass with respect to the total mass of 100 parts by mass of the components other than the solvent in the photosensitive composition. The following degrees can be mentioned.

Examples of the thermal polymerization inhibitor used in the photosensitive composition according to the first aspect include hydroquinone, hydroquinone monoethyl ether and the like. Further, examples of the defoaming agent include silicone-based and fluorine-based compounds, and examples of the surfactant include anionic, cationic and nonionic compounds.

[Method for preparing photosensitive composition]
In the photosensitive composition according to the first aspect, the photosensitive composition is prepared by uniformly stirring and mixing each of the above components, uniformly dissolving and dispersing the photosensitive composition, and then, if necessary, a membrane filter having a size of 0.2 μm or less. It can be prepared by filtering with a filter such as a membrane filter having a thickness of 0.5 μm or more and 1 μm or less.

<< Cured product forming method and cured product >>
The cured product forming method is the same as the conventional cured product forming method formed by using the photosensitive composition, except that the above-mentioned photosensitive composition is used.

The method for forming the cured product using the above-mentioned photosensitive composition is not particularly limited, and can be appropriately selected from the conventionally adopted methods. The cured product is formed as a molded product having a desired shape by controlling the shape of the coating film at the time of applying the photosensitive composition and by combining regioselective exposure and development. As a suitable cured product forming method, a method including a coating film forming step of forming a coating film using the above-mentioned photosensitive composition and an exposure step of exposing the coating film to the above-mentioned coating film can be mentioned. When the exposure is regioselective, the exposed coating may be developed with a developer to obtain a patterned cured product.

First, in the coating film forming step, for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), a dispenser, an inkjet, or a spray is placed on a substrate on which a cured product should be formed. The photosensitive composition according to the present invention is applied using a non-contact coating device such as screen printing or a curtain flow coater, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.
For convenience, the droplets piled up on the substrate, the photosensitive composition embedded in the concave portions of the substrate having irregularities, the photosensitive composition filled in the concave portions of the mold, and the like are also referred to as "coating film". ..

The formed coating film is then subjected to an exposure step. The light source is not particularly limited in the exposure process, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an LED. Using such a light source, ArF excimer laser coating, KrF excimer laser, _{F 2} excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beams, X-rays, soft X-ray, g-line, i-line , H line, j line, k line and other radiation or electromagnetic waves are applied to expose the coating film. The exposure to the coating film may be regioselective via a negative mask. Exposure dose varies depending on the composition of the photosensitive composition, for example, 10 mJ / cm ² or more 2000 mJ / cm ² or less are preferred, 100 mJ / cm ² or more 1500 mJ / cm ² and more preferably less, 500 mJ / cm ² or more 1200 mJ / cm ² or less is more preferable.
From the viewpoint of energy saving and reduction of environmental load, LED is preferable as the light source. Examples of the wavelength used in the exposure by the LED include those in the UV region such as 365 to 405 nm, more specifically 385 nm and 395 nm and 405 nm. In general, the energy dose emitted by the LED tends to be small. However, when the photosensitive composition described above contains (C) a sensitizer together with the above-mentioned (A) photopolymerization initiator, it has excellent sensitivity, so that exposure using an LED as a light source is sufficient. It is possible to effectively obtain a cured product having good properties.

The exposed coating film is developed as needed.
The above-mentioned photosensitive composition is difficult to be excessively dissolved in an alkaline developer after exposure. Therefore, by using the above-mentioned photosensitive composition, it is easy to form a well-shaped patterned cured product in which the exposed portion is a convex portion and the unexposed portion is a concave portion.

In the developing step, the exposed coating film is developed with a developing solution to form a cured product patterned into a desired shape. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Then, if necessary, the cured product after exposure or the patterned cured product after development may be post-baked to further heat cure. The temperature of the post bake is preferably 150 ° C. or higher and 270 ° C. or lower.

The cured product is formed using the above-mentioned photosensitive composition. The cured product is preferably an insulating film or a protective film laminated on the photoresist film. When the photosensitive composition does not contain the colorant (D) and is transparent, the cured product has a wavelength in the range of 400 nm or more and 650 nm or less when a sample having a thickness of 3.5 μm (optical path length 3.5 μm) is used. The average value of the transmittance for light rays is usually 90% or more, preferably 93% or more, and more preferably 95% or more. As described above, since the cured product has excellent transmittance, it is suitable as an insulating film for display devices that require an insulating film having excellent transparency, such as an in-cell touch panel type liquid crystal display device and a UHA (Ultra High Aperture) panel. Used for.

Further, when the above-mentioned photosensitive composition is exposed through a halftone mask to form a patterned cured film, the patterned cured product to be formed includes a full-tone exposed portion and a halftone. It is possible to secure a sufficient height of the halftone exposed part while making a sufficient difference in height from the exposed part. Therefore, the cured film formed by using the above-mentioned photosensitive composition is suitably used as a spacer used in a display panel such as a liquid crystal display panel, particularly a black column spacer.

≪Photosensitive adhesive and bonding method≫
The above-mentioned photosensitive composition can be suitably used as a photosensitive adhesive. When the photosensitive composition is used as the photosensitive adhesive, the photosensitive composition may or may not contain the colorant (D) depending on the purpose of imparting visibility and light-shielding property.
As described above, the photosensitive composition used as a photosensitive adhesive has excellent curability (particularly surface curability). Therefore, when the above-mentioned photosensitive composition is used as a photosensitive adhesive, the adhesive is rapidly cured by exposure.
In particular, an adhesive layer having a film thickness of 1 μm or more and 500 μm or less (preferably a film thickness of 3 μm or more and 200 μm or less, more preferably 5 μm or more and 100 μm or less, still more preferably 8 μm or more and 50 μm or less) is formed and bonded. In some cases, the above photosensitive adhesives are preferably used.

In particular, in the manufacture of sealing materials for panels such as organic EL or liquid crystal display elements, automobiles, motorcycles, bicycles, railroad vehicles, aircraft, ships, various building materials, and various products by industrial robots. If the joining work such as welding, screwing, and screwing is changed to the above-mentioned bonding using the photosensitive adhesive, the weight of the finished finished product to be joined can be reduced and metal fatigue when joining by screwing or screwing can be achieved. There are various merits such as no cutting of screws and screws due to the above, and no corrosion due to battery curing when dissimilar metals are joined.

The bonding method using the above-mentioned photosensitive adhesive is not particularly limited. The above-mentioned photosensitive adhesive can be used in the method of adhering the surface to be adhered in various articles.
As a typical bonding method,
Examples thereof include a method of forming an adhesive layer made of a photosensitive adhesive on one or both of facing surfaces to be adhered, and curing the adhesive layer by exposure.

The method for forming the adhesive layer made of the photosensitive adhesive is not particularly limited. Typically, a photosensitive adhesive is applied to one or both of the opposing surfaces to be adhered to form an adhesive layer.
Further, the photosensitive adhesive may be injected into the gap in a state where a gap having a desired width is formed between the surfaces to be adhered.

The number of articles to be bonded may be one or a plurality of two or more. When the material of the article to be bonded is flexible and flexible, the number of articles to be bonded may be one. An example of the case where the number of articles to be bonded is one is a case where one rectangular plastic plate is rolled into a cylindrical shape and the joint portion of the plastic plate is bonded.

The exposure is performed in the same manner as the formation of the cured film described above. When the article to be bonded is transparent, the method of irradiating the adhesive layer with the exposure light is not particularly limited. In this case, the adhesive layer may be irradiated with the exposure light while transmitting the article to be bonded, or the exposure light may be irradiated so that the exposure light is incident from the end face of the adhesive layer.
When the article to be bonded is made of an opaque material such as metal, the exposure is performed so that the exposure light is incident from the end face of the adhesive layer.

≪Other uses≫
The above-mentioned photosensitive composition can be used for various applications in which a photosensitive composition has been conventionally used, such as formation of an etching mask in semiconductor processing, glass processing, and the like.
Further, the above-mentioned photosensitive composition can also be applied to the formation of a photosensitive composition layer in a so-called 3D printing three-dimensional modeling method including a step of forming a photosensitive composition layer.
The lamination of the layers cured by exposure in 3D printing is so-called self-adhesion to the layer of the cured product formed by using the photosensitive composition. Therefore, a three-dimensional modeling method by 3D printing using a photosensitive adhesive composed of the above-mentioned photosensitive composition is also included in the above-mentioned bonding method using a photosensitive adhesive as one aspect.
Since the above-mentioned photosensitive composition has excellent curability (particularly surface curability), even if the film thickness of the photosensitive composition layer is increased, the photosensitive composition layer can be satisfactorily cured by exposure in a short time. can. Therefore, when the above-mentioned photosensitive composition is applied to three-dimensional modeling by 3D printing, the number of times the photosensitive composition layer is laminated and the number of exposures can be reduced by increasing the thickness of the photosensitive composition layer. It is possible to create a three-dimensional model having a desired shape in a short time.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[Synthesis Example 1]
Compound 1 represented by the following formula was synthesized.

(Synthesis of 9,9-di-n-propylfluorene)
6.64 g (40 mmol) of fluorene was dissolved in 27 mL of THF. To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a sodium hydroxide aqueous solution having a concentration of 50% by mass were gradually added under a nitrogen atmosphere. bottom. The obtained mixture was stirred at 80 ° C. for 3 hours to carry out a reaction. After adding 33 g of ethyl acetate and 33 g of water to the mixture after the reaction, the mixture was separated into an organic phase and an aqueous phase. After dehydrating the obtained organic phase with anhydrous sodium sulfate, the solvent was removed from the organic phase using a rotary evaporator to obtain 8.32 g (yield 83%) of 9,9-di-n-propylfluorene. ..

(Synthesis of 2- (2-fluorobenzoyl) -9,9-di-n-propylfluorene)
10.02 g (40 mmol) of 9,9-di-n-propylfluorene and 5.87 g (44 mmol) of aluminum chloride were dissolved in 40 mL of dichloromethane. 6.98 g (44 mmol) of 2-fluorobenzoyl chloride was added dropwise into the dichloromethane solution at a temperature of 5 ° C. or lower while cooling the dichloromethane solution in an ice bath. After the dropping, the temperature of the reaction solution was raised to room temperature over 1 hour while stirring the reaction solution, and then the reaction was continued at room temperature for 3 hours.

The obtained reaction solution was added dropwise to a beaker containing 300 mL of ice water. After transferring the mixture in the beaker to a separating funnel, 200 mL of ethyl acetate was added to the separating funnel and the product was extracted into the organic phase. After separating the organic phase, the product in the aqueous phase was further extracted with 100 mL of ethyl acetate. The organic phase obtained by the two extractions was washed with 300 mL of a 10% aqueous sodium carbonate solution and then with 300 mL of water. The washed organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off from the organic phase using a rotary evaporator to obtain an oily substance. Purify the oily substance by silica gel column chromatography (developing solvent, ethyl acetate: n-hexane = 1: 1 (mass ratio)) to make a pale yellow solid (2- (2-fluorobenzoyl) -9,9-). 14.20 g (yield 95%) of di-n-propylfluorene was obtained.

(Synthesis of 2-fluorophenyl (9,9-di-n-propylfluoren-2-yl) ketooxime ester)
After dissolving 7.45 g (20 mmol) of the obtained pale yellow solid and 1.5 g (21 mmol) of hydroxylamine hydrochloride in 100 mL of ethanol, the ethanol solution was refluxed for 2 hours. After refluxing, ethanol was distilled off from the reaction solution, and then the residue was washed with water. After dissolving the washed residue in ethyl acetate, the ethyl acetate solution was dried over magnesium sulfate. Ethyl acetate was removed from the dried ethyl acetate solution using a rotary evaporator to obtain an oxime (2-fluorophenyl (9,9-di-n-propylfluoren-2-yl) ketooxime) as a residue. .. After dissolving the obtained oxime body in 60 mL of THF, acetyl chloride (3.45 g, 44 mmol) was added to THF, and the reaction was carried out under stirring. After the reaction, triethylamine (4.7 g, 46 mmol) was added dropwise to the reaction solution at room temperature. Sedimentation of salt was confirmed with the dropping. After stirring the reaction solution to which triethylamine was added for 2 hours, 40 ml of water was added to the reaction solution. The product in the reaction was then extracted with 40 mL of ethyl acetate. The organic phase was washed twice with 40 mL of water and then twice with 40 mL of saturated aqueous potassium carbonate solution. The washed organic phase was dried over magnesium sulfate, and then the solvent was removed from the organic phase using a rotary evaporator to obtain a residue. The residue is purified by silica gel column chromatography (developing solvent, ethyl acetate: n-hexane = 1: 1 (mass ratio)) to be a pale yellow solid (2-fluorophenyl (9,9-di-n-propyl). Fluoren-2-yl) ketooxime ester), 6.79 g (15.80 mmol, 79% yield) was obtained.

(Synthesis of Compound 1)
The resulting pale yellow solid 6.44 g (15.0 mmol) of the ones placed in dimethyl sulfoxide _{(DMSO) (85mL), K} 2 CO 3 6.23g (45.0mmol) and 2,2,3, Add 2.05 g (15.5 mmol) of 3-tetrafluoro-1-propanol. The reaction mixture was heated to 40 ° C. and stirred overnight. After cooling to room temperature, the obtained reaction solution was added dropwise to a beaker containing 150 mL of ice water. After transferring the mixture in the beaker to a separating funnel, 100 mL of ethyl acetate was added to the separating funnel and the product was extracted into the organic phase. After separating the organic phase, the product in the aqueous phase was further extracted with 50 mL of ethyl acetate. The organic phase obtained by the two extractions was washed with 150 mL of a 10 mass% sodium carbonate aqueous solution and then with 150 mL of water. The washed organic phase is dried over anhydrous magnesium sulfate, and then the solvent is distilled off from the organic phase using a rotary evaporator to obtain 6.07 g (11.2 mmol, yield 75%) of compound 1 as a pale yellow solid. Obtained.

^{The measurement results of 1} H-NMR of Compound 1 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 7.65-7.73 (m, 2H), 7.63 (m, 1H), 7.42-7.53 (m, 1H), 7. 15-7.38 (m, 6H), 7.00 (d, 1H), 5.60 (t, 1H), 4.30 (bs, 1H), 2.07 (s, 3H), 1.88 (M, 4H), 0.71 (m, 10H).

合成例１に記載の方法について、９，９−ジ−ｎ−プロピルフルオレンを２段階でアシル化する工程において、２−フルオロベンゾイルクロライド６．９８ｇ（４４ｍｍｏｌ）を２−フルオロフェニル酢酸クロライド７．５９ｇ（４４ｍｍｏｌ）に変更すること、及び塩酸ヒドロキシルアミン１．５ｇ（２１．０ｍｍｏｌ）を亜硝酸イソブチル２．１８ｇ（２１．０ｍｍｏｌ）に変更すること以外は、合成例１と同様にして、９，９−ジ−ｎ−プロピルフルオレンから上記式で表される化合物２を６．４２ｇ（１１．２７ｍｍｏｌ、収率７５％）得た。化合物２の^１Ｈ−ＮＭＲの測定結果は以下の通りであった。
^１Ｈ−ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ_３，ｐｐｍ）：７．８１−７．９０（ｍ，２Ｈ），７．６６（ｍ，１Ｈ），７．５０−７．６０（ｍ，１Ｈ），７．０５−７．３８（ｍ，７Ｈ），５．６７（ｔ，１Ｈ），４．３６（ｂｓ，２Ｈ），２．１５（ｓ，３Ｈ），１．９０（ｍ，４Ｈ），０．７３（ｍ，１０Ｈ）． [Synthesis Example 2]
(Synthesis of compound 2)

Regarding the method described in Synthesis Example 1, in the step of acylating 9,9-di-n-propylfluorene in two steps, 6.98 g (44 mmol) of 2-fluorobenzoyl chloride was added to 7.59 g of 2-fluorophenylacetate chloride. 9,9 in the same manner as in Synthesis Example 1, except that the content is changed to (44 mmol) and 1.5 g (21.0 mmol) of hydroxylamine hydrochloride is changed to 2.18 g (21.0 mmol) of isobutyl nitrite. From −di-n-propylfluorene, 6.42 g (11.27 mmol, yield 75%) of compound 2 represented by the above formula was obtained. ^{The measurement results of 1} H-NMR of Compound 2 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 7.81-7.90 (m, 2H), 7.66 (m, 1H), 7.50-7.60 (m, 1H), 7. 05-7.38 (m, 7H), 5.67 (t, 1H), 4.36 (bs, 2H), 2.15 (s, 3H), 1.90 (m, 4H), 0.73 (M, 10H).

合成例１に記載の方法について、９，９−ジ−ｎ−プロピルフルオレンを２段階でアシル化する工程において、２−フルオロベンゾイルクロライド６．９８ｇ（４４ｍｍｏｌ）を２−フルオロベンゾイルクロライド６．９８ｇ（４４ｍｍｏｌ）とｏ−トルイルクロライド６．８０ｇ（４４ｍｍｏｌ）とに変えること以外は、合成例１と同様にして、９，９−ジ−ｎ−プロピルフルオレンから上記式で表される化合物３を７．７８ｇ（１１．８０ｍｍｏｌ、収率７９％）得た。化合物３の^１Ｈ−ＮＭＲの測定結果は以下の通りであった。
^１Ｈ−ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ_３，ｐｐｍ）：７．７５（ｓ，１Ｈ），７．７０（ｄ，１Ｈ），７．６０（ｍ，１Ｈ），７．４０−７．５５（ｍ，６Ｈ），７．２０−７．３５（ｍ，５Ｈ），５．６５（ｔ，１Ｈ），４．３５（ｂｓ，２Ｈ），２．２１（ｓ，３Ｈ），２．０８（ｓ，３Ｈ），１．９４（ｍ，４Ｈ），０．７２（ｍ，１０Ｈ）． [Synthesis Example 3]
(Synthesis of Compound 3)

Regarding the method described in Synthesis Example 1, in the step of acylating 9,9-di-n-propylfluorene in two steps, 6.98 g (44 mmol) of 2-fluorobenzoyl chloride was added to 6.98 g of 2-fluorobenzoyl chloride (44 mmol). Compound 3 represented by the above formula from 9,9-di-n-propylfluorene in the same manner as in Synthesis Example 1, except that it is changed to 6.80 g (44 mmol) of o-toluyl chloride (44 mmol). 78 g (11.80 mmol, 79% yield) was obtained. ^{The measurement results of 1} H-NMR of Compound 3 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 7.75 (s, 1H), 7.70 (d, 1H), 7.60 (m, 1H), 7.40-7.55 (m, 6H), 7.20-7.35 (m, 5H), 5.65 (t, 1H), 4.35 (bs, 2H), 2.21 (s, 3H), 2.08 (s, 3H) ), 1.94 (m, 4H), 0.72 (m, 10H).

[Examples 1 to 3 and Comparative Examples 1 to 3]
The components (A), (B), and (C) of the types and amounts shown in Table 1 below were uniformly mixed to obtain photosensitive compositions of Examples and Comparative Examples.
In Examples 1 to 3, compounds 1 to 3 obtained in the above synthesis examples were used as the (A) photopolymerization initiator, respectively.

On the other hand, in Comparative Examples 1 to 3, comparative compounds 1 to 3 represented by the following formulas were used, respectively.

Further, in each Example and Comparative Example, the acylphosphine oxide-based photopolymerization initiator compound (A) represented by the following formula as another photopolymerization initiator (A') other than the compound represented by the above formula (1). '-1) was used.

In each Example and Comparative Example, propylene oxide-modified neopentyl glycol diacrylate (trade name: EBECRYL145; manufactured by Dycel Ornex) was used as the (B) photopolymerizable compound.
(C) 2-Isopropyl-9H-thioxanthene-9-one was used as a sensitizer.

<Evaluation of tackiness in LED exposure (wavelength 405 nm) and broadband exposure>
After dropping one drop of the obtained photosensitive composition onto the substrate with a dropper,
^{(1) at 1000 mJ / cm 2} using a commercially available LED lamp (wavelength 405 nm) for 120 seconds, or (2) using an exposure machine (trade name TME-150RTO; manufactured by Topcon, light source: ultrahigh pressure mercury lamp). The droplets (thickness 10 to 20 μm) of the photosensitive composition were irradiated with broadband light.
The tack (stickiness) of the exposed droplets was evaluated based on the following evaluation criteria 1 to 5.
1: Did not cure.
2: There is a solid substance, but it was easily removed by wiping it off with a wiper.
3: Even if it was wiped off with a wiper, it partially adhered to the glass.
4: There was tack, but the inside of the droplet was cured.
5: There was almost no tack.
The evaluation results are shown in Table 1.

As is clear from the results shown in Table 1, in the LED exposure of 405 nm, the curing was insufficient in Comparative Examples 1 to 3, while the curing progressed in Examples 1 to 3 although there was a tack. I understand.
Further, in the broadband exposure, although the curing progressed in Comparative Examples 1 to 3, the tack remained, whereas in Examples 1 to 3, the curing progressed sufficiently and there was almost no tack.

Claims (11)

A photosensitive composition containing (A) a photopolymerization initiator and (B) a photopolymerizable compound, wherein the (A) photopolymerization initiator is the following formula (1):.

(In the above formula (1), R ^a1 is an independently hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 and R ^a3 are chain-like groups which may have a substituent, respectively. It is an alkyl group, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom ( excluding a polymerizable group as ^{Ra 2} and Ra ³ ). R ^a2 and R ^a3 may be bonded to each other to form a ring, R ^a4 is a monovalent organic group, and R ^a5 may have a hydrogen atom or a substituent and has 1 carbon atom. It is an aryl group which may have an aliphatic hydrocarbon group of 20 or more or a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.
Including compounds represented by
The compounds represented by the formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C −.
3) R ^a5 is a substituent containing a group represented by _{HX 2} C −.
A photosensitive composition that satisfies at least one of the above (where X is an independent halogen atom). A photosensitive composition containing (A) a photopolymerization initiator and (B) a photopolymerizable compound, wherein the (A) photopolymerization initiator is the following formula (1):.

(In the above formula (1), R ^a1 Are each independently a hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 And R ^a3 Is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. ^a2 And R ^a3 May be coupled to each other to form a ring, R ^a4 Is a monovalent organic group, R ^a5 Is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n1 is an integer of 0 or more and 4 or less. Yes, n2 is 0 or 1. )
Including compounds represented by (however, the following compounds A1 and A2 are excluded).
The compounds represented by the formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 or more and 4 or less, and R ^a1 At least one of HX ₂ C- or H ₂ It is a substituent containing a group represented by XC-.
2) R ^a4 Is HX ₂ It is a substituent containing a group represented by C-.
3) R ^a5 Is HX ₂ It is a substituent containing a group represented by C-.
A photosensitive composition that satisfies at least one of the above (where X is an independent halogen atom).

When the 1), halogenated including the ^{R a1} is _HX 2 C-or _H 2 halogenated alkoxy group containing a group represented by the XC, or _HX 2 C-or _H 2 group represented by XC A group having an alkoxy group
Wherein 2) or 3) when the ^{R a4} or ^{R a5} is _HX 2 C - is a group having a halogenated alkoxy group containing a group represented by The photosensitive composition according to claim 1 or 2. The photosensitive composition according to claim 3 , wherein the group having a halogenated alkoxy group is an aromatic group substituted with a halogenated alkoxy group. The photosensitive composition according to claim 4 , wherein the aromatic group substituted with the halogenated alkoxy group is a group represented by the following formula (1-a).

(In the formula ^{(1-a), R a6} is a halogenated alkyl group containing a group represented by _HX 2 C-or _H 2 ^{XC, R a7} is a monovalent substituent, and * It is a combiner, n3 is 1 or 2, and n3 + n4 is an integer of 1 or more and 5 or less.) The photosensitive composition according to any one of claims 1 to 5 , wherein X is a fluorine atom. A photosensitive composition containing (A) a photopolymerization initiator and (B) a photopolymerizable compound, wherein the (A) photopolymerization initiator is the following formula (1):.

(In the above formula (1), R ^a1 is an independently hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 and R ^a3 are chain-like groups which may have a substituent, respectively. It is an alkyl group, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and Ra ² and Ra ³ are bonded to each other to form a ring. R ^a4 may be a monovalent organic group, and R ^a5 may have a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or a substituent. It may be an aryl group, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.)
Including compounds represented by
The compounds represented by the formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
3) R ^a5 is a substituent containing a group represented by _{HX 2} C- or H _{2 X C-.}
Satisfy at least one of (where X is an independent halogen atom),
(A) the photopolymerization initiator further comprises an acylphosphine oxide-based photopolymerization initiator, sensitive light composition. The following formula (1):

(In the above formula (1), R ^a1 is an independently hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 and R ^a3 are chain-like groups which may have a substituent, respectively. It is an alkyl group, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom ( excluding a polymerizable group as ^{Ra 2} and Ra ³ ). R ^a2 and R ^a3 may be bonded to each other to form a ring, R ^a4 is a monovalent organic group, and R ^a5 may have a hydrogen atom or a substituent and has 1 carbon atom. It is an aryl group which may have an aliphatic hydrocarbon group of 20 or more or a substituent, n1 is an integer of 0 or more and 4 or less, and n2 is 0 or 1.
The compounds represented by the above formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 to ^4, at least one of ^{R a1} is a substituent containing a group represented by _HX 2 C-or _H 2 XC.
2) R ^a4 is a substituent containing a group represented by _{HX 2} C −.
3) R ^a5 is a substituent containing a group represented by _{HX 2} C −.
A compound that satisfies at least one of the above (where X is an independent halogen atom). The following formula (1):

(In the above formula (1), R ^a1 Are each independently a hydrogen atom, a nitro group, or a monovalent organic group, and R ^a2 And R ^a3 Is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. ^a2 And R ^a3 May be coupled to each other to form a ring, R ^a4 Is a monovalent organic group, R ^a5 Is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n1 is an integer of 0 or more and 4 or less. Yes, n2 is 0 or 1. )
The compounds represented by the above formula (1) are the following 1) to 3) :.
1) n1 is an integer of 1 or more and 4 or less, and R ^a1 At least one of HX ₂ C- or H ₂ It is a substituent containing a group represented by XC-.
2) R ^a4 Is HX ₂ It is a substituent containing a group represented by C-.
3) R ^a5 Is HX ₂ It is a substituent containing a group represented by C-.
A compound that satisfies at least one of the above (where X is a halogen atom independently of each other) (excluding the following compounds A1 and A2).

In the case of 1) above, the R ^a1 Is HX ₂ C- or H ₂ Halogenated alkoxy group containing a group represented by XC-, or HX ₂ C- or H ₂ A group having a halogenated alkoxy group including a group represented by XC-.
In the case of 2) or 3), the R ^a4 Or R ^a5 Is HX ₂ The compound according to claim 8 or 9, which is a group having a halogenated alkoxy group including a group represented by C-. A photopolymerization initiator comprising the compound according to any one of claims 8 to 10.