JP6088105B1 - Photosensitive composition, pattern forming method, cured product, and display device - Google Patents

Abstract

[PROBLEMS] To provide a photosensitive composition having sufficient sensitivity to exposure and providing a cured product having sufficient transmittance upon curing, a pattern forming method using the photosensitive composition, and curing formed using the photosensitive composition. And a display device including a cured product. A photosensitive composition comprising a photopolymerization initiator (A1) represented by the formula (1) having no nitro group and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. . In formula (1), R1 is a hydrogen atom or a monovalent organic group, R2 and R3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or R2 and R3 may be bonded to each other to form a ring, R4 is an organic group having a specific cyclic structure, R5 is a hydrogen atom, or a carbon atom that may have a substituent. The alkyl group of number 1-11, or the aryl group which may have a substituent, n is an integer of 0-4. [Selection figure] None

Description

  The present invention relates to a photosensitive composition, a pattern forming method using the photosensitive composition, a cured product formed using the photosensitive composition, and a display device including the cured product.

  In 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. For this reason, in order to form the pattern of an insulating film or a spacer, the photosensitive composition which gives a transparent cured film by exposure is used. By selectively exposing such a photosensitive composition, a transparent cured film pattern can be formed.

  As a photosensitive composition capable of forming a transparent cured film, for example, a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent has been proposed (Patent Document 1). . Specifically, Examples of Patent Document 1 include a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, and a polymerization start represented by any of the following formulas: A photosensitive composition comprising an agent and a mixed solvent comprising 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate is disclosed.

  The photosensitive composition is cured by the photopolymerization initiator contained as a part of its components generating radicals upon exposure and polymerizing the polymerizable compound contained in the photosensitive composition. Therefore, it is known that the sensitivity of the photosensitive composition is affected by the type of photopolymerization initiator contained therein. As a photopolymerization initiator capable of improving the sensitivity of the photosensitive composition, Patent Document 2 proposes an oxime ester compound having a cycloalkyl group. In the examples described in Patent Document 2, compounds represented by the following chemical formulas (a) and (b) are specifically disclosed.

JP 2012-58728 A Published patent gazette No. 101508744 in the People's Republic of China

  However, the photosensitive composition described in Patent Document 1 or Patent Document 2 is not sufficiently sensitive to exposure, and a cured film formed using the photosensitive composition does not have sufficient transmittance.

  The present invention has been made in view of the above-described problems, and is a photosensitive composition that provides a cured product with sufficient sensitivity to exposure and sufficient transmittance upon curing, and pattern formation using the photosensitive composition. An object is to provide a method, a cured product formed using the photosensitive composition, and a display device including the cured product.

  In the photosensitive composition containing a photopolymerization initiator, the present inventors have used a photopolymerization initiator (A1) having a specific structure as the photopolymerization initiator and light having an aromatic ring skeleton to which a nitro group is bonded. It has been found that the above-mentioned problems can be solved by using the polymerization initiator (A2), and the present invention has been completed.

（Ｒ^１は水素原子又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、置換基を有していてもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^２とＲ^３とは相互に結合して環を形成してもよく、Ｒ^４は下記式（Ｒ４−１）又は（Ｒ４−２）で表される基であり、Ｒ^５は水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎは０〜４の整数である。但し、式（１）で表される光重合開始剤はニトロ基を有しない。）

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７及びＲ^８はそれぞれ１価の有機基であり、ｐは０〜４の整数であり、Ｒ^７及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^７とＲ^８とが相互に結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^９は１価の有機基である。） The first aspect of the present invention includes a photopolymerization initiator (A1) represented by the following formula (1) and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. It is a composition.

(R ¹ is a hydrogen atom or a monovalent organic group, and R ² and R ³ are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or R ² and R ³ may be bonded to each other to form a ring, and R ⁴ is a group represented by the following formula (R4-1) or (R4-2); R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n is an integer of 0 to 4, provided that (The photopolymerization initiator represented by the formula (1) does not have a nitro group.)

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each a monovalent organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are on the benzene ring. When present at adjacent positions, R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3) is an integer, and R ⁹ is a monovalent organic group.)

  The second aspect of the present invention is to form a coating film or a molded body using the photosensitive composition according to the first aspect, irradiate the coating film or the molded body with electromagnetic waves in a predetermined pattern, and develop It is a pattern formation method including doing.

  The third aspect of the present invention is a cured product formed using the photosensitive composition according to the first aspect.

  4th aspect of this invention is a display apparatus provided with the hardened | cured material which concerns on 3rd aspect.

  According to the present invention, a photosensitive composition that provides a cured product with sufficient sensitivity to exposure and sufficient transmittance upon curing, a pattern formation method using the photosensitive composition, and the photosensitive composition are used. And a display device provided with the cured product.

≪Photosensitive composition≫
The photosensitive composition according to the present invention includes a photopolymerization initiator (A1) represented by the above formula (1) and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. Hereinafter, each component contained in the photosensitive composition will be described.

<Photopolymerization initiator (A)>
Depending on the type of photopolymerization initiator, the transmittance of the photosensitive composition containing the photopolymerization initiator and the transmittance of the post-baked pattern formed using the photosensitive composition are reduced. There is. Moreover, the transmittance | permeability of the photosensitive composition containing a photoinitiator may fall depending on the kind of photoinitiator. However, when a photosensitive composition containing the photopolymerization initiator (A1) represented by the above formula (1) (hereinafter also referred to as “photopolymerization initiator (A1)” or “(A1) component”) is used. The pattern transmittance due to heating is unlikely to decrease. At the same time, the transmittance of the photosensitive composition may not easily decrease. Further, the photopolymerization initiator (A1) is relatively sensitive to light.
On the other hand, the photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded (hereinafter also referred to as “photopolymerization initiator (A2)” or “component (A2)”) is highly sensitive to light. It is.
The photosensitive composition which concerns on this invention gives the hardened | cured material which maintains the high transmittance | permeability while being excellent in the sensitivity with respect to light by the combination of a photoinitiator (A1) and a photoinitiator (A2). Therefore, by using the photosensitive composition of the present invention, it is possible to form a pattern having a desired shape with a low exposure amount, and the formed pattern has a high transmittance. Moreover, by using the photosensitive composition according to the present invention having excellent sensitivity, pattern peeling at the time of pattern formation can be suppressed, and occurrence of rattling that occurs at the edge of the pattern when forming a line pattern can be suppressed. .

[Photoinitiator (A1) Represented by Formula (1)]
The photosensitive composition concerning this invention contains the photoinitiator (A1) represented by the said Formula (1). A photoinitiator (A1) can be used individually or in combination of 2 or more types.

In Formula (1), R ¹ is a hydrogen atom or a monovalent organic group. R ¹ is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by —CO— on the fluorene ring in the formula (1). As long as this condition is satisfied, the bonding position of R ^{1 to} the fluorene ring in formula (1) is not particularly limited. When the photopolymerization initiator (A1) has one or more R ¹ , one of the one or more R ¹ is in position 2 in the fluorene ring because the synthesis of the photopolymerization initiator (A1) is easy. It is preferable to bind to. When R ¹ is plural, the plural R ¹ may be the same or different.

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

When R ¹ is an alkyl group, number of carbon atoms in the alkyl group is preferably from 1 to 20, 1 to 6 is more preferable. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ 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. When R ¹ is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

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

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of when R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ¹ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ¹ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ¹ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples in the case where R ¹ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, i Examples include a sononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R < ¹ > is a naphthyl alkyl group, 11-20 are preferable and, as for the carbon atom number of a naphthyl alkyl group, 11-14 are more preferable. Specific examples when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ¹ is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and / or O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, thiadiazole ring, isothiazole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, benzofuran ring, benzothiophene ring, indole ring, isoindole ring, indolizine ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, carbazole ring, purine ring, quinoline ring , Isoquinoline ring, quinazoline ring, phthalazine ring, cinnoline ring, quinoxaline ring, piperidine ring, piperazine ring, morpholine ring, piperidine ring, tetrahydropyran ring, tetrahydrofuran ring, etc. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ¹ is a heterocyclyl group.

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

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

Among the groups described above, R ¹ is preferably a group represented by R ⁶ —CO— because the sensitivity tends to be improved. R ⁶ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of a group suitable as R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R ⁶ is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.
In addition, as R ¹ , a hydrogen atom is preferable because transparency tends to be good. When R ¹ is a hydrogen atom and R ⁴ is a group represented by the following formula (R4-2), the transparency tends to be better.

In formula (1), R ² and R ³ are each a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ² and R ³ may be bonded to each other to form a ring. Among these groups, R ² and R ³ are preferably chain alkyl groups which may have a substituent. When R ² and R ³ are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ² and R ³ are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Specific examples in the case where R ² and R ³ are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Group, isononyl group, n-decyl group, isodecyl group and the like. When R ² and R 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, and a methoxypropyl group.

When R ² and R ³ are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples in the case where R ¹ is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples when R ¹ is a heterocyclyl group. When R ¹ is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

When R ² and R ³ 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 ² and R ³ are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R ² and R ³ are chain alkyl groups.

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

When R ² and R ³ 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, preferably 3 to 20, and more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ² and R ³ are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and / or O, such monocycles, or such monocycles Is a heterocyclyl group in which a benzene ring is condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, thiadiazole ring, isothiazole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, benzofuran ring, benzothiophene ring, indole ring, isoindole ring, indolizine ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, carbazole ring, purine ring, quinoline ring , Isoquinoline ring, quinazoline ring, phthalazine ring, cinnoline ring, quinoxaline ring, piperidine ring, piperazine ring, morpholine ring, piperidine ring, tetrahydropyran ring, tetrahydrofuran ring, etc.

R ² and R ³ may be bonded to each other to form a ring. The group consisting of the ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When the group formed by combining R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

Examples of a suitable group among R ² and R ³ described above include a group represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of an alkoxy group, 1-6 are more preferable. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ² and R 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 R ² and R ³ have as a substituent.

Preferable specific examples of R ² and R ³ include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -Pen Group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl- cycloalkylalkyl groups such as an n-butyl group, a 5-cyclopentyl-n-pentyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl- n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl Group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycal Alkoxycarbonylalkyl groups such as nyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

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

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７及びＲ^８はそれぞれ１価の有機基であり、ｐは０〜４の整数であり、Ｒ^７及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^７とＲ^８とが互いに結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^９は１価の有機基である。） In formula (1), R ⁴ is a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each a monovalent organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are on the benzene ring. When present at adjacent positions, R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0. (It is an integer of (r + 3) and R ⁹ is a monovalent organic group.)

Examples of the monovalent organic group for R ⁷ and R ^{8 in} formula (R4-1) are the same as those for R ¹ . R ⁷ is preferably an alkyl group or a phenyl group. When R ⁷ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ⁷ is most preferably a methyl group. When R ⁷ and R ⁸ 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 ⁷ and R ⁸ form a ring include a naphthalen-1-yl group, 1, 2, 3, 4-tetrahydronaphthalen-5-yl group etc. are mentioned. In said formula (R4-1), p is an integer of 0-4, it is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (R4-2), R ⁹ is a monovalent organic group. Examples of the monovalent organic group include the same groups as the monovalent organic group described for R ¹ . Of the monovalent organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. R ⁹ is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and among these, a methyl group is more preferable.

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

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

In formula (1), preferred examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group. Among these, a methyl group or a phenyl group is more preferable.

  In Formula (1), n is an integer of 0-4, the integer of 0-2 is preferable, 0 or 1 is more preferable, and 0 is especially preferable.

As described above, the photopolymerization initiator (A1) does not have a nitro group. That is, none of R ^{1 to} R ⁵ has a nitro group.

The content of the photopolymerization initiator (A1) is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the solid content of the photosensitive composition. More preferably, 1-20 mass% is still more preferable, and 1-10 mass% is especially preferable. When the content of the photopolymerization initiator (A1) is within the above range, the obtained composition maintains good sensitivity to exposure, and the cured product obtained from the composition has sufficient transmittance. Cheap.
Content of a photoinitiator (A1) should just be the range of 1-99.5 mass% with respect to the whole photoinitiator (A), for example, Preferably it is 50-99 mass%, 70 More preferably, it is -98 mass%, and it is still more preferable that it is 80-97 mass%.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びｎは、式（１）と同様である。） The manufacturing method of a photoinitiator (A1) is not specifically limited. In the photopolymerization initiator (A1), preferably, an oxime group (= N—OH) contained in a compound represented by the following formula (2) is converted into an oxime ester group represented by ═N—O—COR ^5. It is manufactured by a method including a step of converting. R ⁵ is the same as ^{R 5} in the formula (1).

(R ¹ , R ² , R ³ , R ⁴ , and n are the same as in formula (1).)

  For this reason, the compound represented by the above formula (2) is useful as an intermediate for synthesis of the photopolymerization initiator (A1).

The method for converting the oxime group (= N—OH) into the oxime ester group represented by ═N—O—COR ⁵ is not particularly limited. Typically, a method of reacting the hydroxyl group in the oxime group with an acylating agent that gives an acyl group represented by —COR ⁵ can be mentioned. Examples of the acylating agent include an acid anhydride represented by (R ⁵ CO) ₂ O and an acid halide represented by R ⁵ COHal (Hal is a halogen atom).

A photoinitiator (A1) is compoundable according to the following scheme, for example. In the following scheme, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a monovalent organic group, the fluorene derivative represented by the formula (1-1) is substituted with a fluorene derivative substituted at the 9-position with R ² and R ³ by a well-known method. ¹ can be obtained. The fluorene derivative substituted at the 9-position with R ² and R ³ is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when R ² and R ³ are alkyl groups. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

An acyl group represented by —CO—CH ₂ —R ⁴ is introduced into the fluorene derivative represented by formula (1-1) by Friedel-Crafts acylation reaction, and represented by formula (2-1). A fluorene derivative is obtained. As the acylating agent for introducing the acyl group represented by —CO—CH ₂ —R ⁴ , a carboxylic acid halide represented by the formula (1-8) is preferable. In formula (1-8), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by changing the Friedel-Crafts reaction conditions as appropriate, or by performing protection and deprotection at other positions where acylation is performed. it can.

Next, the methylene group present between R ⁴ and the carbonyl group in the compound represented by the formula (2-1) is oximed to obtain a ketoxime compound represented by the following formula (2-3). The method for oximation of the methylene group is not particularly limited, and a nitrite represented by the following formula (2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) is reacted in the presence of hydrochloric acid. The method is preferred. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or the following formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting with an acid halide (R ⁵ COHal, Hal is a halogen atom). In the following formulas (1-1), (1-8), (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as in formula (1).

In the following scheme, R ⁴ contained in each of formula (1-8), formula (2-1), and formula (2-3) may be the same or different. That is, R ⁴ in formula (1-8), formula (2-1), and formula (2-3) may undergo chemical modification in the synthesis process shown as the following scheme. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ⁴ may undergo is not limited thereto.

<Scheme>

Preferable specific examples of the photopolymerization initiator (A1) include the following compounds.

[Photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded]
The photosensitive composition according to the present invention contains a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. A photoinitiator (A2) can be used individually or in combination of 2 or more types.

The photopolymerization initiator (A2) is not particularly limited as long as it is a photopolymerization initiator having an aromatic ring skeleton to which a nitro group is bonded. For example, an aromatic ring in which a nitro group and a group having an oxime ester bond are bonded. Examples include compounds having a skeleton.
The aromatic ring skeleton is preferably a part of a fluorene or carbazole skeleton, and may be an aromatic ring that is a part of the fluorene or carbazole skeleton.
In addition, the photopolymerization initiator (A2) is a compound represented by the formula (A2-1C) described later, and a nitro group such as a compound represented by the formula (A2-1N) is bonded to an arylene group or a heteroarylene group. It may be a compound.
In the photopolymerization initiator (A2), the nitro group is preferably bonded to the aromatic ring skeleton directly (that is, not via a linking group such as an alkylene group) or via a linking group such as an alkylene group, More preferably, it is directly bonded to the aromatic ring skeleton. The group having an oxime ester bond is preferably bonded to the aromatic ring skeleton directly or via a carbonyl group. Examples of the group having an oxime ester bond include a group represented by the following formula (3).
^{-C (R 14) = N-} O-C (R 15) = O (3)
(In the formula, R ¹⁴ is a monovalent organic group, and R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. .)

  Specific examples of the photopolymerization initiator (A2) include the following formula (a-1):

（Ｒ^１００は下記式（ａ−２）：

(R ¹⁰⁰ represents the following formula (a-2):

（Ｒ^１１は、水素原子、ニトロ基、又は１価の有機基であり、Ｒ^１２及びＲ^１３は、独立に鎖状アルキル基、環状炭化水素基、又はヘテロアリール基であり、Ｒ^１２とＲ^１３とは相互に結合してスピロ環を形成してもよく、ｎ１は１〜４の整数である。但し、Ｒ^１１の少なくとも１個はニトロ基である。）
で表される基、下記式（ａ−３）：

^{(R 11} is a hydrogen atom, a nitro group, or a monovalent organic ^{group, R 12} and ^{R 13} are independently linear alkyl group, a cyclic hydrocarbon group, or a heteroaryl ^{group, R 12} and R ¹³ may be bonded to each other to form a spiro ring, and n1 is an integer of 1 to 4, provided that at least one of R ¹¹ is a nitro group.
A group represented by formula (a-3):

（Ｒ^２０は、独立に１価の有機基、アミノ基、ハロゲン原子、ニトロ基、又はシアノ基であり、ＡはＳ又はＯであり、ｎ２は１〜４の整数である。但し、Ｒ^２０の少なくとも１個はニトロ基である。）
で表される基、又は下記式（ａ−４）：

(R ²⁰ is independently a monovalent organic group, amino group, halogen atom, nitro group, or cyano group, A is S or O, and n2 is an integer of 1 to 4, provided that R ²⁰ At least one of is a nitro group.)
Or a group represented by the following formula (a-4):

（Ｒ^２１は１価の有機基であり、Ｒ^２２は水素原子、ニトロ基、又は１価の有機基であり、ｎ３は１〜４の整数である。但し、Ｒ^２２の少なくとも１個はニトロ基である。）
で表される基であり、Ｒ^１４は１価の有機基であり、Ｒ^１５は水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｍは０又は１である。）
で表される化合物が挙げられる。

(R ²¹ is a monovalent organic group, R ²² is a hydrogen atom, a nitro group, or a monovalent organic group, and n3 is an integer of 1 to 4, provided that at least one of R ²² is nitro. Group.)
R ¹⁴ is a monovalent organic group, R ¹⁵ has a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or a substituent. And m is 0 or 1. )
The compound represented by these is mentioned.

Examples of suitable monovalent organic groups for R ¹⁴ include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, and a saturated aliphatic group, as described later for R ^11. 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, substituent A benzoyloxy group that may have a substituent, a phenylalkyl group that may have a substituent, a naphthyl group that may have a substituent, a naphthoxy group that may have a substituent, and a substituent May have a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, or a substituent Good Heterocyclyl group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group.

When R < ¹⁴ > is an alkyl group, 1-20 are preferable and, as for the carbon atom number of an alkyl group, 1-6 are more preferable. Further, when R ¹⁴ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹⁴ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ¹⁴ is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R < ¹⁴ > is an alkoxy group, 1-20 are preferable and, as for the carbon atom number of an alkoxy group, 1-6 are more preferable. Further, when R ¹⁴ is an alkoxy group, it may be linear or branched. Specific examples when R ¹⁴ is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. When R ¹⁴ is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ¹⁴ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples when R ¹⁴ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of when R ¹⁴ is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹⁴ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ¹⁴ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ¹⁴ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ¹⁴ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ¹⁴ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ¹⁴ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ¹⁴ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹⁴ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ¹⁴ is a heterocyclyl group.

When R ¹⁴ is an amino group substituted by an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ¹⁴ . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ¹⁴ further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹⁴ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, and 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹⁴ have a plurality of substituents, the plurality of substituents may be the same or different.

R ¹⁴ is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ¹⁴ may have.

Among monovalent organic groups, R ¹⁴ may be an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a substituent on the aromatic ring. Good phenylthioalkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

（式（Ｒ２−１）及び（Ｒ２−２）中、Ｒ^１７及びＲ^１８はそれぞれ１価の有機基であり、ｐ１は０〜４の整数であり、Ｒ^１７及びＲ^１８がベンゼン環上の隣接する位置に存在する場合、Ｒ^１７とＲ^１８とが互いに結合して環を形成してもよく、ｑ１は１〜８の整数であり、ｒ１は１〜５の整数であり、ｓ１は０〜（ｒ１＋３）の整数であり、Ｒ^１９はアルキル基である。） ^Having described ^{R 14,} examples of ^{R 14,} preferably a group represented by the following formula (R2-1) or (R2-2).

(In the formulas (R2-1) and (R2-2), R ¹⁷ and R ¹⁸ are each a monovalent organic group, p1 is an integer of 0 to 4, and R ¹⁷ and R ¹⁸ are on the benzene ring. When present in adjacent positions, R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring, q1 is an integer of 1 to 8, r1 is an integer of 1 to 5, and s1 is 0. (It is an integer of ~ (r1 + 3), and R ¹⁹ is an alkyl group.)

Examples of the organic group for R ¹⁷ and R ^{18 in} formula (R2-1) are the same as those for R ¹⁴ . R ¹⁷ is preferably an alkyl group or a phenyl group. When R ¹⁷ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ¹⁷ is most preferably a methyl group. When R ¹⁷ and R ¹⁸ 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 (R2-1), in which R ¹⁷ and R ¹⁸ form a ring, include a naphthalen-1-yl group, 1, 2, 3, 4-tetrahydronaphthalen-5-yl group etc. are mentioned. In said formula (R2-1), p1 is an integer of 0-4, it is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (R2-2), R ¹⁹ is an alkyl group. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. R ¹⁹ is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and among these, a methyl group is more preferable.

  In said formula (R2-2), r1 is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said formula (R2-2), s1 is 0- (r1 + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (R2-2), q1 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In formula (a-1), R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be contained when R ¹⁵ is an alkyl group include a phenyl group and a naphthyl group. As the substituent that may be possessed when R ¹⁵ is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and is preferably exemplified.

In formula (a-1), R ¹⁵ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, or the like. Among them, a methyl group or a phenyl group is more preferable among these.

In formula (a-2), R ¹¹ represents a hydrogen atom, a nitro group, or a monovalent organic group. R ¹¹ is a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _m — in the formula (a-1) on the fluorene ring in the formula (a-2). Bind to the ring. As long as this condition is satisfied, in the formula (a-2), the bonding position of R ^{11 to} the fluorene ring is not particularly limited. The bonding position of R ^{11 to} the fluorene ring is that the compound represented by the formula (a-1) in which R ¹⁰⁰ is a group represented by the formula (a-2) can be easily synthesized. It is preferable that it is the 2nd position.

When R ¹¹ is a monovalent organic group, R ¹¹ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferable examples when R ¹¹ is a monovalent organic group are the same as R ¹⁴ , such as alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated fat group. Group acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, substituted A benzoyloxy group which may have a group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, and a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, and a substituent Also There heterocyclyl group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ¹⁴ .

Among the groups described above, R ¹¹ is preferably a nitro group or a group represented by R ^11a —CO— because the sensitivity tends to be improved. However, at least one of R ¹¹ is a nitro group. R ^11a is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of a group suitable as R ^11a include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R ^11a is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group.
Further, it is preferable that R ¹¹ is a hydrogen atom because transparency tends to be good. When R ¹¹ is a hydrogen atom and R ¹⁴ is (R2-2) described above, the transparency tends to be better.

In formula (a-2), R ¹² and R ¹³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group. Among these groups, R ¹² and R ¹³ are preferably chain alkyl groups.

When R ¹² and R ¹³ are a chain alkyl group, the chain alkyl group may be a linear alkyl group or a branched alkyl group. When R ¹² and R ¹³ are chain alkyl groups, the chain alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples when R ¹² and R ¹³ are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Group, isononyl group, n-decyl group, isodecyl group and the like. When R ¹² and R ¹³ are chain alkyl groups, the chain alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the chain alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ¹² and R ¹³ are cyclic hydrocarbon groups, the cyclic hydrocarbon group may be an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group.

When R ¹² and R ¹³ are aromatic cyclic hydrocarbon groups, the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond. It is preferably a group formed by condensation of a plurality of benzene rings. When the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings included in the aromatic cyclic hydrocarbon group is particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic cyclic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ¹² and R ¹³ 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, preferably 3 to 20, and more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ¹² and R ¹³ are heteroaryl groups, the heteroaryl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles It is a heteroaryl group condensed with a benzene ring. When the heteroaryl group is a condensed ring, the number of rings is limited to 3. Examples of the heterocyclic ring constituting the heteroaryl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indole. , Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like.

R ¹² and R ¹³ may be bonded to each other to form a spiro ring. The group consisting of a spiro ring formed by R ¹² and R ¹³ is preferably a cycloalkylidene group. When R ¹² and R ¹³ are combined to form a cycloalkylidene group, the spiro ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring. .

When the group formed by combining R ¹² and R ¹³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

  n1 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

In formula (a-3), R ²⁰ is independently a monovalent organic group, amino group, halogen atom, nitro group, or cyano group. When R ²⁰ is a monovalent organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples when R ²⁰ is a monovalent organic group include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; A C2-C7 saturated aliphatic acyloxy group; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a C1-C6 alkyl group, a morpholin-1-yl group, a piperazine- A benzoyl group substituted by a group selected from the group consisting of a 1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino having an alkyl group having 1 to 6 carbon atoms Group; morpholin-1-yl group; piperazin-1-yl group.

In R ²⁰ , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group; nitro group is more preferred. However, at least one of R ²⁰ is a nitro group.

N2 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. If n2 is 1, the binding position of R ^20, to the bond to the phenyl group R ²⁰ is bonded is bonded to the atom A, it is preferably in the para position.
A is preferably S.

In formula (a-4), R ²¹ represents a monovalent organic group. R ²¹ can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R ²¹ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, Phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, and an optionally substituted carbon number 11 to 20 Naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, and the like.

Among R ²¹ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an ethyl group is particularly preferred.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ²⁰ or R ²¹ further have a substituent, the substituent is a C 1-6 alkyl group, a C 1-6 alkoxy group, carbon A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, carbon number Examples thereof include a dialkylamino group having 1 to 6 alkyl groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ²⁰ or R ²¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, and 1-4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ²⁰ or R ²¹ have a plurality of substituents, the plurality of substituents may be the same or different.

In formula (a-4), R ²² represents a hydrogen atom, a nitro group, or a monovalent organic group. R ²² is the same as R ^11, and at least one of R ²² is a nitro group.

  n3 is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

When m is 0, the compound represented by the formula (a-1) can be synthesized according to the following scheme a1, for example. In Scheme a1, a compound represented by the following formula (a1-1) is used as a raw material. For example, when R ¹⁰⁰ is a group represented by the formula (a-2), a fluorene derivative represented by the following formula (a1-1-1) is used as a raw material in the scheme a1. When R ¹¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (a1-1-1) is converted to a fluorene derivative substituted at the 9-position with R ¹² and R ^13. Can be obtained by introducing the substituent R ¹¹ . The fluorene derivative substituted at the 9-position with R ¹² and R ¹³ is, for example, an alkali metal hydroxide when R ¹² and R ¹³ are alkyl groups, as described in JP-A-06-234668. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

A ketone represented by the formula (a1-3) is acylated by the Friedel-Crafts reaction with the halocarbonyl compound represented by the formula (a1-2), and the ketone represented by the formula (a1-3) A compound is obtained. In formula (a1-2), Hal is a halogen atom. Position is acylated by the compound represented by R ¹⁰⁰ formula (a1-2) on the aromatic ring contained in the or by appropriately changing the Friedel-Crafts reaction conditions, formulas for the aromatic ring (a1- It can be selected by a method in which protection and deprotection are applied to other positions acylated by the compound represented by 2).

Next, the resulting ketone compound represented by formula (a1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (a1-4). An oxime compound of the formula (a1-4) and an acid anhydride ((R ¹⁵ CO) ₂ O) represented by the following formula (a1-5) or an acid halide represented by the following formula (a1-6) ( A compound represented by the following formula (a1-7) can be obtained by reacting R ¹⁵ COHal and Hal with a halogen atom.

In addition, Formula (a1-1), (a1-2), (a1-3), (a1-4), (a1-5), (a1-6), (a1-7), and (a1-1) -1), R ¹⁰⁰ , R ¹⁴ , R ¹⁵ , R ¹¹ , R ¹² , and R ¹³ are the same as those in formula (a-1) and formula (a-2).

<Scheme a1>

When m is 1, the compound represented by the formula (a-1) can be synthesized, for example, according to the following scheme a2. In Scheme a2, a compound represented by the following formula (a2-1) is used as a raw material. The compound represented by the formula (a2-1) is obtained by acylating the compound represented by the formula (a1-1) by a Friedel-Crafts reaction in the same manner as in the scheme a1. The compound represented by the formula (a2-1) is reacted with a nitrite represented by the following formula (a2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid. Thus, a ketoxime compound represented by the following formula (a2-3) is obtained. Next, a ketoxime compound represented by the following formula (a2-3) and an acid anhydride ((R ¹⁵ CO) ₂ O) represented by the following formula (a2-4) or the following formula (a2-5) A compound represented by the following formula (a2-6) can be obtained by reacting with an acid halide (R ¹⁵ COHal, Hal is a halogen atom). In the following formulas (a2-1), (a2-3), (a2-4), (a2-5), and (a2-6), R ¹⁰⁰ , R ¹⁴ , and R ¹⁵ are represented by the formula (a -1).
When m is 1, there exists a tendency which can reduce more the generation | occurrence | production of the foreign material in the hardened | cured material formed using the photosensitive composition containing the compound represented by Formula (a-1).

<Scheme a2>

Preferable specific examples of the compound represented by the formula (a-1) include the following compounds.

（式（Ａ２−１Ｃ）中、Ｒ^１はニトロ基を表し、Ｒ^６は、アリーレン基又はヘテロアリーレン基であり、当該アリーレン基又はヘテロアリーレン基は、炭素−炭素二重結合及び炭素−炭素三重結合から選択される１以上の結合を１以上含む鎖状脂肪族炭化水素基を組み合わせた基であってもよい。Ｒ^２及びＲ^３はそれぞれ独立して、置換されていてもよいアルキル基又は水素原子を表し、Ｒ^４は１価の有機基、又は水素原子を表し、Ｒ^５は１価の有機基又は水素原子を表し、ｎは、０又は１を表す。） Moreover, as a photoinitiator (A2), the compound represented by a following formula (A2-1C) can also be used.

(In Formula (A2-1C), R ¹ represents a nitro group, R ⁶ represents an arylene group or a heteroarylene group, and the arylene group or heteroarylene group includes a carbon-carbon double bond and a carbon-carbon triple bond. It may be a group formed by combining chain aliphatic hydrocarbon groups containing one or more bonds selected from the bonds R ² and R ³ are each independently an optionally substituted alkyl group or Represents a hydrogen atom, R ⁴ represents a monovalent organic group or a hydrogen atom, R ⁵ represents a monovalent organic group or a hydrogen atom, and n represents 0 or 1.)

When R ⁶ in formula (A2-1C) is an arylene group, the arylene group is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. The arylene group is preferably a group consisting of one or more benzene rings. When the arylene group includes two or more benzene rings, the plurality of benzene rings may be bonded to each other by a single bond or may be condensed with each other to form a condensed ring such as a naphthalene ring.
The arylene group preferably contains 1 to 3 benzene rings, more preferably 1 or 2 benzene rings.

  Preferred examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene 1,4-diyl group, Naphthalene-1,5-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7 -Diyl group, biphenyl-4,4'-diyl group, biphenyl-3,3'-diyl group, biphenyl-2,2'-diyl group, biphenyl-3,4'-diyl group, biphenyl-3,2 ' -A diyl group and a biphenyl-2,4'-diyl group are mentioned.

When R ⁶ in formula (A2-1C) is a heteroarylene group, the heteroarylene group is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from an aromatic heterocycle. The heteroarylene group is a group consisting of a 5-membered or 6-membered aromatic ring, and preferably a group containing at least one 5-membered or 6-membered aromatic heterocycle.
When the heteroarylene group is a group consisting of a 5-membered or 6-membered aromatic ring and a group containing at least one 5-membered or 6-membered aromatic heterocycle, the plurality of 5-membered or 6-membered aromatic rings are These may be bonded to each other by a single bond or may be condensed with each other to form a condensed ring.
It preferably contains a heteroarylene group, 1 to 3 5-membered or 6-membered aromatic ring, more preferably 1 or 2 5-membered or 6-membered aromatic ring.

  Suitable examples of the heteroarylene group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, iso Two hydrogens bonded to a carbon atom from an aromatic heterocyclic compound such as indole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline Examples include groups other than atoms.

The chain aliphatic hydrocarbon group containing one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond, the number of carbon atoms, the carbon-carbon double bond and the carbon-carbon triple The number of bonds is not particularly limited as long as the object of the present invention is not impaired.
The chain aliphatic hydrocarbon group containing one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond may be linear or branched. Well, straight chain is preferred.

The number of carbon atoms of the chain aliphatic hydrocarbon group containing one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond is preferably 2 to 10, more preferably 2 to 6, 2 to 4 are particularly preferable.
The chain aliphatic hydrocarbon group is preferably an alkenylene group containing one carbon-carbon double bond or an alkynylene group containing one carbon-carbon triple bond.

  Preferable examples of the chain aliphatic hydrocarbon group containing one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond include ethylene-1,2-diyl group, ethyne-1 , 2-diyl group, prop-1-ene-1,2-diyl group, propargylene group and pentynylene group.

For example, as a preferable example of a group in which an arylene group is combined with a chain aliphatic hydrocarbon group including one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond, A divalent group is mentioned.
Preferable examples of the group in which the heteroarylene group is combined with a chain aliphatic hydrocarbon group containing one or more bonds selected from a carbon-carbon double bond and a carbon-carbon triple bond include the following 2 And groups in which the arylene group contained in the valent group is replaced with various heteroarylene groups.

When R ² and R ^{3 in} Formula (A2-1C) are an alkyl group having no substituent, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, and 1-6 Is particularly preferred. Specific examples when R ² and R ³ are alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, Examples include an isononyl group, an n-decyl group, and an isodecyl group.

When R ² and R ^{3 in} Formula (A2-1C) are an alkyl group having a substituent, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. preferable. 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 alkyl group having a substituent may be linear or branched, and is preferably linear.

The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, an alkoxy group, and an alkoxycarbonyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group.
3-10 are preferable and, as for the carbon atom number of a cycloalkyl group, 3-6 are more preferable. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.
The heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and O, or a heterocyclyl group in which such monocycles or such monocycles and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ² and R ³ are heterocyclyl groups, the heterocyclyl group may further have a substituent.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable. Specific examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group. , Sec-pentyloxy group, tert-pentyloxy group, and n-hexyloxy group.
The alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group. N-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, and n-hexyloxycarbonyl group.

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

R ² and R ^{3 in} formula (A2-1C) may be bonded to each other to form a ring. The group consisting of the ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When the group formed by combining R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

Examples of a suitable group among R ² and R ³ described above include a group represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable, as for the carbon atom number of an alkoxy group, 1-6 are more preferable, and 1-4 are especially preferable.
When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable.
When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear.
When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ² and R 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 R ² and R ³ have as a substituent.

Preferable specific examples of R ² and R ³ include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-pentyl, 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 Groups, alkoxyalkyl groups such as 7-ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5 - Cyanoalkyl groups such as non-n-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 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 A phenylalkyl group such as 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-cis Cycloalkylalkyl groups such as clopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n -Pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7 Alkoxycarbonylalkyl groups such as ethoxycarbonyl-n-heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5- Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Examples thereof include a halogenated alkyl group such as a fluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ² and R ³ , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2 -Phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5, 5,5-Heptafluoro-n-pentyl group.

R ⁴ in Formula (A2-1C) is a monovalent organic group or a hydrogen atom. The monovalent organic group is not particularly limited as long as the object of the present invention is not impaired.
Examples of suitable organic groups for R ⁴ may have an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. Phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy group, substituted Phenylalkyl group which may have a group, phenoxyalkyl group which may have a substituent, phenylthioalkyl group which may have a substituent, N-substituted aminoalkyl group, N, N-disubstituted amino An alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, and an optionally substituted naphthoxyca Rubonyl group, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, naphthoxyalkyl group which may have a substituent, naphthyl which may have a substituent Thioalkyl group, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, amino group substituted with 1 or 2 organic group, morpholin-1-yl group, and piperazine A -1-yl group etc. are mentioned.
R ⁴ is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring.

When R ⁴ is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ⁴ is an alkyl group, it may be linear or branched. Specific examples in the case where R ⁴ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ⁴ is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ⁴ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, and more preferably 1-6. Further, when R ⁴ is an alkoxy group, it may be linear or branched. Specific examples when R ⁴ is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. When R ⁴ is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ⁴ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of R ⁴ is a cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group, and the like. Specific examples of R ⁴ is cycloalkoxy groups include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyl group, and cyclooctyl group, and the like.

When R ⁴ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ⁴ is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ⁴ is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ⁴ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ⁴ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, i Examples include a sononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ⁴ is a phenoxyalkyl group, a phenylthioalkyl group, a naphthoxyalkyl group, and a naphthylthioalkyl group, the number of carbon atoms of the alkylene group contained in these groups is preferably 1-20, and 1-6 Is more preferable. The alkylene group may be linear or branched, and is preferably linear.
Specific examples of the phenoxyalkyl group include 2-phenoxyethyl group, 3-phenoxy-n-propyl group, 4-phenoxy-n-butyl group, 5-phenoxy-n-pentyl group, and 6-phenoxy-n-hexyl. Groups.
Specific examples of the phenylthioalkyl group include 2-phenylthioethyl group, 3-phenylthio-n-propyl group, 4-phenylthio-n-butyl group, 5-phenylthio-n-pentyl group, and 6-phenylthio-n. -A hexyl group is mentioned.
Specific examples of the naphthoxyalkyl group include 2- (α-naphthoxy) ethyl group, 3- (α-naphthoxy) -n-propyl group, 4- (α-naphthoxy) -n-butyl group, 5- (α -Naphthoxy) -n-pentyl group, 6- (α-naphthoxy) -n-hexyl group, 2- (β-naphthoxy) ethyl group, 3- (β-naphthoxy) -n-propyl group, 4- (β- A naphthoxy) -n-butyl group, a 5- (β-naphthoxy) -n-pentyl group, and a 6- (β-naphthoxy) -n-hexyl group.
Specific examples of the naphthylthioalkyl group include 2- (α-naphthylthio) ethyl group, 3- (α-naphthylthio) -n-propyl group, 4- (α-naphthylthio) -n-butyl group, 5- (α -Naphthylthio) -n-pentyl group, 6- (α-naphthylthio) -n-hexyl group, 2- (β-naphthylthio) ethyl group, 3- (β-naphthylthio) -n-propyl group, 4- (β- A naphthylthio) -n-butyl group, a 5- (β-naphthylthio) -n-pentyl group, and a 6- (β-naphthylthio) -n-hexyl group.
When R ⁴ is a phenoxyalkyl group, a phenylthioalkyl group, a naphthoxyalkyl group, or a naphthylthioalkyl group, R ⁴ may further have a substituent on the phenyl group or naphthyl group.

When R ⁴ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ⁴ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ⁴ is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ⁴ is a heterocyclyl group.

When R ⁴ is an N-substituted aminoalkyl group or an N, N-disubstituted aminoalkyl group, the substituent bonded to the nitrogen atom is preferably an organic group.
Suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 21 carbon atoms, and saturation having 2 to 21 carbon atoms. An aliphatic acyloxy group, a phenyl group that may have a substituent, a benzoyl group that may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms that may have a substituent, and a substituent; A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group.
The number of carbon atoms of the alkylene group contained in the N-substituted aminoalkyl group or the N, N-disubstituted aminoalkyl group is preferably 1-20, and more preferably 1-6. The alkylene group may be linear or branched.
Specific examples of the N-substituted aminoalkyl group include 2- (methylamino) ethyl group, 2- (ethylamino) ethyl group, 2- (n-propylamino) ethyl group, 2- (n-butylamino) ethyl. Group, 3- (methylamino) n-propyl group, 3- (ethylamino) n-propyl group, 3- (n-propylamino) n-propyl group, 3- (n-butylamino) n-propyl group, 2- (methylamino) n-propyl group, 2- (ethylamino) n-propyl group, 2- (n-propylamino) n-propyl group, 2- (n-butylamino) n-propyl group, 2- (Acetylamino) ethyl group, 2- (propionylamino) ethyl group, 2- (acetoxyamino) ethyl group, 2- (propionyloxyamino) ethyl group, 3- (acetylamino) n-propyl group, 3- Propionylamino) n-propyl group, 3- (acetoxyamino) n-propyl group, 3- (propionyloxyamino) n-propyl group, 2- (acetylamino) n-propyl group, 2- (propionylamino) n- A propyl group, 2- (acetoxyamino) n-propyl group, and 2- (propionyloxyamino) n-propyl group are mentioned.
Specific examples of the N, N-disubstituted aminoalkyl group include 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, 2- (N, N-di-n). -Propylamino) ethyl group, 2- (N, N-di-n-butylamino) ethyl group, 3- (N, N-dimethylamino) n-propyl group, 3- (N, N-diethylamino) n- Propyl group, 3- (N, N-di-n-propylamino) n-propyl group, 3- (N, N-di-n-butylamino) n-propyl group, 2- (N, N-dimethylamino) ) N-propyl group, 2- (N, N-diethylamino) n-propyl group, 2- (N, N-di-n-propylamino) n-propyl group, 2- (N, N-di-n-) Butylamino) n-propyl group, 2- (N, N-diacetylamino) ethyl group, 2- ( , N-dipropionylamino) ethyl group, 2- (N, N-diacetoxyamino) ethyl group, 2- (N, N-dipropionyloxyamino) ethyl group, 3- (N, N-diacetylamino) n -Propyl group, 3- (N, N-dipropionylamino) n-propyl group, 3- (N, N-diacetoxyamino) n-propyl group, 3- (N, N-dipropionyloxyamino) n- Propyl group, 2- (N, N-diacetylamino) n-propyl group, 2- (N, N-dipropionylamino) n-propyl group, 2- (N, N-diacetoxyamino) n-propyl group, 2- (N, N-dipropionyloxyamino) n-propyl group, 2- (N-acetyl-N-acetoxyamino) ethyl group, 2- (N-propionyl-N-propionyloxyamino) ethyl group 3- (N-acetyl-N-acetoxyamino) n-propyl group, 3- (N-propionyl-N-propionyloxyamino) n-propyl group, 2- (N-acetyl-N-acetoxyamino) n-propyl Group, and 2- (N-propionyl-N-propionyloxyamino) n-propyl group.

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

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

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

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

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

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

In formula (A2-1C), R ⁵ represents a monovalent organic group or a hydrogen atom. Examples of the monovalent organic group include an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ⁵ is an alkyl group include a phenyl group and a naphthyl group.

In formula (A2-1C), R ⁵ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, or the like. Among them, a methyl group or a phenyl group is more preferable among these.

（式（Ａ２−１Ｃ−１）及び式（Ａ２−１Ｃ−２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びｎは式（Ａ２−１Ｃ）で示したものと同義である。） Moreover, in the compound represented by a formula (A2-1C), the compound represented by a following formula (A2-1C-1) or a formula (A2-1C-2) is preferable.

(In Formula (A2-1C-1) and Formula (A2-1C-2), R ² , R ³ , R ⁴ , R ⁵ , and n are as defined in Formula (A2-1C). )

（式（Ａ２−１Ｎ）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、及びｎは式（Ａ２−１Ｃ）で示したものと同義である。） Moreover, as a photoinitiator (A2), the compound represented by a following formula (A2-1N) can also be used.

(In Formula (A2-1N), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and n have the same meanings as those shown in Formula (A2-1C).)

（式（Ａ２−１Ｎ−１）及び式（Ａ２−１Ｎ−２）中、Ｒ^２、Ｒ^４、Ｒ^５、及びｎは式（Ａ２−１Ｃ）で示したものと同義である。） Moreover, in the compound represented by a formula (A2-1N), the compound represented by a following formula (A2-1N-1) or (A2-1N-2) is preferable.

(In formula (A2-1N-1) and formula (A2-1N-2), R ² , R ⁴ , R ⁵ , and n have the same meanings as those shown in formula (A2-1C).)

Preferable specific examples of the compound represented by the formula (A2-1C) and the compound represented by the formula (A2-1N) include the following compounds 1 to 71.

The content of the photopolymerization initiator (A2) is preferably 0.05 to 2% by mass and more preferably 0.07 to 1.9% by mass with respect to the solid content of the photosensitive composition. 0.1 to 1.7% by mass is even more preferable, and 0.15 to 1.5% by mass is particularly preferable. When the content of the photopolymerization initiator (A2) is within the above range, the resulting cured product is likely to have sufficient sensitivity to exposure while maintaining good transmittance.
Content of a photoinitiator (A2) should just be the range of 0.1-50 mass% with respect to the whole photoinitiator (A), for example, Preferably it is 0.5-30 mass%. 1 to 20% by mass is more preferable, and 1.5 to 18% by mass is even more preferable.

[Other photopolymerization initiator (A3)]
The photosensitive composition may contain other photopolymerization initiators (A3) other than the component (A1) and the component (A2) as necessary, as long as the object of the present invention is not impaired. Another photoinitiator (A3) can be used individually or in combination of 2 or more types.

  Specific examples of the other photopolymerization initiator (A3) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy). Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4 -Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoate Acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoic acid Acid methyl, 2,4-diethylthioxanthone, 2-chloro Rothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl Anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 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-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (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 ester Ter, 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, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- ( -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- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis- Trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. Is mentioned. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator.

  When the photosensitive composition contains a photopolymerization initiator (A3) other than the components (A1) and (A2), the content of the other photopolymerization initiator (A3) hinders the object of the present invention. The range is not particularly limited. In this case, the content of the other photopolymerization initiator (A3) is typically 99% by mass or less, preferably 50% by mass or less, based on the total amount of the photopolymerization initiator contained in the photosensitive composition. Is more preferable, 30 mass% or less is still more preferable, and 0-10 mass% is especially preferable.

<Polymerizable substrate component (B)>
The photosensitive composition according to the present invention may further contain a polymerizable substrate component (B). The polymerizable substrate component (B) (hereinafter also referred to as “component (B)”) is a component that imparts photopolymerizability and film-forming ability to the photosensitive composition. The polymerizable substrate component (B) is not particularly limited as long as it includes components that can be polymerized by the photopolymerization initiators (A1) and (A2) and can prepare a photosensitive composition capable of forming a film. A polymeric base material component (B) can be used individually or in combination of 2 or more types.

  The polymerizable substrate component (B) typically contains a photopolymerizable compound or a photopolymerizable compound and a resin. The photopolymerizable compound may be a low molecular compound or a high molecular compound such as a resin. Each of a photopolymerizable compound and resin can be used individually or in combination of 2 or more types.

From the viewpoint of photopolymerization, the polymerizable substrate component (B) is a low molecular weight photopolymerizable compound that is not a polymer (hereinafter also referred to as “photopolymerizable monomer”) and / or a crosslinkable group-containing resin. It is preferable to include.
Moreover, when a polymeric base material component (B) contains resin, it is preferable that alkali-soluble resin is included from a developable viewpoint. The alkali-soluble resin may contain a crosslinkable group. Alkali-soluble resins containing a crosslinkable group (containing a crosslinkable group as a substituent in the structural unit) are preferred from the viewpoints of both photopolymerizability and alkali developability.

  Hereinafter, the photopolymerizable monomer, the crosslinkable group-containing resin, and the alkali-soluble resin, which are suitable components included in the component (B), will be described in order.

[Photopolymerizable monomer]
As the photopolymerizable monomer contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. The compound having an ethylenically unsaturated double bond includes a monofunctional monomer and a polyfunctional monomer.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acryle Tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, polytetramethylene glycol di (meth) ) Acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 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, butyre Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxypheny Propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate , Diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethyl Reaction product of hexamethylene diisocyanate, hexamethylene diisocyanate, etc. and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylic Amidomethylene ether, condensate of polyhydric alcohol and N-methylol (meth) acrylamide, triacryl formal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-tris Examples include ethanol triacrylate and 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate. These polyfunctional monomers can be used alone or in combination of two or more.

Among these compounds having an ethylenically unsaturated double bond, a polyfunctional monomer having three or more functional groups is preferable from the viewpoint of obtaining a photosensitive composition that provides a cured product excellent in strength and adhesion to a substrate.
From the viewpoint of controlling the glass transition point (Tg), a monofunctional monomer or a bifunctional monomer may be used in combination with a trifunctional or higher polyfunctional monomer. Among these, 1,6-hexanediol di (meth) acrylate is preferable.

  5-60 mass% is preferable with respect to solid content of the photosensitive composition, and, as for content of a photopolymerizable monomer, 10-50 mass% is more preferable. By setting the content of the photopolymerizable monomer in the photosensitive composition within the above range, the sensitivity, developability, and resolution of the photosensitive composition tend to be easily balanced.

[Crosslinkable group-containing resin]
When the photosensitive composition according to the present invention contains a crosslinkable group-containing resin, it tends to be easier to form a cured product using the photosensitive composition. The crosslinkable group-containing resin is a resin having a crosslinkable group, and preferably contains a unit derived from a (meth) acrylic acid ester having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group capable of crosslinking the crosslinkable group-containing resin mainly by heating, and an epoxy group or an ethylenically unsaturated double bond is preferable. The crosslinkable group includes, for example, at least one selected from the group consisting of a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond. It can be introduced into the containing resin.

  As the crosslinkable group-containing resin, a resin containing a unit derived from a (meth) acrylic acid ester having an epoxy group is preferable. By having such a unit, the adhesiveness and mechanical strength of the insulating film formed using the photosensitive composition to the substrate can be improved.

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

  The (meth) acrylic acid ester having an epoxy group may have an aromatic group. In this specification, an aromatic group is a group having an aromatic ring. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth) acrylic acid ester having an aromatic group and an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (meta ) Acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

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

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

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

Specific examples of the (meth) acrylic acid ester having an alicyclic epoxy group include compounds represented by the following formulas (d2-1) to (d2-16). Among these, in order to make the developability of the photosensitive composition appropriate, compounds represented by the following formulas (d2-1) to (d2-6) are preferable, and the following formulas (d2-1) to The compound represented by (d2-4) is more preferable.
In addition, regarding each of these compounds, the bonding site of the oxygen atom of the ester group to the alicyclic ring is not limited to that shown here, and a part of positional isomers may be included.

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 to ⁶ carbon atoms, and R ^d6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^d5 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^d6 , for example, 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 A phenylene group) is preferred.

  When the (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described above, compared to a (meth) acrylic acid ester having a chain aliphatic epoxy group, A crosslinkable group-containing resin containing a unit derived from the (meth) acrylic acid ester, and thus excellent storage stability of the photosensitive composition, and a temperature range that can be pre-baked when forming an insulating film or the like (pre-baking temperature margin) Is preferable because it becomes wide.

  The crosslinkable group-containing resin also includes a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (in this specification, sometimes referred to as “resin having an ethylenically unsaturated double bond”). It may be. The ethylenically unsaturated double bond is preferably a part constituting a (meth) acryloyloxy group.

Examples of the resin having an ethylenically unsaturated double bond include a resin having a (meth) acryloyloxy group.
The resin having a (meth) acryloyloxy group is, for example, a (meth) acrylic acid ester having at least a part of a carboxy group contained in a polymer containing a unit derived from an unsaturated carboxylic acid and the alicyclic epoxy group. And / or it can prepare by making it react with the (meth) acrylic acid ester which has the said chain | strand-shaped aliphatic epoxy group.

  When the crosslinkable group-containing resin is a resin having an ethylenically unsaturated double bond, it may have photopolymerizability. By containing the photopolymerizable resin having such an ethylenically unsaturated double bond, the crosslinkable group-containing resin can improve the curability of the photosensitive composition and facilitate the pattern formation.

  In the crosslinkable group-containing resin, the amount of the unit derived from the (meth) acrylic acid ester having a crosslinkable group is preferably 20 to 80% by mass and more preferably 30 to 70% by mass with respect to the mass of the resin. Preferably, 33 to 65% by mass is more preferable, and the amount of the unit derived from the (meth) acrylic acid ester having an epoxy group is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and more preferably 20 to 65% by mass. % Is more preferable, and the amount of the unit having an ethylenically unsaturated double bond is preferably 15 to 40% by mass, and more preferably 20 to 35% by mass. As the crosslinkable group-containing resin, a polymer of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester is preferable, and even in the case of the polymer, Content of the unit derived from the (meth) acrylic acid ester having a crosslinkable group is the same as described above with respect to the mass of the resin.

  The crosslinkable group-containing resin may include both a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond, but has an epoxy group ( It may contain either a unit derived from a (meth) acrylate ester or a unit having an ethylenically unsaturated double bond, and a unit derived from a (meth) acrylate ester having an epoxy group as a crosslinkable group The one containing only is preferable.

  The crosslinkable group-containing resin is preferably a resin having a crosslinkable group and an alkali-soluble resin. The photosensitive composition can impart alkali developability to the photosensitive composition by blending such an alkali-soluble resin.

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

  When the crosslinkable group-containing resin is also an alkali-soluble resin, it usually has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group that imparts solubility to the alkali in the crosslinkable group-containing resin, and is preferably a carboxy group or a group that generates a carboxy group by deprotection. It can be introduced into the crosslinkable group-containing resin by including a unit derived from an unsaturated carboxylic acid and by polymerizing a monomer containing a (meth) acrylic acid ester that imparts an alkali-soluble group. In this specification, the (meth) acrylic acid ester that imparts the alkali-soluble group does not include the (meth) acrylic acid ester having the crosslinkable group described above.

  When the crosslinkable group-containing resin is also an alkali-soluble resin, a functional group that suppresses or inhibits the solubility of the crosslinkable group-containing resin in the alkali (hereinafter referred to as “alkali dissolution inhibiting group” or “dissolution inhibiting group”) However, a resin having an alkali-soluble group and a dissolution inhibiting group is preferable. The dissolution inhibiting group can be said to be an alkali hardly soluble group in that it has a function of reducing the solubility of the crosslinkable group-containing resin in alkali. Since the crosslinkable group-containing resin has an alkali-soluble group and a dissolution inhibiting group, the solubility in alkali can be adjusted, whereby the alkali developability of the photosensitive composition can be adjusted. Examples of the dissolution inhibiting group include styrene or styrene derivatives described later; unsaturated imides; (meth) acrylic acid ester having an alicyclic skeleton (excluding those having an epoxy group); benzyl (meth) acrylate And (meth) acrylic acid ester having an aromatic group such as In this specification, the (meth) acrylic acid ester that imparts the dissolution inhibiting group does not include the (meth) acrylic acid ester having the crosslinkable group described above.

  Among the crosslinkable group-containing resins, a polymer of a monomer having an ethylenically unsaturated double bond is obtained because of excellent film-forming properties and easy adjustment of resin properties by selecting a monomer. preferable. As monomers having an ethylenically unsaturated double bond, (meth) acrylic acid; (meth) acrylic acid ester; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Itaconic acid, anhydrides 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- Tilbutyl 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 tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl ethers such as dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, Vinyl methoxyacetate, Vinyls such as nylbutoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate Esters: 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, Acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene Styrene or styrene derivatives such as: 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-olefins such as eicosene; maleimide, N- phenylmaleimide, unsaturated imides such as N- cyclohexyl maleimide; and the like.

  When the crosslinkable group-containing resin is a polymer of a monomer having an ethylenically unsaturated double bond, it usually contains units derived from an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. 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 to 25% by mass, more preferably 8 to 16% by mass with respect to the mass of the resin, and a crosslinkable group. These amounts are particularly preferred when the contained resin has a dissolution inhibiting group described below. When the crosslinkable group-containing resin does not have the below-described dissolution inhibiting group, the amount of the unit derived from the unsaturated carboxylic acid in the resin is preferably 50 to 80% by mass, and 60 to 60%. 70 mass% is more preferable.

  Among the polymers of monomers having ethylenically unsaturated double bonds, which are polymers of one or more monomers selected from the monomers exemplified above, (meth) acrylic acid and (meta ) A polymer of one or more monomers selected from acrylic esters is preferred. 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 for the preparation of a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is particularly within the range not hindering the object of the present invention. It is not limited, It selects suitably from well-known (meth) acrylic acid ester.

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

  Moreover, among polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, it is easy to form an insulating film with high transmittance using a photosensitive composition. Therefore, a resin containing a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton is also preferable. In this specification, the (meth) acrylic acid ester having an alicyclic skeleton does not include the (meth) acrylic acid ester having the above-described crosslinkable group.

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

  Among the (meth) acrylic acid ester having an alicyclic skeleton, the (meth) acrylic acid ester having an alicyclic hydrocarbon group is represented by, for example, the following formulas (d1-1) to (d1-8). Compounds. Among these, compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and compounds represented by the following formula (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 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^d2 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ^d3 is preferably a methyl group or an ethyl group.

  The crosslinkable group-containing resin is a unit derived from one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, and (meth) acrylic acid ester having an alicyclic epoxy group. It is preferable that it is resin containing the unit derived. Such a resin may further be a resin including a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton, and in that case, a (meth) acrylic acid ester having an alicyclic skeleton in the resin. The amount of the unit derived from may be 10 to 35% by mass, 15 to 30% by mass, or 20 to 25% by mass.

  Moreover, in the polymer of the 1 or more types of monomer selected from the (meth) acrylic acid and (meth) acrylic acid ester containing the unit derived from the (meth) acrylic acid ester which has an alicyclic skeleton. A resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group is preferred. A film formed using a photosensitive composition containing such a crosslinkable group-containing resin is excellent in adhesion to a substrate. Further, when such a resin is used, it is possible to cause a self-reaction between a carboxy group contained in the resin and an alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, a film formed by causing a self-reaction between a carboxy group and an alicyclic epoxy group using a method of heating the film or the like. It is possible to improve mechanical properties such as hardness.

  In the resin containing a unit derived from (meth) acrylic acid (excluding those having a crosslinkable group) and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group, the former in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from (meth) acrylic acid, 10-70 mass% is more preferable. In the resin containing the unit derived from the (meth) acrylic acid and the unit derived from the (meth) acrylic acid ester having an alicyclic epoxy group, the (meth) acrylic having an alicyclic epoxy group in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from an acid ester, 10-50 mass% is more preferable.

  One type selected from (meth) acrylic acid and (meth) acrylic acid ester, including a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group Among the above polymer of monomers, it has a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and an alicyclic epoxy group. It may be a resin containing a unit derived from a (meth) acrylic acid ester.

  A unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylic acid ester having an alicyclic epoxy group In the resin to be included, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, and more preferably 10 to 50% by mass. A unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylic acid ester having an alicyclic epoxy group In the resin to be included, the amount of the unit derived from the (meth) acrylic acid ester having an alicyclic hydrocarbon group in the resin is preferably 1 to 95% by mass, and more preferably 10 to 70% by mass. A unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylic acid ester having an alicyclic epoxy group In the resin to be included, the amount of the unit derived from the (meth) acrylic acid ester having an alicyclic epoxy group in the resin is preferably 1 to 95% by mass, and more preferably 30 to 80% by mass.

  The mass average molecular weight of the crosslinkable group-containing resin (Mw: measured value in terms of polystyrene of gel permeation chromatography (GPC). The same applies in the present specification) is preferably 2000 to 200000, and preferably 2000 to 18000. Is more preferable. By setting it as the above range, there is a tendency that the film forming ability of the photosensitive composition and the developability after exposure are easily balanced.

  The content of the crosslinkable group-containing resin in the photosensitive composition is preferably 15 to 95% by mass, more preferably 35 to 85% by mass, and particularly preferably 50 to 70% by mass in the solid content of the photosensitive composition. .

[Alkali-soluble resin]
The alkali-soluble resin can be appropriately selected from resins conventionally blended in various photosensitive compositions. In the present specification, the alkali-soluble resin does not include the above-described crosslinkable group-containing resin. In some cases, the alkali developability of the photosensitive composition can be improved by blending the alkali-soluble resin with the photosensitive composition. However, the photosensitive composition of the present invention may contain no alkali-soluble resin. By using the above-mentioned crosslinkable group-containing resin which is also an alkali-soluble resin, it can have alkali developability.

Suitable alkali-soluble resins include polymers containing structural units having a ring structure in the main chain. Note that in this specification, a polymer containing a structural unit having a ring structure in the main chain does not include a monomer polymer having an unsaturated bond.
Hereinafter, a polymer containing a structural unit having a ring structure in the main chain will be described.

(Polymer containing structural units having a ring structure in the main chain)
The polymer containing a structural unit having a ring structure in the main chain is not particularly limited as long as it is a resin having a predetermined ring structure and a predetermined alkali solubility. As a suitable example of the polymer containing a structural unit having a ring structure in the main chain, a polymer containing a structural unit derived from maleimide (hereinafter also referred to as “structural unit (A2a)”) (hereinafter referred to as “polymer (A2)”). And a polymer containing a structural unit represented by the following formula (A-1) (hereinafter also referred to as “structural unit (A1a)”) (hereinafter also referred to as “polymer (A1)”). Can be mentioned.

  The maleimide-derived structural unit (A2a) contained in the polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having a maleimide skeleton. Examples of the monomer having a maleimide skeleton include N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  In particular, the photosensitive composition containing the polymer (A1) containing the structural unit (A1a) having a ring structure in the main chain has good solubility in a developer.

In formula (A-1), ring A is a C 4-6 saturated aliphatic cyclic group having one oxygen atom as a ring constituent atom. Ring A is preferably a saturated aliphatic cyclic group having 4 or 5 carbon atoms having one oxygen atom as a ring constituent atom, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, still more preferably A tetrahydropyran ring in a structural unit represented by the following formula (A-3) (hereinafter also referred to as “structural unit (A1a1)”) or a structural unit represented by the following formula (A-4) (hereinafter, “structural unit”). It is also a tetrahydrofuran ring in the unit (A1a2) ”.

  The polymer containing the structural unit represented by the above formula (A-1) in the main chain (polymer (A1)) is usually a structural unit represented by the above formula (A-1) in the main chain (constituent unit ( A plurality of A1a)). In the plurality of structural units (A1a), ring A contained in each structural unit (A1a) may be the same or different from each other in one main chain constituting the polymer (A1). Specifically, one main chain constituting the polymer (A1) is a structural unit represented by the above formula (A-1) contained in the main chain, for example, the above formula (A-3). It may have only the structural unit represented, may have only the structural unit represented by the above formula (A-4), or may be represented by the above formula (A-3). And a structural unit represented by the above formula (A-4).

In the above formula (A-1), formula (A-3) and formula (A-4), R ^b1 and R ^b2 are each independently a hydrogen atom or —COOR ^b3 , and R ^b3 is independently a hydrogen atom or It is a C1-C25 hydrocarbon group which may have a substituent. R ^b1 and R ^b2 are preferably —COOR ^b3 . -COOR ^b3 couple | bonded with each ring A, when one main chain which comprises the polymer (polymer (A1)) containing the structural unit represented by the said Formula (A-1) contains the some ring A Are independent of each other, and the same or different groups as -COOR ^b3 may be bonded to each ring A.

Examples of the hydrocarbon group R ^b1 and R ^b2 may 1 to 25 carbon atoms which may have a substituent represented by is not particularly limited. Specific examples of the hydrocarbon group include linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl. Group; aryl group such as phenyl; alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, 1 -An alkyl group substituted with alkoxy such as ethoxyethyl; an alkyl group substituted with an aryl group such as benzyl; and the like.

When R ^b1 and R ^b2 are hydrocarbon groups, the number of carbon atoms of the hydrocarbon group is preferably 8 or less. As a hydrocarbon group having 8 or less carbon atoms, it is difficult to desorb by an acid or heat, so that a free bond at the end of the hydrocarbon group is bonded to a primary carbon atom or a secondary carbon atom. The hydrocarbon group is preferred. As such a hydrocarbon group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. .
Specific examples of such a hydrocarbon group include methyl, ethyl, cyclohexyl, benzyl and the like, and a methyl group is preferable.

When a plurality of structural units (A1a) are contained in one main chain constituting the polymer (polymer (A1)) containing the structural unit represented by formula (A-1) (structural unit (A1a)) R ^b1 and R ^b2 bonded to each structural unit (A1a) may be the same or different between the structural units (A1a).
When the same or different ring A is contained between the respective structural units (A1a), R ^b1 and R ^b2 are independent of each other without depending on the kind of each ring A to be bonded.

Specifically, when a plurality of structural units represented by the formula (A-3) (structural unit (A1a1)) are contained in one main chain constituting the polymer (A1), each structural unit ( R ^b1 and R ^b2 in A1a1) may be the same or different between the structural units (A1a1).

When one main chain constituting the polymer (A1) contains a plurality of structural units represented by the above formula (A-4) (structural unit (A1a2)), R ^b1 in each structural unit (A1a2) And R ^b2 may be the same or different between the structural units (A1a2).
Furthermore, in one main chain constituting the polymer (A1), a structural unit represented by the above formula (A-3) (structural unit (A1a1)) and a structural unit represented by the above formula (A-4) ( If the structural unit (A1A2)) and is contained, the ^{R b1} and ^{R b2} in the ^{R b1} and ^{R b2} in each of the structural units (A1A1) each of the structural units (A1A2) or different may be the same Also good.

（式（Ａ−５）及び式（Ａ−６）中、Ｒ^ｂ１及びＲ^ｂ２はそれぞれ独立に上記と同様である。） The structural unit represented by the above formula (A-3) (structural unit (A1a1)) is a repeating unit represented by the following formula (A-5) (hereinafter also referred to as “repeating unit (ar1)”). It may be a part. The structural unit represented by the above formula (A-4) (structural unit (A1a2)) is a repeating unit represented by the following formula (A-6) (hereinafter also referred to as “repeating unit (ar2)”). It may be a part.

(In Formula (A-5) and Formula (A-6), R ^b1 and R ^b2 are each independently the same as described above.)

（上記式中、Ｒ^ｂ３はそれぞれ独立に上記と同様である。） Examples of the monomer that gives each repeating unit represented by the above formulas (A-5) and (A-6) include 1,6-dienes represented by the following formulas.

(In the above formula, R ^b3 is independently the same as described above.)

  In a monomer composition that gives a polymer (polymer (A1)) containing a structural unit represented by the above formula (A-1) (structural unit (A1a)) in the main chain, a repeating unit containing the structural unit (A1a) The content ratio of the monomer (A1ma) that gives the structural unit (A1a1) and the structural unit (A1a2) is preferably 1% by mass to 60% by mass with respect to the total amount of monomers in the monomer composition. %, More preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass.

  The polymer (A1) preferably has a repeating unit (A1b) having an acid group in the side chain. If the polymer (A1) has a repeating unit (A1b) having an acid group in the side chain, a photosensitive composition having excellent alkali developability can be obtained. As the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain, for example, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, itaconic acid, ω- Monomers having a carboxyl group such as carboxy-polycaprolactone monoacrylate; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Of these, (meth) acrylic acid is preferred.

  In the monomer composition giving the polymer (A1), the content ratio of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain is based on the total amount of monomers in the monomer composition. Preferably they are 1 mass%-50 mass%, More preferably, they are 5 mass%-40 mass%, More preferably, they are 10 mass%-35 mass%.

  Preferably, the polymer (A1) has a repeating unit (A1c) having a carbon double bond in the side chain. The repeating unit (A1c) having a carbon double bond in the side chain is formed by reacting part or all (preferably part) of the acid group of the repeating unit (A1b) having an acid group in the side chain as a reaction point. It can be obtained by adding a compound having a heavy bond.

  When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxyl group, the compound having a carbon double bond is a compound having an epoxy group and a double bond, an isocyanate group and a double bond. Or the like. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinyl. Examples include benzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxylic anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.

  The polymer (A1) may further have other repeating units (A1e) derived from the monomer (A1ma), the monomer (A1mb) and / or another monomer (A1me) copolymerizable with the monomer (A1mc).

As another monomer (A1me), you may further have a repeating unit which has a 2 or more oxyalkylene group in a side chain, for example. Examples of the repeating unit having two or more oxyalkylene groups in the side chain include a repeating unit represented by the following formula.

In the above formula, R ^b7 , R ^b8 and R ^b9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R ^b10 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. And preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. More preferably a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and still more preferably a linear alkyl group having 1 to 5 carbon atoms, A phenyl group or a biphenyl group, particularly preferably a methyl group, a phenyl group or a biphenyl group. The alkyl group, alkenyl group, and aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2. The repeating unit having two or more oxyalkylene groups in the side chain may contain one or more oxyalkylene groups. x represents an integer of 0-2. y represents 0 or 1; z represents the average addition mole number of an oxyalkylene group, is 2 or more, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 15.

（上記式中、Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９、Ｒ^ｂ１０、ＡＯ、ｘ、ｙ及びｚは、上記で説明した通りである。） The repeating unit having two or more oxyalkylene groups in the side chain is composed of a monomer having two or more oxyalkylene groups in the side chain. As this monomer, the monomer represented by a following formula is mentioned, for example.

(In the above formula, R ^b7 , R ^b8 , R ^b9 , R ^b10 , AO, x, y and z are as described above.)

  Examples of the monomer having two or more oxyalkylene groups in the side chain include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO 4 mol). ), Methoxypolyethylene glycol (meth) acrylate (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2 -Ethylhexyl diethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolypropylene Examples include propylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (EO 4-17 mol), nonylphenoxypolypropylene glycol (meth) acrylate (PO 5 mol), EO-modified cresol (meth) acrylate (EO 2 mol), and the like. . These monomers may be used alone or in combination of two or more. Among them, ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), methoxypolyethylene glycol (meth) acrylate (EO 9 mol), and methoxypolyethylene glycol (meth) acrylate (EO 13 mol) are preferable. More preferred are ethoxylated o-phenylphenol acrylate (EO 2 mol), methoxypolyethylene glycol acrylate (EO 9 mol), and methoxypolyethylene glycol acrylate (EO 13 mol). In the present specification, for example, “EO2 mole”, “PO5 mole” and the like represent the average number of moles added of the oxyalkylene group.

  As other monomer (A1me), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, methoxy Ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, methoxypropylene Glycol (meth) acrylate, phenoxyethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, Tricyclodecyloxyethyl (meth) acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, etc. (Meth) acrylic acid esters; (meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylami N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) Acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl ( (Meth) acrylic acid amides such as meth) acrylamide and N, N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; butadiene such as butadiene and isoprene or substituted butadiene Compounds, ethylene, propylene, vinyl chloride, ethylene, or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like. These monomers may be used alone or in combination of two or more.

  The content ratio of the monomer (A1me) giving other repeating units (A1e) in the monomer composition giving the polymer (A1) is preferably 0% by mass to 55% by mass with respect to the total amount of monomers in the monomer composition. More preferably, it is 5 mass%-50 mass%, More preferably, it is 10 mass%-45 mass%.

  The polymer (A1) may be a random copolymer or a block copolymer. As a polymer (A1), it can use individually or in combination of 2 or more types.

  The weight average molecular weight of the polymer (A1) is preferably a value measured by gel permeation chromatography (GPC) with a tetrahydrofuran (THF) solvent, preferably 3,000 to 200,000, more preferably It is 3,500-100,000, More preferably, it is 4,000-50,000. If it is such a range, the photosensitive composition which can ensure heat resistance and has a viscosity suitable for film formation can be obtained.

  The polymer (A1) can be obtained by polymerizing the monomer composition giving the polymer (A1) by any appropriate method. Examples of the polymerization method include a solution polymerization method.

  The monomer composition that provides the polymer (A1) can comprise any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl. Examples include esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the monomer composition is preferably 5% by mass to 90% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 10% by mass to 50% by mass. .

  The monomer composition that provides the polymer (A1) can comprise any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-amyl peroxy-2. Organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate). The content of the polymerization initiator is preferably 0.1 parts by mass to 15 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of all monomers in the monomer composition.

  The polymerization temperature when polymerizing the polymer (A1) by the solution polymerization method is preferably 40 ° C to 150 ° C, more preferably 60 ° C to 130 ° C.

  When obtaining the polymer (A1) having the repeating unit (A1c) having a carbon double bond in the side chain, the compound having the carbon double bond is added to the obtained polymer after the polymerization. Any appropriate method can be adopted as a method for adding a compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted with part or all (preferably part) of the acid group of the repeating unit (A1b) having an acid group in the side chain. Thus, a repeating unit (A1c) having a carbon double bond in the side chain can be formed.

  The addition amount of the compound having a carbon double bond is preferably 5 parts by mass or more with respect to 100 parts by mass of the polymer after the polymerization (that is, the polymer before adding the compound having a carbon double bond). More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more, Most preferably, it is 20 mass parts or more. If it is such a range, the photosensitive composition excellent in exposure sensitivity can be obtained. If such a photosensitive composition is used, it is easy to form a dense cured coating film, and a pattern excellent in substrate adhesion tends to be obtained. Further, when the addition amount of the compound having a carbon double bond is within the above range, a photosensitive composition having a sufficient hydroxyl group generated by the addition of the compound having a carbon double bond and having excellent solubility in an alkali developer is obtained. be able to. The upper limit of the amount of the compound having a carbon double bond is preferably 170 parts by mass or less with respect to 100 parts by mass of the polymer after the polymerization (that is, the polymer before adding the compound having a carbon double bond). More preferably, it is 150 mass parts or less, More preferably, it is 140 mass parts or less. If the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained.

  Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

The alkali-soluble resin described above may contain a resin other than this polymer together with a polymer containing a structural unit having a ring structure in the main chain.
The content of the alkali-soluble resin in the photosensitive composition is preferably 40% by mass or less, more preferably 30 to 10% by mass, and particularly preferably 25 to 15% by mass with respect to the mass of the solid content of the photosensitive composition. preferable. Moreover, 80 mass% or less is preferable, as for content of alkali-soluble resin in polymeric base material component (B), 60-20 mass% is more preferable, and 50-30 mass% is especially preferable.

<Other ingredients>
The photosensitive composition according to the present invention may contain various additives as necessary. Specifically, a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor. , Thermal polymerization inhibitors, antifoaming agents, surfactants, chain transfer agents and the like. Any additive can be used as the additive. Examples of the surfactant include an anionic compound, a cationic compound, and a nonionic compound. Examples of the adhesion improver include conventionally known silane coupling agents. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of antifoaming agents include silicone compounds and fluorine compounds.
Examples of the chain transfer agent include mercaptan compounds, halogen compounds, quinone compounds, and α-methylstyrene dimer. By containing the chain transfer agent, the pattern shape (in particular, the CD change of the hole pattern and the exposure margin) can be controlled well. Of these, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferred in that it can reduce sublimation, coloring and odor in addition to the above effects.

  Examples of the solvent used in the photosensitive composition according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, dipropylene glycol (Poly) alkylene glycol mono, such as coal monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkyl ethers: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate 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; methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Hydroxyethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl pro Pionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide. 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, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone and 3-methoxybutyl acetate are the above-mentioned (A1 ) Component, (A2) component, and optionally used component (B), since they exhibit excellent solubility, it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate. The content of the solvent may be appropriately determined according to the use of the photosensitive composition. As an example, the solvent content is about 50 to 900 parts by mass with respect to a total of 100 parts by mass of the solid content of the photosensitive composition. .

<Method for preparing photosensitive composition>
The photosensitive composition according to the present invention can be prepared by stirring, mixing and dissolving the above components using a magnetic stirrer, and filtering with a filter such as a 0.2 μm membrane filter as necessary.

  In the photosensitive composition according to the present invention, since the transmittance of the obtained cured product is likely to be sufficient, the transmittance with respect to light having a wavelength of 400 nm measured with an optical path length of 3 μm is preferably 95% or more, and 98% or more. It is more preferable that

≪Pattern forming method, cured product, and display device≫
The pattern forming method according to the present invention is the same as the conventional pattern forming method formed using the photosensitive composition except that the above-described photosensitive composition is used.

  A method for forming a pattern using the above-described photosensitive composition is not particularly limited, and can be appropriately selected from conventionally employed methods. As a suitable pattern forming method, a coating film or molded body forming step for forming a coating film or a molded body using the above-described photosensitive composition, and electromagnetic waves are irradiated in a predetermined pattern on the coating film or the molded body. And a developing step of developing a coating film or molded body irradiated with electromagnetic waves to form a pattern.

  First, in the coating film or molded body forming step, for example, a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), curtain flow coater, etc. on a substrate on which a pattern is to be formed. The photosensitive composition according to the present invention is applied using a non-contact type coating apparatus such as the above, and if necessary, the solvent is removed by drying (prebaking) and / or the above photosensitive property is obtained by a known molding method. The composition is molded to form a coating film or molded body.

Next, the formed coating film or molded body is subjected to an exposure process. In the exposure process, an ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, softening is applied to the coating film or molded product through a negative mask. Radiation such as X-rays, g-rays, i-rays, and h-rays or electromagnetic waves are irradiated to partially expose the coating film or the molded body in a predetermined pattern. The amount of exposure varies depending on the composition of the photosensitive composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  The above-mentioned photosensitive composition is hardly dissolved in an alkali developer after exposure. For this reason, by using the above-mentioned photosensitive composition, it is easy to form a pattern having a good shape in which the exposed portion is a convex portion and the unexposed portion is a concave portion.

  In the developing step, a predetermined pattern is formed by developing the coating film or molded body irradiated with electromagnetic waves with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  If necessary, a cured pattern can be obtained by subjecting the developed pattern to post baking and heat curing. The post-baking temperature is preferably 150 to 270 ° C.

  The cured product according to the present invention is formed using the above-described photosensitive composition. The cured product is preferably an insulating film or a protective film laminated on a photoresist film. When the cured product is a sample having a thickness of 3 μm (optical path length of 3 μm), the transmittance for light with a wavelength of 400 nm is usually 95% or more, preferably 98% or more. As described above, since the cured product has excellent transmittance, it is suitable as an insulating film for a display device that requires an insulating film having excellent transparency, such as an in-cell touch panel type liquid crystal display device or a UHA (Ultra High Aperture) panel. Used for.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

(Preparation of photosensitive composition)
65 parts by mass of a crosslinkable group-containing resin, 35 parts by mass of a photopolymerizable monomer, a photopolymerization initiator of the type and amount shown in Table 1, and a mixed solvent (mass ratio) of diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether acetate 55:45) were mixed to obtain a uniform solution, and a photosensitive composition having a solid content concentration of 24% by mass was prepared. The total amount of the photopolymerization initiator is 4.5 parts by mass in Example 11, 4 parts by mass in Example 12, and the other implementations, with the total amount of the crosslinkable group-containing resin and the photopolymerizable monomer being 100 parts by mass. In the examples and all comparative examples, the amount was 5 parts by mass.
Moreover, in Examples 1-12 and Comparative Examples 1-22, the crosslinkable group containing resin A shown below was used, and in Example 13 and Example 14, the crosslinkable group containing resin B shown below was used.

  As the crosslinkable group-containing resin A, a resin composed of structural units represented by the following formula was used. The mass ratio I-1: I-2: II-1: III-1 between the structural units was 25: 20: 14: 41. The mass average molecular weight (Mw) of the crosslinkable group-containing resin A determined by gel permeation chromatography (GPC) was 7000.

As the crosslinkable group-containing resin B, a resin composed of structural units represented by the following formula was used. The mass ratio I-3: II-1: III-2 between the structural units was 71:12:17. The mass average molecular weight (Mw) of the crosslinkable group-containing resin B determined by gel permeation chromatography (GPC) was 10200.
As the structural unit I-3, a structural unit having the structure of I-3α which is a partially positional isomer with the structure of I-3 shown below was used.

  Dipentaerythritol hexaacrylate was used as the photopolymerizable monomer.

  As the photopolymerization initiator, initiators 1 to 11 represented by the following formula are prepared, and initiators 1 and 3 to 11 are used for the preparation of the photosensitive composition, and for evaluation and measurement of sensitivity and transmittance. It was.

Photopolymerization initiator (A1)
Initiator 1: Compound represented by the following formula (A1-1) Initiator 2: Compound represented by the following formula (A1-2)

Photopolymerization initiator (A2)
Initiator 3: Compound represented by the following formula (A2-1) Initiator 4: Compound represented by the following formula (A2-2) Initiator 5: Represented by the following formula (A2-3) Compound / initiator 7: Compound represented by the following formula (A2-4) / Initiator 9: Compound represented by the following formula (A2-5) / Initiator 12: Represented by the following formula (A2-6) Compound

Other photopolymerization initiator (A3)
Initiator 6: Compound represented by the following formula (A3-1) Initiator 8: Compound represented by the following formula (A3-2) Initiator 10: Represented by the following formula (A3-3) Compound / Initiator 11: Compound represented by the following formula (A3-4)

  About the photosensitive composition obtained by each Example and the comparative example, the sensitivity and the transmittance | permeability were evaluated and measured according to the following method. The evaluation results are shown in Table 1.

(sensitivity)
After spin-coating the photosensitive composition prepared in each of the above Examples and Comparative Examples on a glass substrate with a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Co., Ltd.), the coating film was dried at 100 ° C. for 100 seconds. A photosensitive resin layer was formed. Subsequently, the exposure amount was changed for every experiment with the exposure apparatus (MPA600FA, Canon Inc.), and the photosensitive resin layer was exposed. Next, paddle development was performed at 23 ° C. for 100 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass as a developing solution to form a hole pattern having holes having a pore diameter of 10 μm. After development, the pattern was post-baked at 230 ° C. for 20 minutes. The film thickness of the pattern after post-baking was 3 μm. The film thickness of the pattern was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC, Inc.). The exposure amount that the post-baking treatment and the hole diameter at the bottom of the hole was 8 μm was determined as the appropriate sensitivity. When the exposure amount was 35 mJ / cm ² or less, it was evaluated that the sensitivity was good, and when the exposure amount was more than 35 mJ / cm ² , the sensitivity was evaluated as poor. The exposure amount is preferably 30 mJ / cm ² or less.

(Transmittance)
Instead of exposing the photosensitive resin layer by varying the exposure amount for each experiment, the exposure amount was fixed at the appropriate sensitivity, and the photosensitive resin layer was exposed in the same manner as the sensitivity evaluation method. A cured film of the post-baked photosensitive composition was formed. The thickness of the cured film was 3 μm. The transmittance | permeability in wavelength 400nm of the formed cured film was measured using MCPD-3000 (made by Otsuka Electronics Co., Ltd.). When the transmittance was 95% or more, the transmittance was evaluated as good, and when the transmittance was less than 95%, the transmittance was evaluated as poor. The transmittance is preferably 98% or more.

  As can be seen from Table 1, the photosensitive composition of the present invention comprising a photopolymerization initiator (A1) represented by formula (1) and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded. Was confirmed to give a cured product having sufficient sensitivity to exposure and sufficient transmittance by curing.

Claims (9)

A photosensitive composition comprising a photopolymerization initiator (A1) represented by the following formula (1) and a photopolymerization initiator (A2) having an aromatic ring skeleton to which a nitro group is bonded.

(R ¹ is a hydrogen atom or a monovalent organic group, and R ² and R ³ are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, Or R ² and R ³ may be bonded to each other to form a ring, and R ⁴ is a group represented by the following formula (R4-1) or (R4-2); R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n is an integer of 0 to 4, provided that (The photopolymerization initiator represented by the formula (1) does not have a nitro group.)

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each a monovalent organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are on the benzene ring. When present at adjacent positions, R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3) is an integer, and R ⁹ is a monovalent organic group.)   The photosensitive composition according to claim 1, wherein the aromatic ring skeleton is a part of a fluorene or carbazole skeleton, an arylene group, or a heteroarylene group.   The photosensitive composition of Claim 1 or 2 whose content of the said photoinitiator (A2) is 0.05-2 mass% of solid content of the said photosensitive composition.   Furthermore, the polymeric base material component (B) is included, The said polymeric base material component (B) contains a photopolymerizable compound or a photopolymerizable compound and resin. The photosensitive composition as described.   The photosensitive composition of any one of Claims 1-4 whose transmittance | permeability with respect to the light of wavelength 400nm measured by optical path length 3micrometer is 95% or more.   Forming a coating film or a molded body using the photosensitive composition according to any one of claims 1 to 5, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, and developing the coating film or the molded body. A pattern forming method.   Hardened | cured material formed using the photosensitive composition of any one of Claims 1-5.   The cured product according to claim 7, which is an insulating film or a protective film laminated on a photoresist film.   A display device comprising the cured product according to claim 8.