JP6713112B2 - Compound and method for producing the same - Google Patents

Description

The present invention relates to a compound which can be used as a photopolymerization initiator and gives a photosensitive composition having excellent sensitivity, and a method for producing the compound.

2. Description of the Related Art A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes which are opposed to each other and which form a pair are formed. Then, inside one of the substrates, a color filter including pixel regions of respective colors of red (R), green (G), blue (B) and the like is formed. In this color filter, a black matrix is usually formed so as to partition each pixel region of red, green, blue and the like.

Generally, color filters are manufactured by a lithographic method. That is, first, a black photosensitive composition is applied onto a substrate, dried, and then exposed and developed to form a black matrix. Next, coating, drying, exposure, and development are repeated for each photosensitive composition of each color such as red, green, and blue to form pixel regions of each color at specific positions to manufacture a color filter.

In recent years, in the manufacture of a display device such as a liquid crystal display, an attempt has been made to improve the light-shielding property of a black matrix to further improve the contrast of an image displayed on the display device. For this purpose, it is necessary to add a large amount of light-shielding agent to the photosensitive composition for forming the black matrix. However, when the photosensitive composition contains a large amount of the light-shielding agent as described above, when the film of the photosensitive composition coated on the substrate is exposed to light, light for curing the photosensitive composition forms a film. It becomes difficult to reach the bottom of the composition, which leads to a curing failure due to a marked decrease in sensitivity of the curable composition.

In the photosensitive composition, the photopolymerization initiator contained as a part of the component generates a radical upon exposure. This radical cures the photosensitive composition by polymerizing the polymerizable compound contained in the photosensitive composition. Therefore, it is known that the sensitivity of the photosensitive composition is influenced by the type of photopolymerization initiator contained therein.
Further, in recent years, the production amount of color filters has increased along with the increase in the production number of display devices such as liquid crystal display displays. Therefore, from the viewpoint of further improving productivity, there is a demand for a highly sensitive photosensitive composition capable of forming a pattern with a low exposure amount.
Under such circumstances, Patent Document 1 proposes an oxime ester compound having a cycloalkyl group as a photopolymerization initiator capable of improving the sensitivity of the photosensitive composition. In the examples described in Patent Document 1, compounds represented by the following chemical formulas (a) and (b) are specifically disclosed.

People's Republic of China Published Patent Publication No. 101508744

However, when manufacturing panels for various display devices using the photosensitive composition, the exposure amount when exposing the coating film made of the photosensitive composition is from the viewpoint of improving the productivity of the panel. A decline is desired. Even the photosensitive composition containing the compound described in Patent Document 1 may not be able to sufficiently meet such requirements. For this reason, there is a demand for a photosensitive composition which is more excellent in sensitivity than the photosensitive composition containing the compound described in Patent Document 1.

The present invention has been made in view of the above problems, and a compound that can be used as a photopolymerization initiator and that provides a photosensitive composition having excellent sensitivity, and a method for producing the compound, are provided. To do.

In the oxime ester compound containing a carbazole ring or a fluorene ring as a main skeleton, the present inventors have an aryl group, a heteroaryl group, a carbon-carbon double bond and an electron-withdrawing group on the carbazole ring or the fluorene ring, respectively. It was found that the above problems can be solved by introducing a chain aliphatic hydrocarbon group containing at least one bond selected from carbon-carbon triple bonds, or a group combining these, and the present invention is completed. Came to.

（式（１）中、Ｒ^１は電子吸引基を表し、Ｒ^６は、アリーレン基、ヘテロアリーレン基、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、又はこれらを組み合わせた基であり、前記Ｒ^６は、電子吸引基、チオール基及び１価の有機基から選択される１以上の置換基を有していてもよく、Ｒ^４は一価の有機基、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を表し、Ｔは下記式（Ｔ_Ｃ）又は式（Ｔ_Ｎ）：

で表される基を表し、
式（Ｔ_Ｃ）及び式（Ｔ_Ｎ）中、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、＊は結合手を表し、
式（Ｔ_Ｃ）中、Ｒ^２及びＲ^３は組み合わさって環を形成していてもよい。） The first aspect of the present invention is a compound represented by the following formula (1).

(In the formula (1), R ¹ represents an electron-withdrawing group, and R ⁶ represents one or more bonds selected from an arylene group, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond. It is a chain aliphatic hydrocarbon group containing, or a group combining these, and R ⁶ may have one or more substituents selected from an electron-withdrawing group, a thiol group and a monovalent organic group. well, R ⁴ represents an organic group, or a hydrogen atom, monovalent, R ⁵ represents a monovalent organic group or a hydrogen atom, n is 0 or 1, T is of the formula (T _C), or formula ( _TN ):

Represents a group represented by
Wherein (T _C) and formula (T _N), R ² and R ³ are each independently optionally substituted alkyl group, or a hydrogen atom, * represents a bond,
In formula (T _C ), R ² and R ³ may combine to form a ring. )

（式（１ａ）中、Ｔは前記の通り。）
で表される環骨格に、クロスカップリング反応により−Ｒ^６−Ｒ^１で表される基を導入することと、
（ＩＩ）前記式（１ａ）で表される環骨格に、−ＣＯ−Ｒ^４で表されるアシル基を導入した後、−ＣＯ−Ｒ^４で表される基を、−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基に変換し、さらに、−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基をエステル化して−Ｃ（＝Ｎ−Ｏ−ＣＯ−Ｒ^５）−Ｒ^４で表される基に変換することと、を含む、方法である。 A second aspect of the present invention is a method for producing the compound according to the first aspect, which is represented by formula (1) and n is 0,
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by (II) Formula (1a), after introducing an acyl group represented by ^{-CO-R 4,} a group represented by ^{-CO-R 4, -C (=} N- converted into a group represented by OH) -R ^4, further, -C (= N-OH) -C esterifying a group represented by ^{-R 4 (= N-O-} CO-R 5) - It includes converting the group represented by R ^4, a, is a method.

（式（１ａ）中、Ｔは前記の通り。）
で表される環骨格に、クロスカップリング反応により−Ｒ^６−Ｒ^１で表される基を導入することと、
（ＩＩ）前記式（１ａ）で表される環骨格に、−ＣＯ−ＣＨ_２−Ｒ^４で表されるアシル基を導入した後、−ＣＯ−ＣＨ_２−Ｒ^４で表される基を、−ＣＯ−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基に変換し、さらに、−ＣＯ−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基をエステル化して−ＣＯ−Ｃ（＝Ｎ−Ｏ−ＣＯ−Ｒ^５）−Ｒ^４で表される基に変換することと、を含む、方法である。 A third aspect of the present invention is a method for producing the compound according to the first aspect, which is represented by formula (1) and n is 1,
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by (II) Formula (1a), after introducing an acyl group represented by _-CO-CH 2 -R ^4, a group represented by _-CO-CH 2 -R ^4, -CO-C (= N-OH ) is converted into a group represented by -R ^4, further, -CO-C (= N- OH) a group represented by -R ⁴ was esterified -CO-C ^{(= N-O-CO-} R 5) -R includes converting the group represented by ^4, and a method.

According to the present invention, it is possible to provide a compound which can be used as a photopolymerization initiator and gives a photosensitive composition having excellent sensitivity, and a method for producing the compound.

It is a schematic diagram which shows the cross-sectional shape of the width direction of the pattern formed using the photosensitive composition, (a) is a figure which shows the cross-sectional shape of a normal pattern, (b) produced the undercut 21. It is a figure which shows the cross-sectional shape of a pattern.

<<Compound>>
Hereinafter, the compound represented by the following formula (1) will be described.

（式（１）中、Ｒ^１は電子吸引基を表し、Ｒ^６は、アリーレン基、ヘテロアリーレン基、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、又はこれらを組み合わせた基であり、前記Ｒ^６は、電子吸引基、チオール基及び１価の有機基から選択される１以上の置換基を有していてもよく、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を表し、Ｔは下記式（Ｔ_Ｃ）又は式（Ｔ_Ｎ）：

で表される基を表し、
式（Ｔ_Ｃ）及び式（Ｔ_Ｎ）中、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、＊は結合手を表し、
式（Ｔ_Ｃ）中、Ｒ^２及びＲ^３は組み合わさって環を形成していてもよい。）

(In the formula (1), R ¹ represents an electron-withdrawing group, and R ⁶ represents one or more bonds selected from an arylene group, a heteroarylene group, a carbon-carbon double bond and a carbon-carbon triple bond. It is a chain aliphatic hydrocarbon group containing or a group combining these, and R ⁶ may have one or more substituents selected from an electron-withdrawing group, a thiol group and a monovalent organic group. Often, R ⁴ represents a monovalent organic group or a hydrogen atom, R ⁵ represents a monovalent organic group or a hydrogen atom, n represents 0 or 1, and T represents the following formula (T _C ) or a formula: ( _TN ):

Represents a group represented by
Wherein (T _C) and formula (T _N), R ² and R ³ each independently represent an optionally substituted alkyl group or a hydrogen atom, * represents a bond,
In formula (T _C ), R ² and R ³ may combine to form a ring. )

(Regarding R ¹ and R ⁶ )
The compound represented by the formula (1) has a group containing an electron-withdrawing group represented by R ¹ -R ^6- and a group having another predetermined structure on a fluorene ring or a carbazole ring. Therefore, the sensitivity is excellent.

The substituent that R ⁶ may have and the electron withdrawing group as R ¹ are not particularly limited as long as they are functional groups generally recognized as electron withdrawing groups in the chemical field.
Preferable examples of the electron-withdrawing group include a benzenesulfonyl group, a toluenesulfonyl group, an alkanesulfonyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom, and a halogenated alkyl group. Among these electron withdrawing groups, a nitro group is preferable because of its chemical stability, the sensitivity of the compound represented by formula (1) to light, and the ease with which the compound represented by formula (1) can be synthesized. , A cyano group, and a fluoroalkyl group having 1 to 6 carbon atoms are preferable.

R ⁶ is an arylene group, a heteroarylene group, a chain aliphatic hydrocarbon group containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond, or a group combining these. is there. Further, R ⁶ may have one or more substituents selected from an electron-withdrawing group, a thiol group and a monovalent organic group.

When R ⁶ 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 composed of one or more benzene rings. When the arylene group contains 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, and more preferably 1 or 2 benzene rings.

Preferable 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' -Diyl group, and biphenyl-2,4'-diyl group.

When R ⁶ 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 composed of a 5-membered or 6-membered aromatic ring and is a group containing at least one 5-membered or 6-membered aromatic heterocycle, a plurality of 5-membered or 6-membered aromatic rings are , 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, a 1-3 membered 5- or 6-membered aromatic ring, and more preferably a 1- or 2-membered 5- 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 and iso Two hydrogens attached 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 excluding atoms.

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

The number of carbon atoms of the chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bonds and carbon-carbon triple bonds is preferably 2 to 10, more preferably 2 to 6, 2-4 are especially 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 at least one bond selected from carbon-carbon double bond and carbon-carbon triple bond include ethylene-1,2-diyl group and ethyne-1. , 2-diyl group, prop-1-ene-1,2-diyl group, propargylene group and pentynylene group.

For example, preferred examples of groups in which an arylene group and a chain aliphatic hydrocarbon group containing at least one bond selected from carbon-carbon double bond and carbon-carbon triple bond are combined are as follows. A divalent group is mentioned.
Preferred examples of the group in which a heteroarylene group and a chain aliphatic hydrocarbon group containing one or more bonds selected from carbon-carbon double bond and carbon-carbon triple bond are combined are as follows. Examples thereof include groups in which the arylene group contained in the valent group is replaced with various heteroarylene groups.

Regarding R ⁶ , an arylene group, a heteroarylene group, or a chain aliphatic hydrocarbon group containing at least one bond selected from a carbon-carbon double bond and a carbon-carbon triple bond is an electron-withdrawing group or a thiol group. It may have one or more substituents selected from a group and a monovalent organic group.
The electron withdrawing group is as described above. Examples of the monovalent organic group as a substituent that R ⁶ may have include an alkyl group (eg, methyl group, ethyl group) and an alkoxy group (eg, methoxy group, ethoxy group).

As the group including the electron-withdrawing group represented by R ¹ -R ⁶ — described above, an aryl group substituted with a nitro group is preferable, and a phenyl group substituted with a nitro group is more preferable.
The substitution number of the nitro group in the aryl group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
Specific examples of the aryl group substituted with a nitro group include o-nitrophenyl, m-nitrophenyl group, p-nitrophenyl group, 2,3-dinitrophenyl group, 2,4-dinitrophenyl group and 2,5. -Dinitrophenyl group, 2,6-dinitrophenyl group, 3,4-dinitrophenyl group, 3,5-dinitrophenyl group, 2-nitronaphthalen-1-yl group, 3-nitronaphthalen-1-yl group, 4 -Nitronaphthalen-1-yl group, 5-nitronaphthalen-1-yl group, 6-nitronaphthalen-1-yl group, 7-nitronaphthalen-1-yl group, 8-nitronaphthalen-1-yl group, 3 Examples include a -nitronaphthalen-2-yl group, a 6-nitronaphthalen-2-yl group, and a 7-nitronaphthalen-2-yl group.
Among these groups, the m-nitrophenyl group and the p-nitrophenyl group are more preferable.

(For ^{R 2} and ^{R 3} are included in formula _{(T C)} and formula _{(T N))}
T in the formula (1) is a group represented by the group represented by the aforementioned formula _{(T C),} or Formula _{(T N).} R ² and R ³ included in the formula (T _C ) and the formula ( _TN ) are an optionally substituted alkyl group or a hydrogen atom. In formula (T _C ), R ² and R ³ may combine with each other to form a ring. Of these groups, R ² and R ³ are preferably an optionally substituted alkyl group. When R ² and R ³ are an optionally substituted alkyl group, the alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ² and R ³ are alkyl groups having no substituent, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. When R ² and R ³ are alkyl groups, specific examples thereof 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 thereof include isononyl group, n-decyl group, and isodecyl group.

When R ² and R ³ are alkyl groups having a substituent, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. 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. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable.
Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group and a heterocyclyl group.
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, a cyclooctyl group and the like.
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 is a heterocyclyl group in which such monocycles are condensed with each other or the monocycle is condensed with a benzene ring. 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. The heterocyclic ring constituting the heterocyclyl group, 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. To be 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 thereof 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 preferred number of substituents depends on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

R ² and R ³ may combine with 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 combine to form a cycloalkylidene group, the ring forming 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 which may be condensed with the cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring and a pyridine ring. Ring, pyrazine ring, pyrimidine ring and the like.

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

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable, 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, 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 groups 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 which 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 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- Alkoxyalkyl groups such as hexyl group, 7-ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, Cyanoalkyl groups such as 5-cyano-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- Phenylalkyl group such as octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group , A cycloalkylalkyl group such as a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group 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 Group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group An alkoxycarbonylalkyl group such as a 7-ethoxycarbonyl-n-heptyl group and an 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. Examples thereof include 3-trifluoropropyl group and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

As R ² and R ³ , groups suitable 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. It is a 5,5-heptafluoro-n-pentyl group.

(About R ⁴ )
R ⁴ 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 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. Phenyl group, phenoxy group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, 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 Alkyl group, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, substituted A naphthoyloxy group which may have a group, a naphthylalkyl group which may have a substituent, a naphthoxyalkyl group which may have a substituent, a naphthylthioalkyl group which may have a substituent, A heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted by 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group Groups and the like.
R ⁴ 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.

When R ⁴ is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 6 carbon atoms. When R ⁴ is an alkyl group, it may be linear or branched. When R ⁴ is an alkyl group, specific examples thereof 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, isononyl group, Examples thereof include n-decyl group and isodecyl group. Further, 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 in the alkoxy group is preferably 1-20, more preferably 1-6. When R ⁴ is an alkoxy group, it may be linear or branched. When R ⁴ is an alkoxy group, specific examples thereof 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-octyoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. Further, when R ⁴ 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 ⁴ is a cycloalkyl group or a cycloalkoxy group, the cycloalkyl group or the cycloalkoxy group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 6 carbon atoms. When R ⁴ is a cycloalkyl group, specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where R ⁴ 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 ⁴ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the saturated aliphatic acyl group or the saturated aliphatic acyloxy group preferably has 2 to 21 carbon atoms, and more preferably has 2 to 7 carbon atoms. When R ⁴ is a saturated aliphatic acyl group, specific examples thereof 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-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. When R ⁴ is a saturated aliphatic acyloxy group, specific examples thereof 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, etc. are mentioned.

When R ⁴ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. Specific examples of the case where 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 Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ⁴ is a phenylalkyl group, the phenylalkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 10 carbon atoms. Moreover, when R ⁴ is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, and more preferably 11 to 14.
When R ⁴ is a phenylalkyl group, specific examples include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
When R ⁴ is a naphthylalkyl group, specific examples thereof 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 the naphthyl group.

When R ⁴ is a phenoxyalkyl group, a phenylthioalkyl group, a naphthoxyalkyl group, and a naphthylthioalkyl group, the alkylene group contained in these groups preferably has 1 to 20 carbon atoms, and 1 to 6 carbon atoms. Is more preferable. Further, 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 group. Groups.
Specific examples of the phenylthioalkyl group include a 2-phenylthioethyl group, a 3-phenylthio-n-propyl group, a 4-phenylthio-n-butyl group, a 5-phenylthio-n-pentyl group, and a 6-phenylthio-n group. A hexyl group.
Specific examples of the naphthoxyalkyl group include a 2-(α-naphthoxy)ethyl group, a 3-(α-naphthoxy)-n-propyl group, a 4-(α-naphthoxy)-n-butyl group, and a 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- Examples include naphthoxy)-n-butyl group, 5-(β-naphthoxy)-n-pentyl group, and 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 and 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- Examples thereof include 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 the naphthyl group.

When R ⁴ is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and O, or such monocycles are condensed with each other or such monocycles and benzene rings are condensed. It is a 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. The heterocyclic ring constituting the heterocyclyl group, 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. To be 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 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 21 carbon atoms, and a saturated alkyl group having 2 to 21 carbon atoms. An aliphatic acyloxy group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. A naphthyl group which may be substituted, a naphthoyl group which may be substituted, a naphthylalkyl group having 11 to 20 carbon atoms which may be substituted, 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 to 20, and more preferably 1 to 6. Further, the alkylene group may be linear or branched.
Specific examples of the N-substituted aminoalkyl group include a 2-(methylamino)ethyl group, a 2-(ethylamino)ethyl group, a 2-(n-propylamino)ethyl group, and a 2-(n-butylamino)ethyl group. 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-(propionyl) Amino)n-propyl group, 3-(acetoxyamino)n-propyl group, 3-(propionyloxyamino)n-propyl group, 2-(acetylamino)n-propyl group, 2-(propionylamino)n-propyl group And a 2-(acetoxyamino)n-propyl group and a 2-(propionyloxyamino)n-propyl group.
Specific examples of the N,N-disubstituted aminoalkyl group include a 2-(N,N-dimethylamino)ethyl group, a 2-(N,N-diethylamino)ethyl group, and a 2-(N,N-di-n group. -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,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-propionyl And oxyamino)n-propyl group, 2-(N-acetyl-N-acetoxyamino)n-propyl group, and 2-(N-propionyl-N-propionyloxyamino)n-propyl group.

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁴ 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 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 a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms , A dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁴ further have substituents, the number of the substituents is not limited as long as the object of the present invention is not impaired, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ⁴ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the organic groups, R ⁴ is an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group or a phenylthio which may have a substituent on the 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 which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. 5-10 are preferable, as for the carbon atom number of the cycloalkyl group contained in a cycloalkylalkyl group, 5-8 are more preferable, and 5 or 6 is especially preferable. 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, the 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 the 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 preferred.

Further, 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 preferably a monovalent hydrocarbon group.

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

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

Specific preferred examples of the group represented by —A ³ —CO—O—A ⁴ include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, and a 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.

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７及びＲ^８はそれぞれ有機基であり、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は有機基である。） Having described ^{R 4,} as is ^{R 4,} preferably 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 an organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are adjacent positions on the benzene ring. R ⁷ and R ⁸ may combine with 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. ) And R ⁹ is an organic group.)

Examples of the organic group for R ⁷ and R ^{8 in} formula (R4-1) are the same as for R ¹ . R ⁷ is preferably an alkyl group or a phenyl group. When R ⁷ is an alkyl group, its carbon atom number is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, it is most preferable that R ⁷ is a methyl group. When R ⁷ and R ⁸ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (R4-1) in which R ⁷ and R ⁸ form a ring include naphthalen-1-yl group, 1, 2, 3, and 4-tetrahydronaphthalen-5-yl group and the like can be mentioned. In the above formula (R4-1), p is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

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

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

(About R ⁵ )
In formula (1), R ⁵ is a monovalent organic group or a hydrogen atom. The monovalent organic group is, for example, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferable examples of the substituent that R ⁵ may have when R ⁵ is an alkyl group include a phenyl group and a naphthyl group. When R ¹ is an aryl group, examples of the substituent that the aryl group may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (1), R ⁵ is preferably exemplified by hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like. Of these, a methyl group or a phenyl group is more preferable.

（式（１Ｃ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、及びｎは前記の通り。） When T in the formula (1) is a group represented by the formula (T _C), as the compound represented by formula (1), a compound represented by the following formula (1C) are preferred.

(In the formula (1C), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and n are as described above.)

Further, among the compounds represented by the formula (1C), the compounds represented by the following formula (1C-1) or (1C-2) are preferable.

（式（１Ｎ）中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、及びｎは前記の通り。） When T in the formula (1) is a group represented by the formula ( _TN ), the compound represented by the formula (1) is preferably a compound represented by the following formula (1N).

(In the formula (1N), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and n are as described above.)

Further, among the compounds represented by the formula (1N), the compounds represented by the following formula (1N-1) or (1N-2) are preferable.

Suitable specific examples of the compound represented by the formula (1) include the following compounds 1 to 144.

The compound represented by the formula (1) described above has high sensitivity and gives a photosensitive composition excellent in sensitivity.

（式（１ａ）中、Ｔは前記の通り。）
で表される環骨格に、クロスカップリング反応により−Ｒ^６−Ｒ^１で表される基を導入することと、
（ＩＩ）式（１ａ）で表される環骨格に、−ＣＯ−Ｒ^４で表されるアシル基を導入した後、−ＣＯ−Ｒ^４で表される基を、−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基に変換し、さらに、−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基をエステル化して−Ｃ（＝Ｎ−Ｏ−ＣＯ−Ｒ^５）−Ｒ^４で表される基に変換することと、を含む、方法により製造される。 ≪Compound production method≫
The method for producing the compound represented by the above formula (1) is not particularly limited.
When n is 0, the compound represented by the formula (1) is, for example,
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by formula (II) (1a), after introducing an acyl group represented by ^{-CO-R 4,} a group represented by ^{-CO-R 4, -C (=} N-OH ) -R into a group represented by ^4, further, -C (= N-OH) -C esterifying a group represented by ^{-R 4 (= N-O-} CO-R 5) -R ^And converting to a group represented by ⁴ .

（式（１ａ）中、Ｔは前記の通り。）
で表される環骨格に、クロスカップリング反応により−Ｒ^６−Ｒ^１で表される基を導入することと、
（ＩＩ）式（１ａ）で表される環骨格に、−ＣＯ−ＣＨ_２−Ｒ^４で表されるアシル基を導入した後、−ＣＯ−ＣＨ_２−Ｒ^４で表される基を、−ＣＯ−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基に変換し、さらに、−ＣＯ−Ｃ（＝Ｎ−ＯＨ）−Ｒ^４で表される基をエステル化して−ＣＯ−Ｃ（＝Ｎ−Ｏ−ＣＯ−Ｒ^５）−Ｒ^４で表される基に変換することと、を含む、方法により製造される。 Further, in the case where n is 1, the compound represented by the formula (1) is, for example,
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by formula (II) (1a), after introducing an acyl group represented by _-CO-CH 2 -R ^4, a group represented by _-CO-CH 2 -R ^4, - CO-C (= N-OH ) is converted into a group represented by -R ^4, further, -CO-C (= N- OH) is esterified to a group represented by -R ⁴ -CO-C ( = includes converting the group represented by ^{N-O-CO-R 5} ) -R 4, and is manufactured by the method.

In the above method, either step (I) or step (II) may be performed first. Further, although the step (II) includes a multi-step operation, the step (I) may be performed at any timing of the step (II).

The method of converting the oxime group (=N-OH) to the oxime ester group represented by =N-O-COR ⁵ in step (II) in the above method is not particularly limited. Typically, a method of reacting a hydroxyl group in the oxime group with an acylating agent which 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).

When n is 0, the compound represented by the formula (1) can be synthesized according to the following scheme 1 as an example.
Note that in Scheme 1 below, a cross-coupling reaction is performed using a halogenated compound having a ring skeleton represented by the formula (1a) and a boron compound containing a group represented by —R ⁶ —R ^1. However, the cross-coupling reaction may be performed using a boron compound having a ring skeleton represented by the formula (1a) and a halogenated compound containing a group represented by —R ⁶ —R ¹ .
In addition, the cross coupling reaction
After introducing an acyl group represented by —CO—R ⁴ into the ring skeleton represented by the formula (1a),
The · ^-CO-R group represented by ⁴ is represented by -C (= N-OH) was converted to a group represented by -R ^4, and · -C (= N-OH) -R 4 based on may be implemented in any timing after conversion into the group represented by esterified -C (= N-O-CO -R 5) -R 4 that.

First, a compound 1B is obtained by introducing an acyl group represented by —CO—R ⁴ into compound 1A by a Friedel-Crafts acylation reaction. The acylating agent for introducing the acyl group represented by —CO—R ⁴ may be a halocarbonyl compound represented by Hal—CO—R ⁴ , and may be (R ⁴ CO) ₂ O acid anhydride. May be As the acylating agent, a halocarbonyl compound represented by Hal-CO-R ⁴ is preferable. Hal is a halogen atom. The position at which the acyl group is introduced can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, or by performing protection and deprotection on the other position of the acylated position.

When T in compound 1A is a group represented by the formula _{(T C),} for example, halogenated fluorene, such as bromo fluorene (preferably 2-bromo fluorene), a base such as potassium tert- butoxide, ^{R 2} Compound 1A is obtained by reacting with —Hal and R ³ —Hal. R ² -Hal, and the ^R 3 -Hal, Hal is a halogen atom, a bromine atom.
In addition, when T is a group represented by the formula (T _C ), a compound in which two R ² or two R ³ are bonded to the 9-position on the fluorene ring is a secondary compound when synthesizing the compound 1A. It may live. In this case, only the desired product may be collected according to a known method such as column chromatography.

Then, the compound 1B and a boron compound containing a group represented by R ¹ -R ⁶ -, such as R ¹ -R ⁶ -B(OH) ₂ are condensed by so-called Suzuki-Miyaura coupling reaction, Compound 1C is obtained.
The cross-coupling reaction is not limited to the Suzuki-Miyaura coupling reaction, and can be appropriately selected and used from known cross-coupling reactions.
The type of boron compound is not particularly limited as long as it can introduce the group represented by R ¹ -R ^6- into compound 1B.
The catalyst used in the Suzuki-Miyaura coupling reaction is not particularly limited as long as it has been conventionally used in the reaction. For example, as a suitable catalyst, [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride/dichloromethane adduct (Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ ), tetrakis(triphenylphosphine) ) palladium _{(0) (Pd (PPh 3} ) 4), [1,2- bis (diphenylphosphino ethane) palladium (II) dichloride _{(PdCl 2 (dppe)),} [1,3- bis (diphenylphosphino Propane)]palladium(II) dichloride (PdCl ₂ (dppp)), [1,1′-bis(diphenylphosphino)ferrocene]nickel(II) dichloride/dichloromethane adduct (Ni(dppf)Cl ₂ ·CH ₂ Cl ₂ ), bis(triphenylphosphine)nickel(II) dichloride (NiCl ₂ (PPh ₃ ) ₂ ) and the like. Further, palladium acetate or palladium chloride and an appropriate ligand may be mixed and used in the system.
The solvent used in this reaction is not particularly limited as long as it does not inhibit the progress of the reaction, and examples thereof include tetrahydrofuran (THF), methanol, ethanol, propanol, n-butanol, 2-butanol, toluene, ethyl acetate, N-methylpyrrolidone, Cyclopentyl methyl ether, dimethylformamide, dimethylacetamide, water and the like can be used.

Then, a group represented by ^{-CO-R 4} in the compound 1C, converted into a group represented by -C (= N-OH) -R 4, to obtain a compound 1D. The method for converting the group represented by —CO—R ⁴ into the group represented by —C(═N—OH)—R ⁴ is not particularly limited, but oximation with hydroxylamine is preferable. A compound represented by the formula (1) in which n is 0 by reacting the compound 1D with an acid anhydride ((R ⁵ CO) ₂ O) or an acid halide (R ⁵ COHal, where Hal is a halogen atom). The compound can be obtained.

<Scheme 1>

When n is 1, the compound represented by the formula (1) can be synthesized according to the following scheme 2 as an example.
In Scheme 2 below, a cross-coupling reaction is performed using a halogenated compound having a ring skeleton represented by the formula (1a) and a boron compound containing a group represented by —R ⁶ —R ^1. However, the cross-coupling reaction may be performed using a boron compound having a ring skeleton represented by the formula (1a) and a halogenated compound containing a group represented by —R ⁶ —R ¹ .
In addition, the cross coupling reaction
The ring structure represented by the formula (1a), after introducing an acyl group represented by _-CO-CH 2 -R ^4,
· A _-CO-CH 2 -R ^4, a group represented by the after conversion to a group represented by -CO-C (= N-OH ) -R 4, and · -CO-C (= N- OH ) -R ⁴ in the group represented by esterifying -CO-C (= N-O -CO-R 5) at any time after conversion to a group represented by -R ⁴ may be performed ..

In Scheme 2, the above compound 1A is used as a raw material. Compound 1E is obtained by introducing an acyl group represented by —CO—CH ₂ —R ⁴ into Compound 1A by Friedel-Crafts reaction in the same manner as in Scheme 1. The acylating agents, carboxylic acid halide represented by _Hal-CO-CH 2 ^{-R 4} are preferred.
Then, the compound 1E and the boron compound represented by R ¹ -R ⁶ -B(OH) ₂ are condensed by a so-called Suzuki-Miyaura coupling reaction to obtain a compound 1F. The condensation method by Suzuki-Miyaura coupling reaction is the same as in Scheme 1.
The methylene group existing between R ⁴ and the carbonyl group in the obtained compound 1F is oxime-ized to obtain compound 1G. The method of converting the methylene group into an oxime is not particularly limited, but a method of reacting a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid is preferable. Then, the compound 1G is reacted with an acid anhydride ((R ⁵ CO) ₂ O) or an acid halide (R ⁵ COHal, where Hal is a halogen atom), and n is 1 in the formula (1). The compounds represented can be obtained.

<Scheme 2>

In Scheme 1, compound 1B, compound 1C, compound 1D, and R ⁴ contained in the final product may be the same or different. That is, compound 1B, compound 1C, compound 1D, and R ⁴ contained in the final product may be chemically modified in the synthetic process shown as scheme 1. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, and substitution of a hydrogen atom in an amino group with an organic group. The chemical modification that R ⁴ may undergo is not limited to these.
R ⁴ included in the compound 1E, the compound 1F, the compound 1G, and the final product in the scheme 2 may be the same or different. R ⁴ contained in the compound 1E, the compound 1F, the compound 1G, and the final product may be chemically modified in the same manner as in the scheme 1 in the synthetic process shown as the scheme 12.

The compound represented by the formula (1), which can be synthesized by the method described above, is suitable for use as a photosensitizer such as a photopolymerization initiator after being appropriately produced according to a conventional method such as washing with a solvent, recrystallization and column purification. Used for.
The use of the compound represented by the formula (1) is not limited to the photopolymerization initiator. The compound represented by the formula (1) can be used for various photosensitizer applications in which an oxime ester compound has been conventionally used.

<<Example of application of compound represented by formula (1)>>
The compound represented by the formula (1) is preferably used as a photopolymerization initiator in a photosensitive composition containing a photopolymerizable compound. Such a photosensitive composition may contain a colorant, a solvent and the like. The components contained in the photosensitive composition will be described below.

<Photopolymerizable compound>
The photopolymerizable compound contained in the photosensitive composition is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, resins or monomers having an ethylenically unsaturated group are preferable, and it is more preferable to combine these. By combining the resin having an ethylenically unsaturated group and the monomer having an ethylenically unsaturated group, the curability of the photosensitive composition can be improved and pattern formation can be facilitated.

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

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

Among them, the compound represented by the following formula (a1) is preferable. The compound represented by the formula (a1) is preferable because it has high photocurability.

In the above formula (a1), X represents a group represented by the following formula (a2).

In the above formula (a2), R ^1a's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^2a's each independently represent a hydrogen atom or a methyl group, W represents a single bond or a group represented by the following structural formula (a3). In addition, in formula (a2) and structural formula (a3), "*" means the terminal of the bond of a divalent group.

In the above formula (a1), Y represents a residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro. Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula (a1), Z represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride and the like. Further, in the formula (a1), a represents an integer of 0-20.

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

The mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1,000 to 40,000, more preferably 2,000 to 30,000. When the mass average molecular weight is 1000 or more, good heat resistance and film strength can be obtained, which is preferable. Further, when the mass average molecular weight is 40,000 or less, good developability can be obtained, which is preferable.

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

Examples of 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-methyl propane sulfonic acid, tert-butyl acrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3 -Tetrafluoropropyl (meth)acrylate, half (meth)acrylate of a phthalic acid derivative and the like can be mentioned. These monofunctional monomers may be used alone or in combination of two or more.

As the polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di( (Meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (Meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)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, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether Poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth) Examples thereof include polyfunctional monomers such as acrylamide methylene ether, a condensation product of polyhydric alcohol and N-methylol (meth)acrylamide, and triacrylformal. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable compound is preferably 10 to 99.9 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition. By setting the content of the photopolymerizable compound to 10 parts by mass or more with respect to 100 parts by mass of the total solid content, a film excellent in heat resistance, chemical resistance, and mechanical strength can be obtained using the photosensitive composition. Easy to form.

<Photopolymerization initiator>
As the photopolymerization initiator, the compound represented by the above formula (1) is used. The compound represented by the formula (1) may be used in combination with a conventionally known photopolymerization initiator other than the compound represented by the formula (1).
Since the photosensitive composition contains the compound represented by the formula (1) as a photopolymerization initiator, it has excellent sensitivity. Therefore, by using the photosensitive composition containing the compound represented by the formula (1) as a photopolymerization initiator, it is possible to form a pattern having a desired shape with a low exposure amount. Further, by using a photosensitive composition having excellent sensitivity, it is possible to suppress pattern peeling during pattern formation and to prevent rattling that occurs at the edge of the pattern when forming a line pattern.

In particular, when the photosensitive composition contains a light-shielding agent as a colorant, the bottom portion of the coating film of the photosensitive composition is difficult to cure due to the influence of the light-shielding agent, so that an undercut is likely to occur in the formed pattern. ..

For example, in the case of forming a line-shaped black matrix pattern using a photosensitive composition, as shown in FIG. 1A, a cross-section 1 which is a cross section in the width direction of the pattern is smaller than a width of a bottom side 1a. It is generally desired that the top side 1b has a trapezoidal shape with a slightly narrow width. At this time, the angle θ formed by the cross section 1 of the pattern and the color filter substrate (not shown) is an acute angle close to 90°.

However, when a black matrix is formed using a conventional photosensitive composition containing a light-shielding agent, as shown in FIG. 1(b), a part of the bottom of the pattern is dissolved during development, so that the pattern is removed. Undercuts 21 may occur at both ends of the bottom side 2a in the cross section 2 which is the cross section in the width direction of the. At this time, the angle θ formed by the cross section 2 of the pattern and the substrate (not shown) is an obtuse angle.

When an undercut occurs in a pattern formed by using a photosensitive composition containing a light-shielding agent, for example, when a display device is formed using such a pattern as a black matrix, bubbles are left in the undercut portion. There is a problem that the image quality of the display device is degraded. However, when the photosensitive composition contains a photopolymerization initiator containing a compound represented by the formula (1) together with a light-shielding agent, an undercut of a pattern formed using such a photosensitive composition may occur. Occurrence can be suppressed.

The content of the photopolymerization initiator is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and 0.1 to 30 parts by mass based on 100 parts by mass of the total solid content of the photosensitive composition. It is more preferably 5 to 10 parts by mass.
Further, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, and 0.5 to 30% by mass with respect to the total mass of the photopolymerizable compound and the mass of the photopolymerization initiator. Is more preferable, and 1 to 20 mass% is further preferable.
The content of the compound represented by the formula (1) in the photopolymerization initiator may be, for example, in the range of 1 to 100 mass% with respect to the entire photopolymerization initiator, and preferably 50 mass% or more, 70 It is more preferable that the content is ˜100% by mass.

<Colorant>
The photosensitive composition may further contain a colorant. Since the photosensitive composition contains a colorant, it is preferably used as a color filter forming application in a display device such as a liquid crystal display. In addition, the photosensitive composition contains a light-shielding agent as a colorant, and thus is preferably used for forming a black matrix in a color filter of a display device.

The colorant to be blended in the photosensitive composition is not particularly limited, but is, for example, a compound classified as Pigment in the color index (CI; issued by The Society of Dyers and Colorists). Specifically, it is preferable to use the compounds having the following color index (CI) numbers.

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

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

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

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

Examples of suitable blue pigments include C.I. I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, and only the numbers are described). 2, 15, 15:3, 15:4, 15:6, 16, 22, 22, 60, 64 , And 66.

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

When the colorant is used as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigment include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, complex oxides, metal sulfides, Various pigments can be used regardless of organic substances or inorganic substances such as metal sulfates or metal carbonates. Among these, it is preferable to use carbon black having a high light-shielding property.

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

Resin-coated carbon black has lower conductivity than carbon black without resin coating. Therefore, when a black matrix is formed using a photosensitive composition containing resin-coated carbon black, a leak of current in a display element such as a liquid crystal display is small, and a highly reliable display with low power consumption can be manufactured. ..

Further, in order to adjust the color tone of carbon black, the above organic pigment may be appropriately added as an auxiliary pigment.

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

The inorganic pigment and the organic pigment may be used alone or in combination of two or more kinds. When used in combination, the organic pigment is preferably used in the range of 10 to 80 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. ..

The amount of the colorant used in the photosensitive composition may be appropriately determined depending on the application of the photosensitive composition. As an example, 5 to 70 parts by mass is preferable and 25 to 60 parts by mass is more preferable for 100 parts by mass of the total solid content of the photosensitive composition. The above range is preferable because the black matrix and each colored layer can be formed in a desired pattern.

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

The colorant is preferably added to the photosensitive composition after forming a dispersion liquid in which the colorant is dispersed at an appropriate concentration using a dispersant.

<Alkali-soluble resin>
The photosensitive composition may contain an alkali-soluble resin as a resin other than the resin used as the photopolymerizable compound. By adding an alkali-soluble resin to the photosensitive composition, it is possible to impart alkali developability to the photosensitive composition.

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

Among the alkali-soluble resins, a polymer of a monomer having an ethylenically unsaturated double bond is preferable because it has excellent film-forming properties and the characteristics of the resin can be easily adjusted by selecting the monomer. Examples of the monomer having an ethylenically unsaturated double bond include (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, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, And vinyl ethers such as vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. Vinyl esters such as vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene. , Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene , Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene Len, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethyl. Styrenes such as styrene or styrene derivatives; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The alkali-soluble resin, which is a polymer of a monomer having an ethylenically unsaturated double bond, usually contains a unit derived from an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali-solubility. .. The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 to 25% by mass, more preferably 8 to 16% by mass based on the mass of the resin.

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

The (meth)acrylic acid ester used in the preparation of a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester is particularly preferably within the range not impairing the object of the present invention. It is not limited and is appropriately selected from known (meth)acrylic acid esters.

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

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

The (meth)acrylic acid ester having a group having an epoxy group is a group having an alicyclic epoxy group as described below even if it is a (meth)acrylic acid ester having a group having a chain aliphatic epoxy group. (Meth)acrylic acid ester having

The (meth)acrylic acid ester having a group having an epoxy group may contain an aromatic group. A benzene ring and a naphthalene ring are mentioned as an example of the aromatic ring which comprises an aromatic group. Examples of the (meth)acrylic acid ester having an aromatic group and an epoxy group-containing group include 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, and 2-glycidyloxy. Examples thereof include phenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate.

When the film formed using the photosensitive composition is required to be transparent, the (meth)acrylic acid having a group having an epoxy group preferably does not contain an aromatic group.

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

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

Epoxy group in a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester containing a unit derived from (meth)acrylic acid ester having a group having an epoxy group The content of the unit derived from the (meth)acrylic acid ester having a group having is preferably 1 to 95% by mass, and more preferably 40 to 80% by mass, based on the weight of the resin.

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

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton is a group having an alicyclic epoxy group even if it is a group having an alicyclic hydrocarbon group. May be. 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. Further, 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 esters having a group having an alicyclic skeleton, examples of the (meth)acrylic acid ester having a group having an alicyclic hydrocarbon group include the following formulas (d1-1) to (d1- The compound represented by 8) is mentioned. Among these, the compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and the 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 saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or 1 carbon atom. The alkyl groups of 5 are shown. R ^d2 is preferably a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ^d3 is preferably a methyl group or an ethyl group.

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

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^d6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Shows a group and n shows the integer of 0-10. 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. Examples of R ^d6 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

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

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

In a resin containing a unit derived from (meth)acrylic acid and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth)acrylic acid in the resin 1 to 95 mass% is preferable, and 10 to 50 mass% is more preferable. In a resin containing a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, a group having an alicyclic epoxy group in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from the (meth)acrylic acid ester which it has, 30-70 mass% is more preferable.

A unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group are selected from (meth)acrylic acid and (meth)acrylic acid ester. Among polymers of one or more kinds of monomers, a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and an alicyclic epoxy A resin containing a unit derived from a (meth)acrylic acid ester having a group having a group is preferable.

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

The weight average molecular weight of the alkali-soluble resin (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene, the same in the present specification) is preferably 2000 to 200000, and more preferably 2000 to 18000. preferable. Within the above range, the film forming ability of the photosensitive composition and the developability after exposure tend to be easily balanced.

When the photosensitive composition contains an alkali-soluble resin, the content of the alkali-soluble resin in the photosensitive composition is preferably 15 to 95% by mass, more preferably 35 to 85% by mass in the solid content of the photosensitive composition. 50-70 mass% is especially preferable.

<Other ingredients>
The photosensitive composition may contain various additives, if necessary. Specifically, a solvent, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an agglomeration inhibitor, a thermal polymerization inhibitor. Examples include agents, defoaming agents, surfactants and the like.

Examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (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, etc. (Poly)alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2-hydroxy Lactic acid alkyl esters such as methyl propionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3 -Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate , 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, Examples include 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, 3-methoxybutyl acetate, the above (A ) And the component (B) are excellent in solubility and the dispersibility of the component (C) can be improved, which is preferable, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used. Is particularly preferable. The solvent may be appropriately determined depending on the application of the photosensitive composition, but as an example, about 50 to 900 parts by mass can be mentioned with respect to 100 parts by mass of the total solid content of the photosensitive composition.

Examples of the thermal polymerization inhibitor used in the photosensitive composition according to the present invention include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicone-based and fluorine-based compounds, and examples of the surfactant include anionic-based, cation-based and nonionic compounds.

[Method for preparing photosensitive composition]
The photosensitive composition is prepared by mixing all of the above components with a stirrer. When the prepared photosensitive composition does not contain an insoluble component such as a pigment, it may be filtered using a filter so that the photosensitive composition becomes uniform.

<Film forming method>
A method for forming an insulating film or a film used as a color filter using the above-described photosensitive composition will be described below. The film formed using the photosensitive composition may be patterned if necessary.

In order to form a film using the photosensitive composition, first, a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. The photosensitive composition is applied onto the substrate using.

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

Then, this coating film is exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The exposure may be performed position-selectively by, for example, a method of performing exposure through a negative mask. The energy dose for irradiation varies depending on the composition of the photosensitive composition, but is preferably about 40 to 200 mJ/cm ² , for example.

When the coating film is position-selectively exposed, the exposed film is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spray method or the like can be used. The developing solution is appropriately selected according to the composition of the photosensitive composition. When the photosensitive composition is a part containing an alkali-soluble component such as an alkali-soluble resin, the developer may be an organic developer such as monoethanolamine, diethanolamine or triethanolamine, sodium hydroxide or hydroxide. An aqueous solution of potassium, sodium carbonate, ammonia, a quaternary ammonium salt or the like can be used.

Then, post-baking is preferably performed on the developed pattern at about 200 to 250°C.

The pattern thus formed can be preferably used for applications such as an insulating film, pixels constituting a color filter, and a black matrix used in a display device such as a liquid crystal display.

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

[Example 1]
Synthesis of Compound 2 The above-mentioned compound 2 was synthesized according to the following synthetic method. The abbreviations in the following synthetic schemes have the following meanings.
^t Bu: tert-butyl group Pr: n-propyl group Ac: acetyl group

After charging 500 parts by mass of tetrahydrofuran (THF) and 68.7 parts by mass of potassium tert-butoxide to the reaction vessel, 50.0 parts by mass of 2-bromofluorene was added.
Then, 56.1 parts by mass of 1-bromopropane was added dropwise to the reaction vessel, and the mixture was stirred at 40° C. for 3 hours. After the reaction solution was cooled to room temperature, ethyl acetate and water were added thereto for liquid separation and water washing. The oil layer was concentrated to obtain 67.2 parts by mass of 2-bromo-9,9-dipropylfluorene (yield 100%, HPLC purity 92%).
The reaction vessel was charged with 50.0 parts by mass of the obtained 2-bromo-9,9-dipropylfluorene, 500 parts by mass of methylene chloride, and 30.4 parts by mass of anhydrous aluminum chloride, and cooled to 0°C.
After dropping 16.9 parts by mass of propionyl chloride, the mixture was stirred at 10° C. for 3 hours. The reaction solution was poured into ice water, the layers were separated, and the oil layer was washed with 5% aqueous sodium hydrogen carbonate and water. The oil layer was concentrated and isolated and purified by silica gel column chromatography to obtain 46.8 parts by mass of compound 2a (yield 80%, HPLC purity 95%).
To 150 parts by mass of THF was added 30.0 parts by mass of the compound 2a, and then 15.6 parts by mass of 4-nitrophenylboronic acid and 21.5 parts by mass of potassium carbonate were added. Then, [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (0.6 parts by mass) and water (3 parts by mass) were added, and the mixture was stirred at reflux temperature for 5 hours.
The reaction solution was cooled to room temperature, insoluble matter was filtered off, the filtrate was concentrated to dryness, and then isolated and produced by silica gel chromatography to give 24.7 parts by mass of compound 2b (yield 75%, HPLC purity 95%. ) Got.
75.0 parts by mass of methanol, 7.4 parts by mass of hydroxylamine hydrochloride, and 6.9 parts by mass of sodium acetate were added to 15.0 parts by mass of the compound 2b, and the mixture was stirred at 60° C. for 5 hours. The reaction solution was cooled to room temperature, 25 parts by mass of water was added, and the mixture was filtered and washed with methanol and then with water. After drying by blast drying, 15.5 parts by mass of compound 2c (yield 100%, HPLC purity 90%) was obtained.
50.0 parts by mass of ethyl acetate and 9.3 parts by mass of acetic anhydride were added to 10.0 parts by mass of the compound 2c, and the mixture was stirred at 40° C. for 5 hours. After cooling the reaction solution to room temperature, 10.0 parts by mass of methanol was added and the mixture was stirred for 30 minutes, and the precipitated solid was filtered. The obtained solid was isolated and purified by silica gel column chromatography to obtain 5.5 parts by mass of compound 2 (yield 50%, HPLC purity 98%). The structure of the obtained compound 2 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ^{The 1} H-NMR spectrum is shown below.
δ [ppm]: 8.30-8.35 (m:2H), 7.71-7.85 (m:6H), 7.58-7.65 (m:2H), 2.93 (q: 2H), 2.30 (s:3H), 1.98-2.10 (m:4H), 1.24 (t:3H), 0.64-0.76 (m:10H).

[Example 2]
Synthesis of Compound 37 The following compound 37 was prepared in the same manner as in Example 1 except that propionyl chloride was changed to butyryl chloride and 4-nitrophenylboronic acid was changed to 4-cyanophenylboronic acid. Obtained.
The aforementioned compound 37 was synthesized according to the following synthetic method. The abbreviations in the following synthetic schemes have the same meanings as in Example 1.

Compound 37a was obtained in the same manner as in Example 1 except that propionyl chloride was changed to butyryl chloride.
80 parts by mass of THF, 80 parts by mass of methanol, 6.2 parts by mass of sodium acetate and 5.2 parts by mass of hydroxylamine hydrochloride were added to 20 parts by mass of the compound 37a, and the mixture was stirred at 60° C. for 5 hours. The reaction solution was cooled to room temperature, added with 60 parts by mass of water, filtered, and washed with methanol. It was dried by blast drying to obtain 19.8 parts by mass of compound 37b (yield 95%, HPLC purity 90%).
75 parts by mass of THF was added to 15.0 parts by mass of the compound 37b, and then 6.4 parts by mass of 4-cyanophenylboronic acid and 7.6 parts by mass of potassium carbonate were added. Subsequently, 0.3 part by mass of [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct and 3 parts by mass of water were added, followed by stirring at a reflux temperature for 5 hours.
The reaction solution was cooled to room temperature, insoluble matter was filtered off, the filtrate was concentrated to dryness, and then isolated and produced by silica gel chromatography to obtain 8.1 parts by mass of compound 37c (yield 52%, HPLC purity 95%). ) Got.
25.0 parts by mass of ethyl acetate and 2.4 parts by mass of acetic anhydride were added to 5.0 parts by mass of compound 37c, and the mixture was stirred at 40° C. for 5 hours. After cooling the reaction solution to room temperature, 10.0 parts by mass of methanol was added and the mixture was stirred for 30 minutes, and the precipitated solid was filtered. The obtained solid was isolated and purified by silica gel column chromatography to obtain 2.7 parts by mass of compound 37 (yield 50%, HPLC purity 98%).
The structure of the obtained compound 37 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ^{The 1} H-NMR spectrum is shown below.
δ [ppm]: 7.67-7.82 (m:8H), 7.55-7.60 (m:2H), 2.90 (t:2H), 2.30 (s:3H), 1 .93-2.07 (m:4H), 1.65 (sep:2H), 1.12 (t:3H), 0.65-0.70 (m:10H).

[Example 3]
Synthesis of Compound 20 Compound 20 shown below was prepared in the same manner as in Example 1 except that propionyl chloride was changed to butyryl chloride and 4-nitrophenylboronic acid was changed to 3-nitrophenylboronic acid. Obtained.

The structure of the obtained compound 20 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ^{The 1} H-NMR spectrum is shown below.
δ [ppm]: 8.52 (t: 1H), 8.19-8.25 (m: 1H), 7.96-8.02 (m: 1H), 7.58-7.86 (m: 7H), 2.91 (q:2H), 2.29 (s:3H), 1.96-2.12 (m:4H), 1.58-1.70 (m:2H), 1.02. (T:3H), 0.58-0.75 (m:10H)

プロピオニルクロライドをブチリルクロライドに変更することと、４−ニトロフェニルボロン酸を３−ニトロフェニルボロン酸に変更することとを除いて、実施例１と同様にして化合物２８ｂを得た。
化合物２８ｂ２０質量部に、ＴＨＦ１５０質量部、３５％塩酸１２．０質量部を加えた。亜硝酸イソペンチル８．１質量部を室温でゆっくり加え、７時間撹拌を継続した。得られた反応液を濃縮乾固し、シリカゲルカラムクロマトグラフィーにより単離精製して、化合物２８ｃ１１．９質量部（収率５５％、ＨＰＬＣ純度９５％）を得た。
得られた化合物２８ｃ１０．０質量部に酢酸エチル１００質量部、無水酢酸２．６質量部を加え、４０℃で５時間撹拌した。反応液を室温まで冷却後、濃縮乾固し、シリカゲルカラムクロマトグラフィーにより単離精製して、化合物２８を８．２質量部（収率７５％、ＨＰＬＣ純度９７％）得た。
得られた化合物２８の構造は、^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）により確認した。^１Ｈ−ＮＭＲスペクトルを以下に示す。
δ［ｐｐｍ］：８．５３（ｔ：１Ｈ）、８．２０−８．２６（ｍ：１Ｈ）、８．０７−８．１６（ｍ：２Ｈ）、７．９６−８．０２（ｍ：１Ｈ）、７．８３（ｑ：２Ｈ），７．５８−７．６８（ｍ：３Ｈ）、２．８５（ｑ：２Ｈ）、２．３０（ｓ：３Ｈ）、１．９６−２．１５（ｍ：４Ｈ）、１．２２（ｔ：３Ｈ）、０．５８−０．８０（ｍ：１０Ｈ） [Example 4]
Synthesis of Compound 28 The above-mentioned Compound 28 was synthesized according to the following synthetic method. The abbreviations in the following synthetic schemes have the same meanings as in Example 1.

Compound 28b was obtained in the same manner as in Example 1 except that propionyl chloride was changed to butyryl chloride and 4-nitrophenylboronic acid was changed to 3-nitrophenylboronic acid.
To 20 parts by mass of compound 28b, 150 parts by mass of THF and 12.0 parts by mass of 35% hydrochloric acid were added. 8.1 parts by mass of isopentyl nitrite was slowly added at room temperature, and stirring was continued for 7 hours. The obtained reaction solution was concentrated to dryness, and isolated and purified by silica gel column chromatography to obtain 11.9 parts by mass of compound 28c (yield 55%, HPLC purity 95%).
100 parts by mass of ethyl acetate and 2.6 parts by mass of acetic anhydride were added to 10.0 parts by mass of the obtained compound 28c, and the mixture was stirred at 40° C. for 5 hours. The reaction solution was cooled to room temperature, concentrated to dryness, and isolated and purified by silica gel column chromatography to obtain 8.2 parts by mass of compound 28 (yield 75%, HPLC purity 97%).
The structure of the obtained compound 28 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ^{The 1} H-NMR spectrum is shown below.
δ [ppm]: 8.53 (t: 1H), 8.20-8.26 (m: 1H), 8.07-8.16 (m: 2H), 7.96-8.02 (m: 1H), 7.83 (q:2H), 7.58-7.68 (m:3H), 2.85 (q:2H), 2.30 (s:3H), 1.96-2.15. (M:4H), 1.22 (t:3H), 0.58-0.80 (m:10H)

[Example 5]
Synthesis of Compound 138 Changing 2-bromo-9,9-dipropylfluorene to N-ethyl-3-bromocarbazole, changing 4-nitrophenylboronic acid to 3-nitrophenylboronic acid, and propionyl The following compound 138 was obtained in the same manner as in Example 1 except that the chloride was changed to 4-((1-methoxypropan-2-yl)oxy)-2-methylbenzoic acid chloride.

The structure of the obtained compound 138 was confirmed by ¹ H-NMR spectrum (CDCl ₃ ). ^{The 1} H-NMR spectrum is shown below.
δ [ppm]: 8.54 (brs: 1H), 8.30 (brs: 2H), 8.00-8.20 (m: 2H), 7.86 (dd: 1H), 7.75 (dd) :1H), 7.63 (t: 1H), 7.42 (d: 1H), 7.40 (d: 1H), 7.08 (d: 1H), 6.85-6.95 (m: 2H), 4.60-4.70 (m:1H), 4.42 (q:2H), 3.50-3.70 (m:2H), 3.46 (s:3H), 2.18. (S:3H), 2.12 (s:3H), 1.50 (t:3H), 1.60 (d:3H)

[Examples 6 to 18, Comparative Example 1, and Comparative Example 2]
In Examples and Comparative Examples, resin A and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) were used as photopolymerizable compounds. The resin A used was one synthesized according to the following formulation.

First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), tetramethylammonium chloride 110 mg, 2,6-di-tert-butyl-4-methylphenol 100 mg, and acrylic acid 72.0 g. Was charged and heated and dissolved at 90 to 100° C. while blowing air at a rate of 25 ml/min. Next, the temperature of the solution was gradually increased in a cloudy state and heated to 120° C. to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but the stirring was continued as it was. During this period, the acid value was measured and heating and stirring were continued until the acid value was less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenolfluorene type epoxy acrylate represented by the following structural formula (a4).

Then, after adding and dissolving 600 g of 3-methoxybutyl acetate to 307.0 g of the above-obtained bisphenolfluorene type epoxy acrylate, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, and the temperature was gradually raised to react at 110 to 115° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to obtain a resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum. The resin A corresponds to the compound represented by the above formula (a1).

In the examples, the following compounds 1, compounds 4 to 10 and compounds 13 to 17 were used as photopolymerization initiators. The following Compound 1, Compounds 4 to 10, and Compounds 13 to 17 were synthesized by the same method as in Examples 1 to 5.

In Comparative Examples, the following Comparative Compound 1 and Comparative Compound 2 were used as photopolymerization initiators.

Resin A 25 parts by mass, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 10 parts by mass, photopolymerization initiator 5 parts by mass of the kind shown in Table 1, carbon dispersion (CF black, Mikuni dye stock) 60 parts by mass) was diluted with a mixed solvent consisting of 3-methoxybutyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate so that the solid content concentration became 15% by mass, and then these components were homogenized. By mixing, the photosensitive compositions of Examples 6 to 18, Comparative Example 1 and Comparative Example 2 were obtained. The mass ratio of each solvent in the mixed solvent was 60/20/20 as 3-methoxybutyl acetate/cyclohexanone/propylene glycol monomethyl ether acetate.

[Sensitivity evaluation]
The sensitivity was evaluated according to the following procedure. First, the photosensitive compositions of Examples and Comparative Examples were applied on a glass substrate (10 cm×10 cm) using a spin coater and prebaked at 90° C. for 120 seconds to give a film thickness of 1.0 μm on the surface of the glass substrate. To form a coating film. After that, a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used, and the coating film was irradiated with ultraviolet rays through a negative mask having a pattern with a width of 10 μm and an exposure gap of 50 μm. .. The exposure amount was set to three levels of 30, 60, 1200 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26° C. for 30 seconds, and post-baked at 230° C. for 30 minutes to obtain a pattern of each exposure amount. The line width of the pattern at each exposure amount was measured with an optical microscope, and the exposure amount at which a line width of 10 μm was obtained was calculated from the line width at each exposure amount and the exposure amount by approximation calculation by the least square method. Table 1 shows the calculated sensitivity (mJ/cm ² ) data at a developing time of 30 seconds. The sensitivity data shown in Table 1 shows the amount of exposure required to form a pattern (10 μm) having a predetermined line width, and the smaller the value, the higher the sensitivity of the photosensitive composition. To do.

[Evaluation of OD value]
The photosensitive composition of each Example and Comparative Example was coated on a 6-inch glass substrate (1737 glass manufactured by Dow Corning), and then dried at 90° C. for 60 seconds to form a coating film. Next, this coating film was irradiated with ghi rays at an exposure dose of 60 mJ/cm ² . Then, post-baking was performed on the hot plate at 230° C. for 20 minutes to form a light shielding curtain. The formed light-shielding films had three levels of 0.8 μm, 1.0 μm, and 1.2 μm. With respect to this light-shielding film, the OD value at each film thickness was measured using D200-II (manufactured by Macbeth), and the OD value per 1 μm was calculated using an approximate curve. The calculated OD value of the light-shielding film formed using the photosensitive composition of each of Examples and Comparative Examples was 4.8/μm.

[Line pattern evaluation]
The photosensitive compositions of Examples and Comparative Examples were applied on a glass substrate (100 mm×100 mm) using a spin coater and prebaked at 70° C. for 120 seconds to form a coating film. Then, using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the coating film is irradiated with ultraviolet rays through a negative mask having an exposure gap of 50 μm and a line pattern with a width of 10 μm. did. The exposure amount was set to four levels of ²⁰ , 40, 60 and 120 mJ/cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26° C. for 50 seconds, and post-baked at 230° C. for 30 minutes to form a line pattern having a film thickness of 3.5 μm.

(Pattern peeling evaluation)
The formed line pattern was observed with an optical microscope to confirm the presence or absence of pattern peeling. Table 1 shows the results of confirmation of the presence or absence of pattern peeling.

(Taper angle)
The taper angle was evaluated for the line pattern formed with the exposure amount of 40 mJ/cm ² . Based on the measured taper angle, the cross-sectional shape of the line pattern was judged according to the following criteria.
A: The taper angle is 70° or more and 85° or less.
◯: The taper angle is more than 85° and 90° or less.
Δ: The taper angle is more than 90° and 100° or less.
X: The taper angle is more than 100°.

The taper angle was measured as a bonding angle between the pattern and the substrate with a scanning electron microscope. This taper angle corresponds to the angle θ in FIGS. 1(a) and 1(b). Table 1 shows the measured taper angles. The closer the taper angle is to 90° C., the closer the shape of the pattern cross section is to the desired rectangular shape. When the taper angle is an acute angle and is considerably smaller than 90° C., an undercut does not occur in the pattern, but the shape of the pattern cross section is not the desired rectangular shape. When the taper angle is obtuse, the pattern has undercuts.

According to Table 1, it can be seen that the photosensitive compositions of Examples containing a photopolymerizable compound and a compound having a structure represented by the formula (1) as a photopolymerization initiator have excellent sensitivity.
According to Examples 13 to 18, when the compound in which n in the formula (1) is 1 is used, it is easy to obtain a photosensitive composition having particularly excellent sensitivity.
Further, it can be seen from Table 1 that by using the photosensitive composition of the example, it is possible to form a line pattern which is difficult to peel off from the substrate and has a desired rectangular cross section.

On the other hand, it can be seen that the photosensitive composition of Comparative Example containing a photopolymerization initiator having a structure not included in the formula (1) is inferior in sensitivity. When a line pattern is formed using the photosensitive composition of Comparative Example, pattern peeling occurs depending on the exposure dose, and the taper angle is obtuse, resulting in undercut in the line pattern.

1 Cross section in the width direction in a pattern without undercut 2 Cross section in the width direction in a pattern with undercut

Claims (5)

A compound represented by the following formula (1).

(In the formula (1), R ¹ represents a nitro group , R ⁶ represents a phenylene group , R ⁴ represents a monovalent organic group or a hydrogen atom, and R ⁵ represents a monovalent organic group or a hydrogen atom. the stands, n is 0 or 1, T is of the formula _{(T C)} or formula _(T n):

Represents a group represented by
Wherein (T _C) and formula (T _N), R ² and R ³ are each independently optionally substituted alkyl group, or a hydrogen atom, * represents a bond,
In formula (T _C ), R ² and R ³ may combine to form a ring. ) The compound according to claim 1, which is represented by the following formula (1C).

(In the formula (1C), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and n are as described above.) The compound according to claim 1, which is represented by the following formula (1N).

(In the formula (1N), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , and n are as described above.) The method for producing the compound according to claim 1, which is represented by the formula (1), and n is 0.
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by (II) Formula (1a), after introducing an acyl group represented by ^{-CO-R 4,} a group represented by ^{-CO-R 4, -C (=} N- converted into a group represented by OH) -R ^4, further, -C (= N-OH) -C esterifying a group represented by ^{-R 4 (= N-O-} CO-R 5) - Converting to a group represented by R ⁴ . The method for producing the compound according to claim 1, which is represented by the formula (1), and n is 1.
(I) The following formula (1a):

(In the formula (1a), T is as described above.)
Introducing a group represented by -R ⁶ -R ¹ into the ring skeleton represented by
The ring structure represented by (II) Formula (1a), after introducing an acyl group represented by _-CO-CH 2 -R ^4, a group represented by _-CO-CH 2 -R ^4, -CO-C (= N-OH ) is converted into a group represented by -R ^4, further, -CO-C (= N- OH) a group represented by -R ⁴ was esterified -CO-C ^{(= N-O-CO-} R 5) -R includes converting the group represented by ^4, the method.

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