JP2002080821A - Photosensitizer and visible light photocuring resin composition using the photosensitizer and its usage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a visible light sensitive resin composition having enough sensitivity to visible light region, especially, to second harmonics of He-Cd laser, argon laser, and YAG laser, excellent in storage stability, and capable of forming an excellent photosensitive layer for a visible light laser. SOLUTION: This photosensitizer contains at least an indolizine compound represented by formula (1) (wherein ring A represents an indolizine ring which may have a substituent, and X, Y, and Z show the meaning shown in the detailed description of the patent), and this visible light curing resin composition contains the photosensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitizer using an indolizine compound having a specific structure, and a visible light having high sensitivity to light in the visible light region by containing the photosensitizer. The present invention relates to a photocurable resin composition. In addition, the present invention relates to a visible light curable resin composition which has improved curing inhibition due to oxygen and exhibits high sensitivity to light in the visible light region and has excellent curability.

Further, the present invention relates to a visible light curable resin composition used under a specific safety light irradiation environment.

[0003]

2. Description of the Related Art In recent years, in the field of information using a photopolymerization reaction or in the field of image recording, an original electronically edited by a computer has been used as it is, instead of a conventional recording method using ultraviolet light using a film original. A method of directly outputting and recording using a laser is being studied. This method has the advantage that the recording and image forming steps can be greatly simplified by direct writing with a laser.

[0004] At present, many high power and stable laser light sources generally used have an output wavelength in the visible region. Specifically, the wavelength 488 nm and 51
Argon laser with stable oscillation line at 4.5 nm, or YAG with emission line at 532 nm as second harmonic
A laser such as a He-Cd laser having an oscillation line at 430 nm is widely used.
A blue-violet laser having an oscillation line has been developed. Therefore, compounds that are highly sensitive to these wavelengths are desired, but in the case of a conventional photosensitive agent for ultraviolet light,
It could not be used due to low sensitivity in the visible region. Also,
With the addition of pyrylium salts or thiopyrylium salts,
Although the sensitivity in the visible region can be improved, the storage stability of the photosensitive layer is low and it has been difficult to use it.

As compounds having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazoylcoumarin (common name: coumarin-6) or bis [3
-(7-diethylaminocoumaryl)] ketone (common name:
Ketocoumarin) is known, but since these have a maximum absorption wavelength of about 450 nm, they have a shorter wavelength than 488 nm of an argon laser and have insufficient sensitivity. Further, 4-substituted-3 compounds described in JP-A-4-18088.
-The benzothiazoyl coumarin compound shows high photosensitivity at 488 nm of an argon laser, but is 514.5.
532 which is the second harmonic of nm or YAG laser
nm has almost no absorption, leaving room for improvement in sensitivity.

[0006] Further, European Patent No. 0619520, US Patent No. 5,498,641, JP-A-9-258444, JP-A-8-179504, and JP-A-8-952.
No. 44, JP-A-8-76377, JP-A-8-76377
JP-A-6245, JP-A-7-225474, JP-A-7-219223, JP-A-7-5685, and JP-A-5-241338 disclose dipyrromethene-based boron compounds. If used,
There is room for improvement in the sensitivity to the laser light and the storage stability of the photosensitive layer.

On the other hand, conventionally, in order to form a conductive circuit such as a printed wiring board, a resist pattern is formed on a substrate coated with a photosensitive resist by exposure / development,
Unnecessary portions are removed by etching.

As an exposure method, there are a method of exposing through a photomask and a method of directly drawing a resist with a laser. The method of exposing through a photomask requires a considerable amount of time for positioning the photomask, and has problems such as difficulty in positioning the photomask if the resist surface is sticky.

In the method of directly writing a resist with a laser, the exposure time is extremely short, and therefore, the resist is required to have high sensitivity. For this reason, it is general to maintain high sensitivity by covering the resist surface with an oxygen blocking layer such as a cover coat or a cover film so as to prevent active radicals generated by laser irradiation from being deactivated by oxygen in the air, thereby blocking oxygen. There is a problem that it is performed but it is troublesome.

[0010] When the visible light-sensitive resin composition to be cured by visible light as described above is used, a dark red colorant is coated on the outer tube or a dark red film is coated on the outer tube. Electric lights such as fluorescent lamps that are colored by being wound are used as safety lights (working lights). However, under such a dark red safety light environment, it is not easy to inspect the state of the coating film after application, and it is not easy to inspect the coating device, irradiation device, transport device, etc. There is a problem that work efficiency, product quality stability and the like are inferior. Further, when a non-colored fluorescent lamp is used as a safety lamp, the working environment is bright and there is no problem.

[0011]

SUMMARY OF THE INVENTION The present invention is directed to an argon laser having a wavelength of 488, which is a high-power and stable laser light source.
Oscillation line of nm or 514.5 nm, laser light of a long wavelength in a visible light region such as 532 nm which is the second harmonic of YAG laser, or wavelength 430 of He-Cd laser.
photosensitizer which is highly sensitive to laser light in the visible light region such as an oscillation line having a wavelength of 405 nm and an emission line having a wavelength of 405 nm of a blue-violet laser and has excellent storage stability, and a visible light containing the photosensitizer. A curable resin composition is provided.

Further, the present invention provides a method of drawing a resist directly with a visible light laser without using a photomask, wherein active radicals generated in the resist by laser irradiation are hardly deactivated by oxygen in the air.
An object of the present invention is to provide a resist capable of maintaining high sensitivity.

Further, the present invention provides a visible light curable resin composition having excellent sensitivity which can be handled under a specific bright safe light condition.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have developed a visible light photosensitive resin composition using a specific photosensitizer. To solve traditional problems,
The present invention has been completed.

That is, the present invention provides a compound represented by the general formula (1):

[0016]

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In the formula, ring A represents an indolizine ring which may have a substituent, X is a hydrogen atom, a cyano group,
Carboxyl group, the following formula (2)

[0018]

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Wherein Q is independently an optionally substituted alkoxy, aralkyloxy, aryloxy, alkenyloxy, alkylthio, aralkylthio, arylthio, alkenylthio group Or the following formula (3)

[0020]

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(Wherein L ¹ and L ² each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group, an aryl group, or an alkenyl group). Represent. Y represents a carboxyl group, a carbonyl group or a heterocyclic group represented by the formula (2), Z represents an oxygen atom, a sulfur atom, and a compound represented by the following formula (4) )

[0022]

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[Wherein T ¹ and T ² each independently represent a hydrogen atom, a cyano group, a carbonyl group represented by the formula (2), or a compound represented by the following formula (5):

[0024]

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(Wherein M ^{1 to} M ³ are an alkyl group which may be substituted, G is an oxygen atom or a dicyanomethylidenyl group,
* Represents a bonding position. ). ] The present invention relates to a photosensitizer comprising at least one indolizine compound represented by the formula (1).

Further, the present invention relates to a composition containing a photocurable resin (A), a photoreaction initiator (B) and the photosensitizer (C).

Further, a composition for a visible light curable material containing the visible light curable resin composition of the present invention and a solvent, and a visible light containing a visible light curable resin composition on a substrate. It relates to a cured material.

The present invention further relates to a novel indolizine compound represented by the following formula (9).

[0029]

Embedded image [Wherein R ⁵ and R ⁶ are both hydrogen atoms or are bonded to represent a condensed benzene ring, and Y ′ is COOR ″ (R ″ is an alkyl group or an aralkyl group which may have a substituent) Represents ]

In the present invention, the visible light-curable resin composition containing a specific compound as a photosensitizer is a composition having extremely high practical utility. Conventionally, in the information recording field using the photocuring reaction, in the method of directly outputting and recording the original electronically edited by a computer using a laser as it is, the temporal stability of the photosensitive layer is low, and the sensitivity is low, There were problems such as solubility and storage stability.

However, the visible light curable resin composition of the present invention has extremely good compatibility between the photocurable resin and the photosensitizer, and is dissolved in a general-purpose coating solvent, and is uniform on a support. ,
A coated surface excellent in storage stability over time can be obtained.

The indolizine compound photosensitizer having a unique structure used in the present invention has an argon laser having stable oscillation lines at 488 nm and 514.5 nm and an emission line at 532 nm as a second harmonic. YAG laser, He-Cd laser having an oscillation line at 430 nm,
Since it has very high sensitivity to a general-purpose visible laser such as a blue-violet laser having an oscillation line at 405 nm, a photosensitive material obtained using the visible light-curable resin composition of the present invention can be used with such a laser. High-speed scanning exposure is possible. When an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

The visible light-curable resin composition of the present invention can be coated and printed under bright environmental conditions without increasing the viscosity of the composition under environmental conditions of safe light irradiation.
It exerts a remarkable effect that is excellent in safety workability, work efficiency, product quality stability and the like.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that the indolizine compound of the general formula (1) is used as a photosensitizer.

The photosensitizer using the indolizine compound represented by the general formula (1) is excited by absorbing light in the visible light region of 400 to 700 nm, particularly light of 400 to 600 nm, It is a material that interacts with the photocurable resin (A) and the photoreaction initiator (B). The term "interaction" as used herein includes energy transfer and electron transfer from the excited photosensitizer (C) used in the present invention to the photocurable resin (A) or photoreaction initiator (B). Is done.

The present inventors have found that a photosensitizer using an indolizine compound represented by the general formula (1) is extremely useful. The indolizine compound represented by the general formula (1) used in the present invention can be produced using argon laser light or YA
It has a very large absorption at the wavelength of the G laser second harmonic light, and is very sensitive to such light. It is an applicable and extremely useful material as a photosensitizer.

The term "composition for visible light curable material" as used in the present invention means, for example, a photosensitive paint, a photosensitive ink, a photosensitive adhesive, a photosensitive paint containing the visible light curable resin composition of the present invention. It means a photosensitive printing plate material, a photosensitive resist material, a non-photosensitive coating material formed from these materials, and the like.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (1) having an optionally substituted indolizine ring represented by the ring A of the present invention is specifically represented by the following general formula (6) Is done.

[0040]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a cyano group, a hydroxyl group, a halogen atom, an alkyl group which may have a substituent, Aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, acyl group, acyloxy group, heteroaryl group, heteroaryl Oxy group, heteroarylthio group, the following formula (7)

[0042]

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[In the formula, Q represents the same group as Q in the general formula (2). Or a carbonyl group represented by the following formula (8):

[0044]

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[Wherein L ¹ and L ² represent the same groups as Q in formula (3)]. And an amino group represented by R ^{1 to} R ⁵
And the adjacent groups may be bonded to each other to form an alicyclic or aromatic ring which may be substituted, and X, Y and Z represent the same groups as X, Y and Z in the general formula (1) . ]

In the compound represented by formula (6) according to the present invention, specific examples of R ^{1 to} R ⁵ include a hydrogen atom; a cyano group; a hydroxyl group; a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And the like.

Examples of the alkyl group which may have a substituent represented by R ^{1 to} R ⁵ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and an iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-
Methylbutyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, cyclopentyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1- Methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl Group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group,
2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,
5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5
5-trimethylhexyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group,
1-cyclopentyl-2,2-dimethylpropyl group, 1
-Cyclohexyl-2,2-dimethylpropyl group, n-
Nonyl group, n-decyl group, 4-ethyloctyl group, 4-
Ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group , 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, decalyl group, adamantyl group, icosanyl group, 4-
1-20 carbon atoms such as t-butylcyclohexyldecyl group
A straight-chain, branched or cyclic alkyl group;

Chloromethyl, chloroethyl, bromoethyl, iodoethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2,2
Carbon substituted by a halogen atom such as 2-trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group, perfluorodecyl group, perfluoroicosanyl group, etc. An alkyl group of the formulas 1 to 20; a hydroxymethyl group, a 2-hydroxyethyl group,
-Hydroxybutyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-chloropropyl group,
2-hydroxy-3-ethoxypropyl group, 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-
C1-C10 substituted by a hydroxyl group such as a cyclohexyloxypropyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group and a 4-hydroxydecalyl group
An alkyl group; hydroxymethoxymethyl group, hydroxyethoxyethyl group, 2- (2′-hydroxy-1′-
Methylethoxy) -1-methylethyl group, 2- (3′-
Fluoro-2′-hydroxypropoxy) ethyl group, 2
An alkyl group having 2 to 10 carbon atoms substituted with a hydroxyalkoxy group such as-(3'-chloro-2'-hydroxypropoxy) ethyl group or hydroxybutoxycyclohexyl group; hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [ 2 ′-(2′-hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2′-fluoro-
1'-hydroxyethoxy) -1'-methylethoxy]
An alkyl group having 3 to 10 carbon atoms substituted with a hydroxyalkoxyalkoxy group such as an ethoxyethyl group, [2 ′-(2′-chloro-1′-hydroxyethoxy) -1′-methylethoxy] ethoxyethyl group;

Cyanomethyl group, 2-cyanoethyl group, 4
-Cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-
Alkyl having 2 to 10 carbon atoms substituted with a cyano group such as a 3-ethoxypropyl group, a 3-butoxy-2-cyanopropyl group, a 2-cyano-3-cyclohexylpropyl group, a 2-cyanopropyl group, or a 2-cyanobutyl group. Groups: methoxymethyl group, methoxyethyl group, ethoxymethyl group,
Propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, n-hexyloxyethyl group, (4-methylpentoxy) ethyl group, (1,3-dimethylbutoxy) ethyl Group, (2-ethylhexyloxy) ethyl group, n-octyloxyethyl group, (3,5,5-trimethylhexyloxy) ethyl group, (2-methyl-1-
(iso-propylpropoxy) ethyl group, (3-methyl-1-iso-propylbutyloxy) ethyl group, 2-
An ethoxy-1-methylethyl group, a 3-methoxybutyl group, a (3,3,3-trifluoropropoxy) ethyl group, a (3,3,3-trichloropropoxy) ethyl group,
An alkyl group having 2 to 15 carbon atoms substituted with an alkoxy group such as adamantyloxyethyl; a methoxymethoxymethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, a butoxyethoxyethyl group, a cyclohexyloxyethoxyethyl group, Decalyloxypropoxyethoxy group, (1,2-dimethylpropoxy) ethoxyethyl group, (3-methyl-1-
(iso-butylbutoxy) ethoxyethyl group, (2-methoxy-1-methylethoxy) ethyl group, (2-butoxy-1-methylethoxy) ethyl group, 2- (2′-ethoxy-1′-methylethoxy)- 1-methylethyl group,
An alkyl group having 3 to 15 carbon atoms and substituted with an alkoxyalkoxy group such as a (3,3,3-trifluoropropoxy) ethoxyethyl group or a (3,3,3-trichloropropoxy) ethoxyethyl group; a methoxymethoxymethoxymethyl group Methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, cyclohexyloxy, propoxypropoxypropoxy group, (2,2,2-trifluoroethoxy) ethoxyethoxyethyl group, (2,2,2- C4 to C15 substituted with an alkoxyalkoxyalkoxy group such as trichloroethoxy) ethoxyethoxyethyl group
An alkyl group of

Phenoxymethyl, phenoxyethyl, (4-t-butylphenoxy) ethyl, naphthyloxymethyl, biphenyloxyethyl, (3-methylphenyl) oxyethyl, 4- (1-pyrenyloxy) butyl An alkyl group having 7 to 15 carbon atoms substituted with an aryloxy group such as benzyloxymethyl group, benzyloxyethyl group, phenethyloxymethyl group, phenethyloxyethyl group, (4-cyclohexyloxybenzyloxy) methyl group, 9- An alkyl group having 8 to 20 carbon atoms substituted by an aralkyloxy group having 8 to 20 carbon atoms such as a fluorenylmethoxyhexyl group; formylmethyl group, 2-oxobutyl group, 3-oxobutyl group, 4-oxobutyl group, 6-dioxocyclohexane-1-
Yl group, 2-oxo-5-t-butylcyclohexane-
An alkyl group having 2 to 10 carbon atoms substituted with an acyl group such as a 1-yl group; formyloxymethyl group, acetoxyethyl group, propionyloxyethyl group, butanoyloxyethyl group, valeryloxyethyl group, (2-ethyl (Hexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyloxy) hexyl group, (3-fluorobutyryloxy) ethyl group, (3 -Chlorobutyryloxy) 2 carbon atoms substituted with an acyloxy group such as an ethyl group
To 15 alkyl groups; formyloxymethoxymethyl group, acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group,
(2-ethylhexanoyloxy) ethoxyethyl group,
(3,5,5-trimethylhexanoyloxy) butoxyethyl group, (3,5,5-trimethylhexanoyloxyethoxy) ethyl group, (2-fluoropropionyloxy) ethoxyethyl group, (2-chloropropionyloxy) An alkyl group having 3 to 15 carbon atoms substituted with an acyloxyalkoxy group such as an ethoxyethyl group;

Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy)
Ethoxyethoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethoxyethyl group, (2
-Fluoropropionyloxy) ethoxyethoxyethyl group, alkyl group having 5 to 15 carbon atoms substituted with acyloxyalkoxyalkoxy group such as (2-chloropropionyloxy) ethoxyethoxyethyl group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxy Carbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, (p-ethylcyclohexyloxycarbonyl) cyclohexyl group, (2,2,3,3-tetrafluoropropoxycarbonyl) methyl group, 2,3
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyl group such as a 3-tetrachloropropoxycarbonyl) methyl group; a phenoxycarbonylmethyl group, a phenoxycarbonylethyl group, a (4-t-butylphenoxycarbonyl) ethyl group, a naphthyloxy group An alkyl group having 8 to 15 carbon atoms substituted by an aryloxycarbonyl group such as a carbonylmethyl group or a biphenyloxycarbonylethyl group; a benzyloxycarbonylmethyl group, a benzyloxycarbonylethyl group, a phenethyloxycarbonylmethyl group, a (4-cyclohexyloxy) group; An alkyl group having 9 to 15 carbon atoms substituted by an aralkyloxycarbonyl group having 9 to 15 carbon atoms such as benzyloxycarbonyl) methyl group; vinyloxycarbonylmethyl group, vinyloxycarbonyl An alkyl group having 4 to 10 carbon atoms, which is substituted by an alkenyloxycarbonyl group such as an aryl group, an allyloxycarbonylmethyl group, an octenoxycarbonylmethyl group; a methoxycarbonyloxymethyl group, a methoxycarbonyloxyethyl group, an ethoxycarbonyloxyethyl group , Butoxycarbonyloxyethyl group, (2,
An alkyl group having 3 to 15 carbon atoms and substituted with an alkoxycarbonyloxy group such as a 2,2-trifluoroethoxy) carbonyloxyethyl group or a (2,2,2-trichloroethoxy) carbonyloxyethyl group; methoxymethoxycarbonyloxymethyl Group, methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, (2,2,2-trifluoroethoxy) ethoxycarbonyloxyethyl group, (2,2,2-trichloroethoxy) An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxycarbonyloxy group such as an ethoxycarbonyloxyethyl group;

Dimethylaminomethyl, diethylaminomethyl, di-n-butylaminomethyl, di-n-hexylaminomethyl, di-n-octylaminomethyl, di-n-decylaminomethyl, N- Isoamyl-
N-methylaminomethyl group, piperidinomethyl group, di (methoxymethyl) aminomethyl group, di (methoxyethyl) aminomethyl group, di (ethoxymethyl) aminomethyl group, di (ethoxyethyl) aminomethyl group, di (propoxyethyl) ) Aminomethyl group, di (butoxyethyl)
Aminomethyl group, bis (2-cyclohexyloxyethyl) aminomethyl group, dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group, di-n-hexylaminoethyl group, di-n-octylaminoethyl Group, di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group, piperidinoethyl group, di (methoxymethyl) aminoethyl group, di (methoxyethyl) aminoethyl group, di (ethoxymethyl) aminoethyl Group, di (ethoxyethyl) aminoethyl group, di (propoxyethyl) aminoethyl group, di (butoxyethyl) aminoethyl group, bis (2-cyclohexyloxyethyl) aminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, Di-n-butylaminopropyl group, di-n Hexyl aminopropyl group, di -
n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxymethyl) aminopropyl group, di (methoxyethyl) aminopropyl group Di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis (2-cyclohexyloxyethyl) aminopropyl group, dimethyl Aminobutyl group, diethylaminobutyl group, di-n-butylaminobutyl group, di-n
-Hexylaminobutyl group, di-n-octylaminobutyl group, di-n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group, piperidinobutyl group,
Di (methoxymethyl) aminobutyl group, di (methoxyethyl) aminobutyl group, di (ethoxymethyl) aminobutyl group, di (ethoxyethyl) aminobutyl group, di (propoxyethyl) aminobutyl group, di (butoxyethyl) An alkyl group having 3 to 20 carbon atoms substituted with a dialkylamino group such as an aminobutyl group or a bis (2-cyclohexyloxyethyl) aminobutyl group;

Substitution with an acylamino group such as an acetylaminomethyl group, an acetylaminoethyl group, a propionylaminoethyl group, a butanoylaminoethyl group, a cyclohexanecarbonylaminoethyl group, a p-methylcyclohexanecarbonylaminoethyl group, and a succiniminoethyl group. An alkyl group having 3 to 10 carbon atoms; the number of carbon atoms substituted with an alkylsulfonamino group such as a methylsulfonaminomethyl group, a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, and an octylsulfonaminoethyl group. 2 to 10 alkyl groups; methylsulfonylmethyl group, ethylsulfonylmethyl group, butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, butylsulfonylethyl group, 2-E Hexyl sulfonyl ethyl group,
An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonyl group such as a (2,2,3,3-tetrafluoropropyl) sulfonylmethyl group or a (2,2,3,3-tetrachloropropyl) sulfonylmethyl group; Benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group, benzenesulfonylbutyl group,
Toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylenesulfonylethyl group, xylenesulfonylpropyl group,
An alkyl group having 7 to 12 carbon atoms substituted with an arylsulfonyl group such as a xylenesulfonylbutyl group; a thiadiazolinomethyl group, a pyrrolinomethyl group, a pyrrolidinomethyl group, a pyrazolidinomethyl group, an imidazolidinomethyl group;
Examples thereof include an alkyl group having 2 to 13 carbon atoms substituted with a heterocyclic group such as an oxazolyl group, a triazolinomethyl group, a morpholinomethyl group, an indolinomethyl group, a benzimidazolinomethyl group, and a carbazolinomethyl group.

Examples of the aralkyl group which may have a substituent of R ^{1 to} R ⁵ include the aralkyl group having the same substituent as the above-mentioned alkyl group, preferably a benzyl group or a nitro group. Benzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl, trifluoromethylbenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, hydroxynaphthylmethyl, methylnaphthylmethyl, trifluoromethylnaphthylmethyl And an aralkyl group having 7 to 15 carbon atoms such as a fluorene-9-ylethyl group.

Examples of the aryl group which may have a substituent of R ^{1 to} R ⁵ include the same aryl group as the above-mentioned alkyl group, preferably a phenyl group or a nitro group. Phenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group,
Trifluoromethylnaphthyl group, methoxycarbonylphenyl group, 4- (5′-methylbenzoxazole-2 ′
And aryl groups having 6 to 15 carbon atoms such as -yl) phenyl group and dibutylaminocarbonylphenyl group.

Examples of the alkenyl group which may have a substituent of R ^{1 to} R ⁵ include the alkenyl group having the same substituent as the above-mentioned alkyl group, preferably a vinyl group, a propenyl group. Group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group,
2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, 2
-Cyano-2-methylsulfone vinyl group, styryl group,
An alkenyl group having 2 to 10 carbon atoms such as a 4-phenyl-2-butenyl group is exemplified.

Examples of the alkoxy group which may have a substituent of R ^{1 to} R ⁵ include a methoxy group, an ethoxy group and an n-
Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group,
tert-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group,
1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy Group, 2,
3-dimethylbutoxy group, 1,1,2-trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-
Ethyl butoxy group, 2-ethyl butoxy group, 1-ethyl-2-methylpropoxy group, cyclohexyloxy group,
Methylcyclopentyloxy group, n-heptyloxy group, 1-methylhexyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 4-methylhexyloxy group, 5-methylhexyloxy group, 1,1
-Dimethylpentyloxy group, 1,2-dimethylpentyloxy group, 1,3-dimethylpentyloxy group, 1,
4-dimethylpentyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethylpentyloxy group,
2,4-dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 1-ethylpentyloxy group, 2-ethylpentyloxy group, 3-ethylpentyloxy group, 1, 1,2-
Trimethylbutoxy group, 1,1,3-trimethylbutoxy group, 1,2,3-trimethylbutoxy group, 1,2,2
-Trimethylbutoxy group, 1,3,3-trimethylbutoxy group, 2,3,3-trimethylbutoxy group, 1-ethyl-1-methylbutoxy group, 1-ethyl-2-methylbutoxy group, 1-ethyl-3 -Methylbutoxy group, 2-ethyl-1-methylbutoxy group, 2-ethyl-3-methylbutoxy group, 1-n-propylbutoxy group, 1-isopropylbutoxy group, 1-isopropyl-2-methylpropoxy group, methyl Cyclohexyloxy group, n-octyloxy group, 1-methylheptyloxy group, 2-methylheptyloxy group, 3-methylheptyloxy group, 4-
Methylheptyloxy group, 5-methylheptyloxy group, 6-methylheptyloxy group, 1,1-dimethylhexyloxy group, 1,2-dimethylhexyloxy group,
1,3-dimethylhexyloxy group, 1,4-dimethylhexyloxy group, 1,5-dimethylhexyloxy group, 2,2-dimethylhexyloxy group, 2,3-dimethylhexyloxy group, 2,4-dimethyl Hexyloxy group, 2,5-dimethylhexyloxy group, 3,3-dimethylhexyloxy group, 3,4-dimethylhexyloxy group, 3,5-dimethylhexyloxy group, 4,4-
Dimethylhexyloxy group, 4,5-dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxy group, 1-n-propylpentyloxy group, 2-n -Propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyloxy group, 1
-Ethyl-2-methylpentyloxy group, 1-ethyl-
3-methylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2
-Ethyl-3-methylpentyloxy group, 2-ethyl-
4-methylpentyloxy group, 3-ethyl-1-methylpentyloxy group, 3-ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3
-Ethyl-4-methylpentyloxy group, 1,1,2-
Trimethylpentyloxy group, 1,1,3-trimethylpentyloxy group, 1,1,4-trimethylpentyloxy group, 1,2,2-trimethylpentyloxy group,
1,2,3-trimethylpentyloxy group, 1,2,4
A trimethylpentyloxy group, a 1,3,4-trimethylpentyloxy group, a 2,2,3-trimethylpentyloxy group, a 2,2,4-trimethylpentyloxy group,
2,3,4-trimethylpentyloxy group, 1,3,3
-A trimethylpentyloxy group, a 2,3,3-trimethylpentyloxy group, a 3,3,4-trimethylpentyloxy group, a 1,4,4-trimethylpentyloxy group,
2,4,4-trimethylpentyloxy group, 3,4,4
-Trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-t
tert-butylbutoxy group, 1-n-propyl-1-methylbutoxy group, 1-n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-
Isopropyl-1-methylbutoxy group, 1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy group, 1,1-diethylbutoxy group, 1,2
-Diethylbutoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group, 1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethyl Butoxy group, 2-ethyl-1,
2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2-ethyl-2,3-dimethylbutoxy group, 1,1,3,3-tetramethylbutoxy group, 1,2
-Dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group, 1,4-dimethylcyclohexyloxy group, ethylcyclohexyloxy group, n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n
-Dodecyloxy group, 1-adamantyloxy group, n-
A linear, branched or cyclic unsubstituted alkoxy group having 1 to 15 carbon atoms such as a pentadecanyloxy group;

Methoxymethoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy,
Isopropoxyethoxy group, n-butoxyethoxy group,
Isobutoxyethoxy group, tert-butoxyethoxy group, sec-butoxyethoxy group, n-pentyloxyethoxy group, isopentyloxyethoxy group, tert
-Pentyloxyethoxy group, sec-pentyloxyethoxy group, cyclopentyloxyethoxy group, n-hexyloxyethoxy group, ethylcyclohexyloxyethoxy group, n-nonyloxyethoxy group, (3,5,
5-trimethylhexyloxy) ethoxy group, (3,
5,5-trimethylhexyloxy) butoxy group, n-
Decyloxyethoxy group, n-undecyloxyethoxy group, n-dodecyloxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3- (n-propoxy) propoxy group, 2-isopropoxypropoxy group, 2 A C2-C2-substituted alkoxy group such as a methoxybutoxy group, a 2-ethoxybutoxy group, a 2- (n-propoxy) butoxy group, a 4-isopropoxybutoxy group, a decalyloxyethoxy group, or an adamantyloxyethoxy group; 15 alkoxy groups; methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propoxymethoxymethoxy group, butoxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group,
Propoxyethoxymethoxy group, butoxyethoxymethoxy group, methoxypropoxymethoxy group, ethoxypropoxymethoxy group, propoxypropoxymethoxy group,
Butoxypropoxymethoxy group, methoxybutoxymethoxy group, ethoxybutoxymethoxy group, propoxybutoxymethoxy group, butoxybutoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group,
Propoxymethoxyethoxy group, butoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxypropoxyethoxy group, ethoxypropoxyethoxy group, propoxypropoxyethoxy group, butoxypropoxy group Methoxybutoxyethoxy group, ethoxybutoxyethoxy group, propoxybutoxyethoxy group, butoxybutoxyethoxy group, methoxymethoxypropoxy group, ethoxymethoxypropoxy group, propoxymethoxypropoxy group, butoxymethoxypropoxy group, methoxyethoxypropoxy group, ethoxyethoxypropoxy group Propoxyethoxypropoxy, butoxyethoxypropoxy, methoxypropoxy Cipropoxy group, ethoxypropoxypropoxy group, propoxypropoxypropoxy group, butoxypropoxypropoxy group, methoxybutoxypropoxy group, ethoxybutoxypropoxy group, propoxybutoxypropoxy group, butoxybutoxypropoxy group, methoxymethoxybutoxy group, ethoxymethoxybutoxy group Butoxy group, butoxymethoxybutoxy group, methoxyethoxybutoxy group,
Ethoxyethoxybutoxy group, propoxyethoxybutoxy group, butoxyethoxybutoxy, methoxypropoxybutoxy group, ethoxypropoxybutoxy group, propoxypropoxybutoxy group, butoxypropoxybutoxy group, methoxybutoxybutoxy group, ethoxybutoxybutoxy group, ethoxybutoxybutoxy group Butoxybutoxybutoxy group, (4-ethylcyclohexyloxy) ethoxyethoxy group, (2-ethyl-1-hexyloxy) ethoxypropoxy group, 4- (3,5,5
A trimethylhexyloxybutoxyethoxy group or the like;
A linear, branched or cyclic C3-C15 alkoxy group substituted with an alkoxyalkoxy group;

Methoxycarbonylmethoxy, ethoxycarbonylmethoxy, n-propoxycarbonylmethoxy, isopropoxycarbonylmethoxy, 4′-
An alkoxy group having 3 to 10 carbon atoms substituted by an alkoxycarbonyl group such as ethylcyclohexyloxycarbonylmethoxy group; an alkoxy group having 3 to 10 carbon atoms substituted by an acyl group such as acetylmethoxy group, ethylcarbonylmethoxy group, octylcarbonylmethoxy group A group having 3 carbon atoms substituted by an acyloxy group such as an acetyloxymethoxy group, an acetyloxyethoxy group, an acetyloxyhexyloxy group, a butanoyloxycyclohexyloxy group;
10 to 10 alkoxy groups; methylaminomethoxy group, 2-
Methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutoxy group, 1-
Methylaminopropan-2-yloxy group, 3-methylaminopropoxy group, 2-methylamino-2-methylpropoxy group, 2-ethylaminoethoxy group, 2- (2-
Ethylaminoethoxy) ethoxy group, 3-ethylaminopropoxy group, 1-ethylaminopropoxy group, 2-isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propoxy group, An alkoxy group having 2 to 10 carbon atoms substituted with an alkylamino group such as 4- (cyclohexylamino) butyloxy group; methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropoxy group, ethylaminoethoxypropoxy group, 4 -(2 '
An alkoxy group having 3 to 10 carbon atoms, which is substituted with an alkylaminoalkoxy group such as -isobutylaminopropoxy) butoxy group;

Dimethylaminomethoxy, 2-dimethylaminoethoxy, 2- (2-dimethylaminoethoxy) ethoxy, 4-dimethylaminobutoxy, 1-
Dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy group, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2
-(2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-diisopropylaminoethoxy group, 2-
3 to 15 carbon atoms substituted by a dialkylamino group such as a (di-n-butylamino) ethoxy group, a 2-piperidylethoxy group or a 3- (di-n-hexylamino) propoxy group.
A dimethylaminomethoxymethoxy group;
A C4-15 alkoxy group substituted by a dialkylaminoalkoxy group such as a dimethylaminoethoxyethoxy group, a dimethylaminoethoxypropoxy group, a diethylaminoethoxypropoxy group, or a 4- (2'-diisobutylaminopropoxy) butoxy group; a methylthiomethoxy group A 2-methylthioethoxy group, a 2-ethylthioethoxy group, a 2-n-propylthioethoxy group, a 2-isopropylthioethoxy group, a 2-n-butylthioethoxy group,
An alkoxy group having 2 to 15 carbon atoms substituted by an alkylthio group such as a 2-isobutylthioethoxy group and a (3,5,5-trimethylhexylthio) hexyloxy group; and the like, preferably a methoxy group and an ethoxy group , N-propoxy group, iso-propoxy group, n-butoxy group, i
so-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neopentoxy group, 2-methylbutoxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group , Decalyloxy group, methoxyethoxyethoxy group,
An alkoxy group having 1 to 10 carbon atoms such as an ethoxyethoxyethoxy group, a methoxyethoxy group, and an ethoxyethoxy group is exemplified.

Examples of the aralkyloxy group which may have a substituent of R ^{1 to} R ⁵ include the aralkyloxy group having the same substituent as the above-mentioned alkyl group, preferably benzyloxy group. Group, nitrobenzyloxy group, cyanobenzyloxy group, hydroxybenzyloxy group, methylbenzyloxy group, trifluoromethylbenzyloxy group, naphthylmethoxy group, nitronaphthylmethoxy group, cyanonaphthylmethoxy group, hydroxynaphthylmethoxy group, methylnaphthyl Examples thereof include an aralkyloxy group having 7 to 15 carbon atoms such as a methoxy group, a trifluoromethylnaphthylmethoxy group, and a fluoren-9-ylethoxy group.

Examples of the aryloxy group which may have a substituent represented by R ^{1 to} R ⁵ include an aryloxy group having the same substituent as the above-mentioned alkyl group, and preferably a phenoxy group 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-
An aryloxy group having 6 to 10 carbon atoms such as a methoxyphenoxy group, a 4-iso-propylphenoxy group and a naphthoxy group is exemplified.

Examples of the alkenyloxy group which may have a substituent of R ^{1 to} R ⁵ include an alkenyloxy group having the same substituent as the above-mentioned alkyl group, preferably a vinyloxy group. , Propenyloxy group, 1-
Butenyloxy group, iso-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxy group, 2-methyl-2-butenyloxy group, 2,2
-Dicyanovinyloxy group, 2-cyano-2-methylcarboxylvinyloxy group, 2-cyano-2-methylsulfonvinyloxy group, styryloxy group, 4-phenyl-2-butenyloxy group, cinnamylalkoxy group, and other carbon atoms And 2 to 10 alkenyloxy groups.

Examples of the alkylthio group which may have a substituent represented by R ^{1 to} R ⁵ include the alkylthio groups having the same substituents as the above-mentioned alkyl groups, preferably a methylthio group, an ethylthio group. Group, n-propylthio group, iso-propylthio group, n-butylthio group, is
o-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neopentylthio group, 2-methylbutylthio group, methylcarboxylethylthio group, 2-ethylhexylthio group, 3 , 5,5-trimethylhexylthio group, decalylthio group and the like, and alkylthio groups having 1 to 10 carbon atoms.

Examples of the aralkylthio group which may have a substituent of R ^{1 to} R ⁵ include the aralkylthio group having the same substituent as the above-mentioned alkyl group, preferably a benzylthio group. , Nitrobenzylthio, cyanobenzylthio, hydroxybenzylthio, methylbenzylthio, trifluoromethylbenzylthio, naphthylmethylthio, nitronaphthylmethylthio, cyanonaphthylmethylthio, hydroxynaphthylmethylthio, methylnaphthylmethylthio And an aralkylthio group having 7 to 12 carbon atoms such as a trifluoromethylnaphthylmethylthio group and a fluoren-9-ylethylthio group.

Examples of the arylthio group which may have a substituent represented by R ^{1 to} R ⁵ include an arylthio group having the same substituent as the above-mentioned alkyl group.
Phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group,
And an arylthio group having 6 to 10 carbon atoms such as a naphthylthio group.

Examples of the alkenylthio group which may have a substituent of R ^{1 to} R ⁵ include the alkenylthio group having the same substituent as the above-mentioned alkyl group, preferably a vinylthio group, Examples thereof include an alkenylthio group having 2 to 10 carbon atoms such as an allylthio group, a butenylthio group, a hexanedienylthio group, a styrylthio group, a cyclohexenylthio group, and a decenylthio group.

Examples of the acyl group which may have a substituent represented by R ^{1 to} R ⁵ include acyl groups having the same substituents as the above-mentioned alkyl groups, preferably formyl group, methyl Carbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group,
n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group Acyl having 1 to 15 carbon atoms such as methylbenzoyl group, ethylbenzoyl group, tolylcarbonyl group, propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyl group, cinnamoyl group, etc. Groups.

Examples of the acyloxy group which may have a substituent represented by R ^{1 to} R ⁵ include an acyloxy group having the same substituent as the above-mentioned alkyl group, preferably a formyloxy group, Methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group Group, n-pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxy group, methylbenzoyloxy group, ethylbenzoyloxy group, tolylcarbonyloxy group, propyl Ben Yloxy group, 4-t-butyl-benzoyloxy group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyloxy group, acyloxy group having 2 to 16 carbon atoms such as cinnamoyl group.

Examples of the heteroaryl group which may have a substituent of R ^{1 to} R ⁵ include a heteroaryl group having the same substituent as the above-mentioned alkyl group, and preferably a furanyl group , Pyrrolyl, 3-pyrrolino, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, 1,2,3-oxadiazolyl, 1,2,3-
Triazolyl group, 1,2,4-triazolyl group, 1,
3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indoleyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, benzotriazol-2-yl group, Benzotriazol-1-yl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group,
Unsubstituted heteroaryl groups such as flavonyl group, phthalimido group, naphthylimido group;

Alternatively, the following substituents: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyl group, 3,5,5-trimethylhexyloxy group and other alkoxy groups Aralkyloxy groups such as benzyloxy group and phenethyloxy group; aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxy group; vinyl group;
Alkenyl groups such as allyl group, butenyl group, butadienyl group, pentenyl group and octenyl group; vinyloxy group,
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, Alkylthio groups such as decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group and trifluoromethylthio group; aralkylthio groups such as benzylthio group and phenethylthio group; phenylthio group, tolylthio group;
Arylthio groups such as naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group and methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group; acetyl group, propionyl group and butanoyl Acyl groups such as methoxycarbonyl group and ethoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, Aryloxycarbonyl groups such as silyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group; vinyloxycarbonyl group; An alkenyloxycarbonyl group such as a ryloxycarbonyl group, a butenyloxycarbonyl group, a butadienyloxycarbonyl group, a pentenyloxycarbonyl group, an octenyloxycarbonyl group; a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group; Butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5
A monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as a 5-trimethylhexylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, a dibutylaminocarbonyl group, a dipentyl Aminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4
An alkylaminocarbonyl group such as a dialkylaminocarbonyl group having 3 to 20 carbon atoms such as -ethylpiperazinocarbonyl group; a furanyl group, a pyrrolyl group, a 3-pyrrolino group,
Pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3-
An oxadiazolyl group, a 1,2,3-triazolyl group,
1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group,
Triazinyl group, benzofuranyl group, indolyl group,
Thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, prenyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group, flavonyl group, etc. A heteroaryl group substituted with a substituent such as a heterocyclic group;

Examples of the heteroaryloxy group which may have a substituent represented by R ^{1 to} R ⁵ include a heteroaryloxy group having the same substituent as the above-mentioned alkyl group. Furanyloxy group, pyrrolyloxy group, 3-pyrrolinoxy group, pyrazolyloxy group, imidazolyloxy group, oxazolyloxy group, thiazolyloxy group, 1,2,3-oxadiazolyloxy group,
1,2,3-triazolyloxy group, 1,2,4-triazolyloxy group, 1,3,4-thiadiazolyloxy group, pyridinyloxy group, pyridazinyloxy group, pyrimidinyloxy group, Pyrazinyloxy, piperazinyloxy, triazinyloxy, benzofuranyloxy, indoleyloxy, thionaphthenyloxy, benzimidazolyloxy, benzothiazolyloxy, benzotriazol-2-yl Yloxy group, benzotriazol-1-yloxy group, purinyloxy group, quinolinyloxy group, isoquinolinyloxy group, coumarinyloxy group, cinnolinyloxy group, quinoxalinyloxy group, dibenzofuranyloxy group, carbazolyl Oxy group, phenanthronylyloxy group, phenothiazinyloxy group, Niruokishi group, phthalimide group, naphthyl imide group, unsubstituted heteroaryloxy groups, such as;

Alternatively, the following substituents: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyl group, 3,5,5-trimethylhexyloxy group and other alkoxy groups Aralkyloxy groups such as benzyloxy group and phenethyloxy group; aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxy group; vinyl group;
Alkenyl groups such as allyl group, butenyl group, butadienyl group, pentenyl group and octenyl group; vinyloxy group,
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, Alkylthio groups such as decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group and trifluoromethylthio group; aralkylthio groups such as benzylthio group and phenethylthio group; phenylthio group, tolylthio group;
Arylthio groups such as naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group and methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group; acetyl group, propionyl group and butanoyl Acyl groups such as methoxycarbonyl group and ethoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, Aryloxycarbonyl groups such as silyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group; vinyloxycarbonyl group; An alkenyloxycarbonyl group such as a ryloxycarbonyl group, a butenyloxycarbonyl group, a butadienyloxycarbonyl group, a pentenyloxycarbonyl group, an octenyloxycarbonyl group; a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group; Butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5
A monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as a 5-trimethylhexylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, a dibutylaminocarbonyl group, a dipentyl Aminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4
An alkylaminocarbonyl group such as a dialkylaminocarbonyl group having 3 to 20 carbon atoms such as -ethylpiperazinocarbonyl group; a furanyl group, a pyrrolyl group, a 3-pyrrolino group,
Pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3-
An oxadiazolyl group, a 1,2,3-triazolyl group,
1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group,
Triazinyl group, benzofuranyl group, indolyl group,
Thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, prenyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group, flavonyl group, etc. A heteroaryloxy group substituted with a substituent such as a heterocyclic group;

Examples of the heteroarylthio group which may have a substituent of R ^{1 to} R ⁵ include a heteroarylthio group having the same substituent as the above-mentioned alkyl group. Furanylthio group, pyrrolylthio group, 3
-Pyrrolinothio, pyrazolylthio, imidazolylthio, oxazolylthio, thiazolylthio, 1,
2,3-oxadiazolylthio group, 1,2,3-triazolylthio group, 1,2,4-triazolylthio group, 1,
3,4-thiadiazolylthio group, pyridinylthio group, pyridazinylthio group, pyrimidinylthio group, pyrazinylthio group, piperazinylthio group, triazinylthio group, benzofuranylthio group, indoleylthio group, thonaphthenylthio group, benzimidazolylthio group, benzo Thiazolylthio group, benzotriazol-2-ylthio group, benzotriazol-1-ylthio group, purinylthio group, quinolinylthio group, isoquinolinylthio group, coumarinylthio group, cinnolinylthio group, quinoxalinylthio group, dibenzofuranylthio group An unsubstituted heteroarylthio group such as a carbazolylthio group, a phenanthronylylthio group, a phenothiazinylthio group, a flavonylthio group, a phthalimidothio group, a naphthylimidothio group;

Alternatively, the following substituents: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyl group, 3,5,5-trimethylhexyloxy group and other alkoxy groups Aralkyloxy groups such as benzyloxy group and phenethyloxy group; aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxy group; vinyl group;
Alkenyl groups such as allyl group, butenyl group, butadienyl group, pentenyl group and octenyl group; vinyloxy group,
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, octenyloxy group; methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, Alkylthio groups such as decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group and trifluoromethylthio group; aralkylthio groups such as benzylthio group and phenethylthio group; phenylthio group, tolylthio group;
Arylthio groups such as naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group and methoxyphenylthio group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group; acetyl group, propionyl group and butanoyl Acyl groups such as methoxycarbonyl group and ethoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, Aryloxycarbonyl groups such as silyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group; vinyloxycarbonyl group; An alkenyloxycarbonyl group such as a ryloxycarbonyl group, a butenyloxycarbonyl group, a butadienyloxycarbonyl group, a pentenyloxycarbonyl group, an octenyloxycarbonyl group; a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group; Butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5
A monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as a 5-trimethylhexylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, a dibutylaminocarbonyl group, a dipentyl Aminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4
An alkylaminocarbonyl group such as a dialkylaminocarbonyl group having 3 to 20 carbon atoms such as -ethylpiperazinocarbonyl group; a furanyl group, a pyrrolyl group, a 3-pyrrolino group,
Pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3-
An oxadiazolyl group, a 1,2,3-triazolyl group,
1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group,
Triazinyl group, benzofuranyl group, indolyl group,
Thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, prenyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group, flavonyl group, etc. And a heteroarylthio group substituted with a substituent such as a heterocyclic group.

Formulas (7) for R ^{1 to} R ⁵

[0077]

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An optionally substituted alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group represented by substituent group Q of the carbonyl group represented by Examples of the group and the alkenylthio group include the same groups as those described for R ^{1 to} R ⁵ .

Preferred examples of the formula (7) include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-
Butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonyl group, 2
-Pentoxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3,5,5-trimethylhexyloxycarbonyl group, decalyloxycarbonyl group, cyclohexyloxycarbonyl group, chloroethoxycarbonyl group, hydroxymethoxycarbonyl group, hydroxyethoxycarbonyl group C2-C11 alkoxycarbonyl groups such as methoxymethoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, propoxyethoxycarbonyl, butoxyethoxycarbonyl, pentoxyethoxycarbonyl, hexyloxyethoxycarbonyl, butoxy Butoxycarbonyl group, hexyloxybutoxycarbonyl group,
An alkoxycarbonyl group having 3 to 11 carbon atoms substituted by an alkoxy group such as a hydroxymethoxymethoxycarbonyl group or a hydroxyethoxyethoxycarbonyl group; a methoxymethoxymethoxycarbonyl group, a methoxyethoxyethoxycarbonyl group, an ethoxyethoxyethoxycarbonyl group, a propoxyethoxyethoxycarbonyl group; Group,
An alkoxycarbonyl group having 4 to 11 carbon atoms substituted by an alkoxyalkoxy group such as a butoxyethoxyethoxycarbonyl group, a pentoxyethoxyethoxycarbonyl group, and a hexyloxyethoxyethoxycarbonyl group;

Benzyloxycarbonyl, nitrobenzyloxycarbonyl, cyanobenzyloxycarbonyl, hydroxybenzyloxycarbonyl, methylbenzyloxycarbonyl, trifluoromethylbenzyloxycarbonyl, naphthylmethoxycarbonyl, nitronaphthylmethoxycarbonyl An aralkyloxycarbonyl group having 8 to 16 carbon atoms, such as a cyanonaphthylmethoxycarbonyl group, a hydroxynaphthylmethoxycarbonyl group, a methylnaphthylmethoxycarbonyl group, a trifluoromethylnaphthylmethoxycarbonyl group, a fluoren-9-ylethoxycarbonyl group; and phenoxycarbonyl Group, 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-t-butylphenoxycarbo Aryloxycarbonyl group having 7 to 11 carbon atoms, such as methoxy group, 2-methoxyphenoxycarbonyl group, 4-iso-propylphenoxycarbonyl group, naphthoxycarbonyl group; vinyloxycarbonyl group, propenyloxycarbonyl group, 1-butenyl An oxycarbonyl group, an iso-butenyloxycarbonyl group, a 1-pentenyloxycarbonyl group, a 2-pentenyloxycarbonyl group, a 2-methyl-1-butenyloxycarbonyl group, a 3-methyl-1-butenyloxycarbonyl group, 2-methyl-2-butenyloxycarbonyl group, 2,2-dicyanovinyloxycarbonyl group, 2-
A carbon number of 3 to 3 such as a cyano-2-methylcarboxylvinyloxycarbonyl group, a 2-cyano-2-methylsulfonevinyloxycarbonyl group, a styryloxycarbonyl group, and a 4-phenyl-2-butenyloxycarbonyl group;
11 alkenyloxycarbonyl groups;

A methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group, a butylaminocarbonyl group, a pentylaminocarbonyl group, a hexylaminocarbonyl group, a heptylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, A monoalkylaminocarbonyl group having 2 to 11 carbon atoms such as a cyclohexylaminocarbonyl group, a 3,5,5-trimethylhexylaminocarbonyl group, a nonylaminocarbonyl group, a decylaminocarbonyl group; a benzylaminocarbonyl group, a phenethylaminocarbonyl group; 3-phenylpropylaminocarbonyl group, 4-ethylbenzylaminocarbonyl group, 4-isopropylbenzylaminocarbonyl group, N-methylbenzylaminocarbo 8 to 11 carbon atoms such as N-ethylbenzylaminocarbonyl, N-allylbenzylaminocarbonyl, N- (2-cyanoethyl) benzylaminocarbonyl, and N- (2-acetoxyethyl) benzylaminocarbonyl. Monoaralkylaminocarbonyl group: anilino group, naphthylaminocarbonyl group, toluidino group, xylidino group, ethylanilino group, isopropylanilino group, methoxyanilino group, ethoxyanilino group, chloroanilino group, acetylanilino group, methoxycarbonylaniline Lino group, ethoxycarbonylanilino group, propoxycarbonylanilino group, N
Monoarylaminocarbonyl group having 7 to 11 carbon atoms such as -methylanilino group, N-ethylanilino group, N-methyltoluidino group; vinylaminocarbonyl group, allylaminocarbonyl group, butenylaminocarbonyl group, pentenylaminocarbonyl group, hexenylamino Carbonyl group, cyclohexenylaminocarbonyl group, octadienylaminocarbonyl group, adamantenylaminocarbonyl group, N-methylvinylaminocarbonyl group, N
A monoalkenylaminocarbonyl group having 3 to 11 carbon atoms, such as -methylallylaminocarbonyl group, N-ethylvinylaminocarbonyl group, N-ethylallylaminocarbonyl group;

Dimethylaminocarbonyl, diethylaminocarbonyl, methylethylaminocarbonyl,
Dipropylaminocarbonyl group, dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group, dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group, pyrrolidino group, piperidino group, morpholino group, bis (methoxyethyl) aminocarbonyl group, bis ( Ethoxyethyl) aminocarbonyl group, bis (propoxyethyl) aminocarbonyl group, bis (butoxyethyl) aminocarbonyl group, di (acetyloxyethyl)
A dialkylaminocarbonyl group having 3 to 17 carbon atoms such as an aminocarbonyl group, a di (hydroxyethyl) aminocarbonyl group, an N-ethyl-N- (2-cyanoethyl) aminocarbonyl group, a di (propionyloxyethyl) aminocarbonyl group; A diaralkylaminocarbonyl group having 15 to 21 carbon atoms, such as a dibenzylaminocarbonyl group, a diphenethylaminocarbonyl group, a bis (4-ethylbenzyl) aminocarbonyl group, a bis (4-isopropylbenzyl) aminocarbonyl group; diphenylaminocarbonyl Group, a ditolylaminocarbonyl group, an N-phenyl-N-tolylaminocarbonyl group, etc.
15 diarylaminocarbonyl groups; divinylaminocarbonyl group, diallylaminocarbonyl group, dibutenylaminocarbonyl group, dipentenylaminocarbonyl group, dihexenylaminocarbonyl group, N-vinyl-N
A C 5-13 dialkenylaminocarbonyl group such as an allylaminocarbonyl group; N-phenyl-N-allylaminocarbonyl group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyl group, N-tolyl −
Alkyl, aralkyl, aryl and alkenyl groups which may have a substituent such as N-methylaminocarbonyl group, N-vinyl-N-methylaminocarbonyl group, N-benzyl-N-allylaminocarbonyl group And a disubstituted aminocarbonyl group having 4 to 11 carbon atoms, which is more selected.

More preferably, C 1 -C having an oxy group at a carbon-carbon bond and / or a carbon-hydrogen bond.
And a substituted alkoxy group having 10 and 1 to 3 oxygen atoms.

[0084] Also represented by substituents L ¹ and L ² of the amino group represented by the formula (8) as the substituent Q, which may have a substituent alkyl group, an aralkyl group, an aryl group, Examples of the alkenyl group include the same groups as those described for R ^{1 to} R ⁵ .

Preferred examples of the formula (8) include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group and a 2-ethylhexylamino group. A monoalkylamino group having 1 to 10 carbon atoms such as a cyclohexylamino group, a 3,5,5-trimethylhexylamino group, a nonylamino group, a decylamino group; a benzylamino group, a phenethylamino group, a 3-phenylpropylamino group, -Ethylbenzylamino group, 4-isopropylbenzylamino group, N-methylbenzylamino group, N-ethylbenzylamino group, N-allylbenzylamino group, N- (2-cyanoethyl) benzylamino group, N- (2- 7-10 carbon atoms such as acetoxyethyl) benzylamino group Monoaralkylamino group; anilino group, naphthylamino group, toluidino group, xylidino group, ethylanilino group, isopropylanilino group, methoxyanilino group, ethoxyanilino group, chloroanilino group, acetylanilino group, methoxycarbonylanilino group, An ethoxycarbonylanilino group, a propoxycarbonylanilino group, an N-methylanilino group, an N-ethylanilino group, an N-methyltoluidino group, etc.
A monoarylamino group of 0;

Vinylamino, allylamino, butenylamino, pentenylamino, hexenylamino, cyclohexenylamino, octadienylamino, adamanthenylamino, N-methylvinylamino, N-methylallylamino , N-ethylvinylamino group, N-ethylallylamino group and the like having 2 to 10 carbon atoms.
Monoalkenylamino group; formylamino group, methylcarbonylamino group, ethylcarbonylamino group, n-
Propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso
-Butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, iso-pentylcarbonylamino group, neopentylcarbonylamino group, 2-methylbutylcarbonylamino group, benzoylamino Group, methylbenzoylamino group, ethylbenzoylamino group,
C1-C15, such as a tolylcarbonylamino group, a propylbenzoylamino group, a 4-t-butylbenzoylamino group, a nitrobenzylcarbonylamino group, a 3-butoxy-2-naphthoylamino group, and a cinnamoylamino group.
A monosubstituted amino group such as an acylamino group;

Dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino, di-n-hexylamino, dicyclohexylamino, dioctylamino, bis (methoxyethyl) amino, bis (methoxyethyl) amino, Ethoxyethyl) amino group, bis (propoxyethyl) amino group, bis (butoxyethyl) amino group, di (acetyloxyethyl) amino group,
Di (hydroxyethyl) amino group, N-ethyl-N-
A dialkylamino group having 2 to 16 carbon atoms such as a (2-cyanoethyl) amino group and a di (propionyloxyethyl) amino group; a dibenzylamino group, a diphenethylamino group, a bis (4-ethylbenzyl) amino group, a bis ( 4-
14 to 2 carbon atoms such as isopropylbenzyl) amino group
0 diaralkylamino group; diphenylamino group, ditolylamino group, diarylamino group having 12 to 14 carbon atoms such as N-phenyl-N-tolylamino group; divinylamino group, diallylamino group, dibutenylamino group, dipentenylamino group, A C 4-12 dialkenylamino group such as a dihexenylamino group or an N-vinyl-N-allylamino group;

Diformylamino, di (methylcarbonyl) amino, di (ethylcarbonyl) amino, di (n-propylcarbonyl) amino, di (iso-propylcarbonyl) amino, di (n-butylcarbonyl) ) Amino, di (iso-butylcarbonyl) amino, di (sec-butylcarbonyl) amino, di (t
-Butylcarbonyl) amino group, di (n-pentylcarbonyl) amino group, di (iso-pentylcarbonyl)
Amino group, di (neopentylcarbonyl) amino group, di (2-methylbutylcarbonyl) amino group, di (benzoyl) amino group, di (methylbenzoyl) amino group, di (ethylbenzoyl) amino group, di (tolylcarbonyl) ) Amino group, di (propylbenzoyl) amino group, di (4-t-butylbenzoyl) amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-
Naphthoyl) amino group, di (cinnamoyl) amino group,
A diacylamino group having 2 to 30 carbon atoms such as an imino succinate group; an N-phenyl-N-allylamino group;
Acetyloxyethyl) -N-ethylamino group, N-tolyl-N-methylamino group, N-vinyl-N-methylamino group, N-benzyl-N-allylamino group and the like. And a disubstituted amino group having 3 to 10 carbon atoms selected from an alkyl group, an aralkyl group, an aryl group, and an alkenyl group.

Examples of the optionally substituted alicyclic ring formed by bonding adjacent groups in R ^{1 to} R ⁵ include those represented by the formula (10) or (11) or the formula (12):

[0090]

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(Wherein, r ^{1 to} r ²⁰ each independently represent a hydrogen atom, a halogen atom represented by R ^{1 to} R ⁵ , a halogen atom similar to an alkyl group or an alkoxy group, an alkyl group, or an alkoxy group; ^{1 to} n ³ represent 0 or 1.) which may be substituted. Preferably -C
_{H 2 CH 2 CH 2 CH 2} - and the like.

Examples of the optionally substituted aromatic ring formed by bonding adjacent groups in R ^{1 to} R ⁵ include those represented by formula (13):

[0093]

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(Wherein r^{twenty one}~ R^{twenty four}Are independently hydrogen sources
Child, R¹~ R^FiveA halogen atom, an alkyl group,
Halogen atom, alkyl group, and alkoxy
Represents a xy group. The optionally substituted aromatic ring represented by
I can do it. Preferably -CH = CH-CH = CH-,-
CH = CH-C (CH_Three) = CH-, -CH = CH-C
(CH_TwoCH _Three) = CH-, -CH = CH-C [CH (C
H_Three)_Two] = CH-, -CH = CH-C (OCH_Three) = C
H- and the like.

The substituents X, Y and Z represented by the formula (6)
Represents the same meaning as X, Y and Z represented by the formula (1).

The substituent X is a hydrogen atom, a cyano group, a carboxyl group, a carbonyl group or a heterocyclic group represented by the above formula (2), and the substituent Q in the formula (2) is It represents the same meaning as the substituent Q. Further, the heterocyclic group is represented by R
It represents the same heterocyclic group and heterocyclic group to be substituted with the heteroaryl group represented by ¹ to R ^5. Preferred examples of X include a hydrogen atom, a cyano group, and a substituted alkoxy group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms having an oxy group at a carbon-carbon bond and / or a carbon-hydrogen bond.

The substituent Y represents a carboxyl group or a carbonyl group or a heterocyclic group represented by the same formula (2) as the substituent X. Preferred examples of Y include a substituted alkoxy group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms having an oxy group at a carbon-carbon bond and / or a carbon-hydrogen bond.

The substituent Z represents an oxygen atom, a sulfur atom or a substituent represented by the above formula (4). T represented by equation (4)
Examples of ¹ and T ² include a hydrogen atom, a cyano group, a carbonyl group represented by the formula (2), and a group represented by the formula (5).

The substituent M in the group represented by the formula (5)
¹ Examples of substituted alkyl group which may be the ~M ^3, include alkyl groups described above.

The method for producing the indolizine compound represented by the general formula (1) of the present invention, specifically, the indolizine compound represented by the general formula (6) is described in J. Org. Chem.,
According to the method described in Vol. 45, No. 25, pp5100-5104 (1980), it can be produced by the following method. That is, typically, for example, Equation (14)

[0101]

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(Wherein R ^{1 to} R ⁵ have the same meanings as R ^{1 to} R ⁵ in the formula (6)) and a compound represented by the formula (15) J-CH ₂ COOR (15) (Wherein J represents a halogen atom and R represents an alkyl group), and optionally heated in the presence or absence of a solvent to obtain a compound of the formula (16)

[0103]

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(Wherein R ^{1 to} R ⁵ , R and J are the same as those of the above R ^{1 to} R
⁵ , represents the same meaning as R and J. ), And then equation (17)

[0105]

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(E ¹ and E ² each represent an alkyl group.)
By reacting with a compound represented by in a solvent such as ethanol in the presence of a base such as potassium carbonate,
Formula (18) wherein X in the formula (6) is a hydrogen atom, Y is an alkoxycarbonyl group, and Z is an oxygen atom

[0107]

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(Wherein, R ^{1 to} R ⁵ and E ² represent the aforementioned R ^{1 to} R 5
⁵ represents an E ² same meaning as. ) Can be obtained.

The compound of the formula (18) is hydrolyzed in a water and / or alcohol solvent in which an acid such as sulfuric acid or an alkali compound such as sodium hydroxide or potassium hydroxide is present to give a compound of the formula (19)

[0110]

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[0111] (wherein, R ¹ to R ⁵ represent. The same meaning as R ¹ to R ⁵ described above) to give a compound represented by, then thionyl chloride to a compound of formula (19), such as Or a compound having at least one of a hydroxyl group, an amino group and a mercapto group using a compound obtained by acid chloride with a chlorinating agent of the formula (19) in the presence of polyphosphoric acid. Reacts with or in the presence of a basic compound such as potassium carbonate,
By reacting with an alkylating agent such as toluenesulfonic acid ester or alkyl iodide in the presence or absence of a solvent, the compound represented by the formula (20)

[0112]

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(Wherein, R ^{1 to} R ⁵ and Y are the same as R ¹ to R ⁵ )
R ⁵ represents the same meaning as Y. ) Can be obtained. Also, for example, Bioorg. Med. Che
m. Lett., 1996, 6 (13), P1543-1546, after amidating the ester of the formula (18) with aqueous ammonia or the like, diphosphorus pentasulfide or the like The compound of the formula (20) in which Y is a thiazole ring can be synthesized by reacting and synthesizing a thioamide compound and further reacting a halogenoketone derivative. Alternatively, for example, as described in JP-A-11-180958, when a halogenoketone derivative is allowed to act on a carboxylic acid of the formula (19) in the presence of an ammonia derivative such as aqueous ammonia or ammonium chloride, Y is converted to oxazole. A compound of formula (20) that is a ring can be obtained.

For the compounds of the formulas (18), (19) and (20), a solvent such as N, N-dimethylformamide, ethanol and acetic acid is used,
After reacting a cyanide compound such as sodium cyanide and potassium cyanide, the compound is reacted with bromine or lead tetraacetate to obtain a compound of the formula (21) wherein X is a cyano group.

[0115]

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(Wherein, R ^{1 to} R ⁵ and Y are the same as R ¹ to R ⁵ )
R ⁵ represents the same meaning as Y. )), A compound of the formula (22) wherein X is a carboxyl group is obtained by hydrolysis with an acid such as aqueous sulfuric acid.

[0117]

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(Wherein, R ^{1 to} R ⁵ and Y are the same as R ¹ to R ⁵ )
R ⁵ represents the same meaning as Y. ), And then a compound obtained by acid-chlorinating the compound of the formula (22) with a chlorinating agent such as thionyl chloride is used in the reaction, or by the presence of a basic compound such as potassium carbonate. By reacting with a compound having at least one of a hydroxyl group, an amino group and a mercapto group using the formula (22), the compound represented by the formula (23)

[0119]

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[0120] (wherein, R ¹ to R ^5, X, Y, the aforementioned R ¹
To R ⁵ , X and Y. ) Can be obtained. Further, in order to introduce a thiazole ring or an oxazole ring as X in the same manner as Y, a halogenoketone derivative is allowed to act on the carboxylic acid of the formula (22) in the presence of an ammonia derivative to obtain a compound of the formula (23) wherein X is an oxazole ring. Can be synthesized, and the compound of the formula (2)
The compound of the formula (23) in which X is a thiazole ring can be synthesized from the compound in which 3) X is an ester group in the same manner as in Y above.

Further, the equations (18), (19) and (2)
0) or the compound of formula (23), for example, by reacting with a sulfur-containing compound such as Lawesson's reagent using a solvent such as dioxane to obtain a compound of formula (24) wherein Z is sulfur.

[0122]

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[0123] (wherein, R ¹ to R ^5, X, Y, the aforementioned R ¹
To R ⁵ , X and Y. )), The compound of the formula (25) T ¹ -CH ₂ -T ² (25) (where T ¹ and T ² are represented by the formula (4) ) Represents the same meaning as T ¹ and T ^2. ), To give a compound of the formula (26)

[0124]

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(Wherein R ^{1 to} R ⁵ , X, Y, T ¹ and T ² are
It has the same meaning as R ^{1 to} R ⁵ , X, Y, T ¹ and T ² described above. ) Can be obtained.

With respect to specific examples of the compound represented by the general formula (6), the following compounds having substituents (1-
1) to (1-20).

[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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The visible light curable resin composition of the present invention comprises a photocurable resin (A), a photoreaction initiator (B) (eg, a photoradical polymerization initiator, a photoacid generator, a photobase generator, etc.) and It is a visible light curable resin composition containing a photosensitizer (C) using an indolizine compound having a unique structure.

The photocurable resin (A) used in the present invention comprises:
It is not particularly limited as long as it is a commonly used photocurable resin having a photosensitive group that can be crosslinked by light irradiation. Examples of the resin include a compound having at least one ethylenically unsaturated double bond, a monomer,
Examples include prepolymers, oligomers such as dimers and trimers, mixtures thereof, and copolymers thereof. In addition, for example, urethane resin, epoxy resin, polyester resin, polyether resin, alkyd resin, polyvinyl chloride resin, fluorine resin, silicone resin, vinyl acetate resin, novolak resin Resin and a resin in which a photopolymerizable unsaturated group is bonded to two or more kinds of modified resins. As the photopolymerizable unsaturated group,
For example, acryloyl group, methacryloyl group, vinyl group,
Examples include a styryl group, an allyl group, a cinnamoyl group, a cinnamylidene group, and an azide group.

In the photocurable resin (A), monofunctional and polyfunctional (meth) acrylates are generally used.
For example, an anionic photocurable resin containing a (meth) acryloyl group as a photosensitive group described in page 2, lower right column, line 6 to page 6, lower left column, line 16 of JP-A-3-223759, photosensitive resin Examples thereof include a photocurable resin containing a cinnamoyl group as a functional group, and a photocurable resin containing an allyl group as a photosensitive group. The photocurable resin (A) is preferably used in combination with the following photoradical polymerization initiator. These photocurable resins (A) may be used alone or may be mixed.

In the publication, the photocurable resin component (a
As specific examples of the esterified product of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid described in 2) of the ethylenically unsaturated compound, polyethylene glycol di (meth) acrylate having a molecular weight of 300 to 1,000 can also be used.

Further, in addition to the photocurable resin (A) described above, polymerization reaction, etherification reaction, pinacol transfer, silanol dehydration reaction, intramolecular dehydration condensation reaction, A compound that is cured (insolubilized) by a reaction such as a decomposition condensation reaction can be used. Examples of the compound include glycidyl ether type epoxy compounds such as bisphenol A type diglycidyl ether, (poly) ethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3,4-type.
Epoxycyclohexanecarboxylate, dicyclopentadienedioxide, epoxycyclohexenecarboxylic acid ethylene glycol diester, 1,3-bis [2- {3- (7-oxabicyclo [4.1.0] heptyl}) ethyl] -tetramethyl Disiloxane (J. Po
lym. Sci .: Part A: See Polym. Chem. 28,479,1990)
And other alicyclic epoxy compounds, butylene glycol divinyl ether, trimethylolpropanedi (1-propenyl) methyl ether, trimethylolpropanedi (1
-Propenyl) butyl ether, trimethylolpropanedi (1-propenyl) octyl ether, trimethylolpropanedi (1-propenyl) phenyl ether,
Vinyl ether compounds such as trimethylolpropanedi (1-propenyl) ether acetate, trimethylolpropanedi (1-propenyl) ether acrylate, and trimethylolpropanedi (1-propenyl) N-butyl carbonate (J. Polym. Sci .: Part A: Polym.
Chem. 34, 2051, 1996), dodecylarene (D
A), diethylene glycol dialene (DEGA), triethylene glycol dialene (TEGA), 1-tetrahydrofurfurylarene ether (THFA), N-
Hexyloxy-1,2-propagen (HA), 1,4
-Di-N-butoxy-1,2-butadiene (DBB),
Alkoxyallene compounds such as 1,4-diethoxy-1,2-butadiene and N-hexylpropadyl ether (HPE) (J. Polym. Sci .: Part A: Polym. Chem. 3)
Oxetane compounds such as 3-ethyl-3-phenoxymethyl-oxetane, phenoxymethyloxetane, methoxymethyloxetane, and 3-methyl-3-methoxymethyl-oxetane (see J. Polym. Sci.
: Part A: Polym. Chem. 33, 1807, 1995), 2-propylidene-4,5-dimethyl-1,3-dioxolane, 2 (propylidene) -4-methyl-1,3-dioxolane, 3,9 -Ketene acetal compounds such as diethylidene-2,4,8,10-tetraoxaspiro [5.5] undecane (J. Polym. Sci .: Part A: Polym. Che
m. 34,3091,1996), 1-phenyl-4-ethyl-
Bicycloorthoester compounds such as 2,6,7-trioxabicyclo [2.2.2] octane (J. Polym. Sc
i .: Polym. Lett. Ed. 23,359,1985), propiolactone, butyrolactone, γ-valerolactone, γ-
Lactone compounds such as caprolactone, γ-caprylolactone, γ-laurylolactone, coumarin, methoxy-
Aromatic vinyl compounds such as α-methylstyrene, heterocyclic vinyl compounds such as vinylcarbazole, melamine compounds such as hexamethylolmelamine and hexamethoxymelamine, and copolymers of P-vinylphenol and P-vinylbenzyl acetate And other aromatic compounds such as trimethylolbenzene and tri (acetoxycarbonylmethyl) benzene. These compounds may have a polymer structure as long as they are cured by protons of an acid.

Further, a compound which is cured (insolubilized) by a polymerization reaction or a condensation reaction using a base generated from the photobase generator as a catalyst, for example, a compound containing a functional group such as an epoxy group or a silanol group can be used.

Further, in addition to the above-mentioned compounds which are cured by a catalyst generated from a photoacid generator or a photobase generator, if necessary, conventionally known acrylic resins, vinyl resins, polyester resins, alkyd resins, Resins that do not contain unsaturated groups, such as epoxy resins, phenolic resins, rubbers, and urethane resins, can be blended.

As the photoreaction initiator (B) used in the present invention, a photoradical polymerization initiator, a photoacid generator and a photobase generator can be used.

As the photo-radical polymerization initiator, conventionally known photo-radical polymerization initiators can be used. Examples thereof include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α′-dichloro-. Acetophenones such as 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone and acetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t Organic peroxides such as -butyldiperoxyisophthalate and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; diphenylio Bromide, diphenyl halonium salts such as diphenyl iodonium chloride; carbon tetrabromide,
Organic halides such as chloroform and iodoform;
Heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone;
2′-azo (2,4-dimethylvaleronitrile), 2,
2-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-
Azo compounds such as azobis (2-methylbutyronitrile); iron-arene complexes (see EP 152377); titanocene compounds (JP-A-63-2211)
No. 10) Bisimidazole compounds; N-arylglycidyl compounds; acridine compounds; combinations of aromatic ketones / amines; peroxyketals (see JP-A-6-321895). Among the above radical photopolymerization initiators, di-t-
Butyldiperoxyisophthalate, 3,3 ', 4
It is preferable to use 4′-tetra (t-butylperoxycarbonyl) benzophenone, iron-arlene complex, and titanocene compound because they have high activity for crosslinking or polymerization.

The photoacid generator is a compound which generates an acid upon exposure to light and cures the above-mentioned compound by using the generated acid as a catalyst. Conventionally known photoacid generators can be used. . Examples thereof include sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, onium salts such as selenium salts,
Iron-arene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfonic esters, sulfonic imide esters, and the like can be used. In addition to the above, JP-A-7-146552 and Japanese Patent Application No. 9-289218.
The photoacid generator described in the above item can also be used.

The photobase generator is a compound that generates a base upon exposure to light, and cures the above-described compound using the generated base as a catalyst. Conventionally known photobase generators can be used. . This includes, for example, nitrobenzyl carbamate compounds such as ((o-nitrobenzyl) oxy) carbonylcyclohexylamine (J. Am. Chem. Soc, Vol. 113, No. 11, 4305, 19).
91), N-[[1-3,5-dimethoxyphenyl)
-1-methyl-ethoxy] carbonyl] cyclohexylamine, N-[[1- (3,5-dimethoxyphenyl)
Photofunctional urethane compounds such as -1-methyl-ethoxy] carbonyl] pyridine (J. Org. Chem. Vol. 55, No. 2
3, 5919, 1990) can be used.

The mixing ratio of the photoreaction initiator is not critical, and can be changed in a wide range depending on the type. In general, 100 parts by mass (solid content) of the photocurable resin is used.
0.1 to 25 parts by mass, preferably 0.2 to 10 parts by mass
Parts by weight. When used in a large amount exceeding 25 parts by mass, the stability of the resulting composition tends to decrease.

The visible light curable resin composition of the present invention contains at least one indolizine compound represented by the general formula (1) as a photosensitizer (C). A known photosensitizer may be contained.

The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer. Ketocoumarin, coumarin-6 and the coumarin compounds described in JP-A-4-18088, and Kaihei 11-322744
And the like.

In this case, the content of the indolizine compound represented by the general formula (1) in the photosensitizer (C) is not particularly limited, but in order to obtain a desired effect in the present invention, The content of the indolizine compound represented by the general formula (1) in the photosensitizer (C) is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably A photosensitizer containing 30% by mass or more and 50% by mass or more is particularly preferable.

The amount of the photosensitizer (C) used depends on the type and amount of the photosensitizer (C) and the photocurable resin (A) to be interacted with.
Depending on the type of component, usually, the photocurable resin (A)
The amount of the photosensitizer (C) to be used is in the range of 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the component. When the amount of the present compound is less than 0.1 part by mass, the photosensitivity of the formed film tends to decrease. When the amount is more than 10 parts by mass, the composition is made uniform from the viewpoint of solubility. It tends to be difficult to keep.

The visible light-sensitive resin composition used in the present invention may further contain, if necessary, a photopolymerizable unsaturated compound (resin) other than the above components. This includes, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol tri (meth) acrylate,
Examples include trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate.

The other photopolymerizable unsaturated compounds described above are preferably in the range of about 0 to 50% by weight, particularly about 0.1 to 40% by weight, based on the total weight (solid content) of the composition.

In the present invention, a radical protecting compound (D) can be blended if necessary. Radicals generated when a resist film formed from a visible light curable resin composition is cured by irradiation with a visible light laser function to prevent deactivation by oxygen, thereby making the resist good even in the presence of oxygen. In the present invention, at least one selected from a phosphite compound and an aromatic compound having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring is used in the present invention.
Kinds of compounds are preferably used as radical protecting compound (D).

In the visible light-sensitive resin composition, when oxygen is present, radicals generated by light irradiation react with oxygen to become peroxy radicals, and usually, the peroxy radicals react with each other to become oxygen molecules and are lost. However, when the radical protecting compound (D) is present according to the present invention, many of the peroxy radicals react with the radical protecting compound (D) to generate another radical, Is considered to contribute to the curing reaction of the resist film. As a result, the visible light-sensitive resin composition of the present invention can maintain high sensitivity without blocking oxygen.

Representative examples of the above phosphite compounds include phosphites such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, bis (2-ethylhexyl) phosphite, diphenyl phosphite, dibenzyl phosphite and the like. A dialkyl, diaryl or diaralkyl ester of
Trialkyl or triaryl esters of phosphites such as trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, triisodecyl phosphite, tris (tridecyl) phosphite; benzyl diethyl Aralkyl dialkyl esters of phosphorous acid, such as phosphorous acid; tris (2,
Examples thereof include tri (haloalkyl) esters of phosphorous acid such as 2,2-trifluoroethyl) phosphorous acid and tris (2-chloroethyl) phosphorous acid.

Representative examples of the aromatic compound having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring include N, N-dimethylaniline and 4-bromo-
N, N-dimethylaniline, 4-t-butyl-N, N-
Dimethylaniline, 2,6-diisopropyl-N, N-
Dimethylaniline, 4,4'-vinylidenebis (N, N
-Dimethylaniline), 4,4'-methylenebis (N,
N-dimethylaniline), 4,4′-methylenebis (2,6-diisopropyl-N, N-dimethylaniline), N, N, 2,4,6-pentamethylaniline,
Examples thereof include N, N-dimethylaniline derivatives such as N, N-dimethyl-m-toluidine, 4- (2-pyridylazo) -N, N-dimethylaniline, and N, N-dimethyl-4-nitrosoaniline.

Of these, an aromatic compound having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring and having a molecular weight of 120 to 400 has a high compatibility with the resin of the resist and the obtained resist film. It is particularly preferable in terms of sensitivity to visible light.

The amount of the specific radical protective compound (D) is not strictly limited, and can be changed according to the type and amount of the photoreaction initiator (B) used. , Solid content of visible light-sensitive resin composition 100
The amount is preferably in the range of 0 to 30 parts by mass, particularly preferably in the range of 1 to 10 parts by mass with respect to the photosensitivity of the resist film, the film strength, and the like.

In the visible light curable resin composition of the present invention, if necessary, adhesion promoters, hydroquinone, 2,6-
Polymerization inhibitors such as di-t-butyl-p-cresol and N, N-diphenyl-p-phenylenediamine; organic resin fine particles such as rubber, vinyl polymer and unsaturated group-containing vinyl polymer; coloring pigment; Contains various pigments such as pigments, metal oxides such as cobalt oxide, plasticizers such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, polyethylene glycol and polypropylene glycol, repelling inhibitors, fluidity regulators, etc. can do.

The above-mentioned adhesion promoters are used to improve the adhesion of the film to the substrate, and include, for example, tetrazole, 1-phenyltetrazole, 5-aminotetrazole, 5-amino-1- Methyltetrazole, 5-amino-2-phenyltetrazole, 5-mercapto-1-phenyltetrazole, 5-
Examples thereof include tetrazoles such as mercapto-1-methyltetrazole, 5-methylthiotetrazole, and 5-chloro-1-phenyl-1H-tetrazole.

The composition of the present invention can be used in a safe light irradiation environment having a maximum relative wavelength and a maximum wavelength selected from the range of 500 to 620 nm. When used with this safe light, the unexposed film formed from the composition has an absorbance of 0.5 or less in a range of ± 30 nm of the maximum wavelength of the safe light.

The conventional safety light is a fluorescent light colored red, but the emission spectrum of the fluorescent light has a wide wavelength range from ultraviolet light to visible light (FIG. 5). Even the visible light-sensitive resin coating that does not require curing is hardened, and a clear resist pattern cannot be formed by the development process. For this reason, the working environment is further darkened because the intensity of the illumination light is reduced. There is such a problem. On the other hand, the safety light used in the present application solves the above problem because it has a sharp wavelength like a sodium lamp, for example.

That is, the safety light used in the present invention is 50
It is a visible light with a large relative luminous efficiency having a maximum wavelength selected from the range of 0 to 620 nm, preferably 510 to 600 nm. This safety light can be obtained, for example, by using a discharge lamp that emits light having a maximum wavelength in the above-described range by discharging in a gas such as sodium. Among them, the sodium lamp mainly emits yellow D-line light having a wavelength of 589 nm from the lamp,
Since the light is monochromatic light, the object can be seen sharply with less chromatic aberration, so that it is excellent in safety, work environment and the like. FIG. 1 shows a spectral distribution diagram of the low-pressure sodium lamp. As shown in the sodium lamp spectral distribution diagram, in addition to the D line which is the maximum wavelength of the sodium lamp, a high energy ray wavelength component (low wavelength region) is provided to such an extent that the visible light curable resin composition is not adversely affected. No problem.

[0176] In addition, a high-energy ray wavelength component other than the D ray cut by applying a filter to the sodium lamp can also be used as safety light. FIG. 2 shows the spectral distribution of the sodium lamp from which high-energy ray wavelength components have been cut. Examples of the filter include “Fantac FD-1081 Scarlet”, “Fantac FC-1431 Sunflower Yellow” (trade name, manufactured by Kansai Paint Co., Ltd.), and “Lintech Lumicool Film No. 190.
5 "(trade name, manufactured by Lintec Corporation).

As the safety light used in the present invention, it is preferable to use a sharp single light color having a light beam of 589 nm like a sodium lamp, but the maximum wavelength is 500 to 6 nm.
Safety light having a wavelength component distributed in a wavelength range of an ultraviolet light region, a visible light region other than the above range, and an infrared light region other than the range of 20 nm may be used. However, when using safety light containing wavelength components distributed outside the range in this way, the distributed wavelength range does not adversely affect the visible light curable resin composition (photosensitivity). It must be an area.

Such a safe high-energy light wavelength region (low-wavelength region) relates to the energy intensity of the distributed light beam and the absorbance of the visible light curable resin composition in that region. Can be used when the composition has a small absorbance, and when the energy intensity of the light beam is small, the composition can have a relatively large absorbance than the former. It is possible to have a high-energy light wavelength range to such an extent that it does not adversely affect the light. However, even if a normal fluorescent lamp having a maximum wavelength in the range of 500 to 620 nm is used as the safety light, the fluorescent light is still less than 5 mm.
Since it has a large light energy intensity of less than 00 nm, particularly 400 to 499 nm, it cannot be used as a safe light of a visible light photosensitive resin composition which is exposed with a visible light laser having an oscillation line at 488 nm or 532 nm.

The absorbance used in the present invention is -log (I
/ I ₀ ). Here, I is the intensity of the transmitted light of the coating obtained by applying the photosensitive resin composition to the surface of the transparent substrate and drying (removing the solvent), and I ₀ is a blank [sample (photosensitive resin composition) is applied. Of a transparent substrate (for example, a polyethylene terephthalate sheet)].

The brightness caused by the light entering the human eye can be represented by relative luminous efficiency. The relative luminous efficiency is JI
As defined in SZ8113, 2005, under certain observation conditions, when it is determined that the monochromatic radiation of a certain wavelength λ has the same brightness as the radiation used as a reference for comparison, the monochromatic radiation of a wavelength λ is determined. It is defined as the reciprocal of the relative value of the radiance, usually normalized such that the maximum value when λ is changed becomes 1. FIG. 3 shows a relative luminous efficiency curve in a wavelength range of visible light of 380 to 780 nm. In FIG. 3, the vertical axis represents the ratio, with the maximum value of the relative luminous efficiency set to 100. From this curve, the conventional red wavelength range of 640 to
At 780 nm, the relative luminous efficiency is low, and it is perceived as dark by human eyes. For example, it can be seen that the radiation intensity must be further increased in order to feel the same brightness as the wavelength of 589 nm. The maximum value of the visibility is about 555 nm (JI
S-Z8113 2008).

The absorbance of the unexposed film formed from the visible light curable resin composition of the present invention is within the range of ± 30 nm (-30 nm to +30 nm) of the maximum wavelength of the safe light having the maximum wavelength selected from the above range. , Preferably in the range of ± 20 nm (−20 nm to +20 nm), more preferably 0.5 or less for the range of ± 10 nm (−10 nm to +10 nm).
Preferably it is 0.2 or less, more preferably 0.1 or less.

In the dried film (containing no solvent) formed from the visible light curable resin composition of the present invention, the absorbance of the non-photosensitive film formed from the composition is selected from the above range of the maximum wavelength of the safe light. The wavelength may be set to 0.5 or less in the range of ± 30 nm of the maximum wavelength, but from the viewpoint of practicality, it is usually 0.1 to 50 μm, preferably 1 to 30 μm.
It is in the range of μm. The absorbance varies depending on the type and the amount of the photoreaction initiator (B) and the photosensitizer (C) contained in the composition, but varies depending on the thickness of the film even with the same composition. That is, in the same composition, as the film thickness increases, the absorbance increases because the concentration of the photoreaction initiator (B), the photosensitizer (C), etc. contained in the film increases,
On the other hand, as the film thickness decreases, the absorbance decreases because the concentration of the above components contained in the film decreases. From these facts, the absorbance can be adjusted so as to fall within the above-mentioned range by adjusting the thickness of the film to be formed.

The visible light curable resin composition of the present invention can be prepared by using known photosensitive materials generally used, for example, paints, inks, adhesives, resist materials, printing plate materials (plate making materials for flat plates and letterpress, offset printing). PS plate for use) It can be used for a wide range of applications such as information recording materials and relief image forming materials.

Next, typical resist materials of the visible light curable resin composition of the present invention (for example, general negative curable resist materials and negative resist materials for electrodeposition coating) will be described.

As a general negative curable resist material, for example, the visible light curable resin composition of the present invention is dispersed or dissolved in a solvent (including water). Fine dispersion) to prepare a photosensitive solution, and apply it to a support using a coating device such as a roller, a roll coater, or a spin coater, and dry the solution. Can be used as

Further, a cover coat layer can be provided in advance on the surface of the film before being exposed to visible light and cured.
The cover coat layer is formed in order to block oxygen in the air, prevent radicals generated by exposure from being deactivated by oxygen, and smoothly cure the coating by exposure.

As the cover coat layer, for example, a resin film (thickness: about 1 to 70 μm) such as polyester resin such as polyethylene terephthalate, acrylic resin, polyethylene, polyvinyl chloride resin or the like is coated on the surface of the coating film. Polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl alcohol-vinyl acetate copolymer, partially saponified polyvinyl acetate-vinyl acetate copolymer, polyvinyl pyrrolidone, water-soluble polysaccharide polymers such as pullulan, basic group An aqueous solution containing an acidic group or a base and containing or dissolving or dispersing aqueous resins such as acrylic resin, polyester resin, vinyl resin, and epoxy resin in water is applied to the surface of the coating film (dry film thickness: about 0.5).
５5 μm) and dried to form a cover coat layer. This cover coat layer is preferably removed after exposing the coating film and before developing. The cover coat layer of the water-soluble polysaccharide polymer or the aqueous resin can be removed with a solvent such as water, an acidic aqueous solution, or a basic aqueous solution which dissolves or disperses the resin.

Solvents used for dissolving or dispersing the visible light curable resin composition include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and esters (ethyl acetate, butyl acetate, methyl benzoate). , Methyl propionate, etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenated hydrocarbons (chloroform,
Trichloroethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, dimethyl sulfoxide, etc.),
Water and the like.

Examples of the support include a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel and iron or an alloy containing them as a component, a printed circuit board whose surface is treated with these metals, and a plastic. , Glass or silicone wafers, carbon and the like.

When using as a negative resist material for electrodeposition coating, first, the visible light-curable resin composition is made into a water dispersion or an aqueous solution.

The water-dispersible or water-soluble visible light curable resin composition may be alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the photocurable resin.
Or when a cationic group such as an amino group is introduced, neutralization with an acid (neutralizing agent). Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Further, examples of the acid neutralizing agent include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent used is the amount of the ionic group 1 contained in the photosensitive resin composition.
0.2 to 1.0 equivalent, particularly 0.3 to 1.0 equivalent per equivalent
A range of 0.8 equivalents is desirable.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol, t- -Butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used is generally
Up to 300 parts by mass per 100 parts by mass of resin solid component,
Preferably it can be up to 100 parts by mass.

Further, in order to increase the amount of coating on the object to be coated, a hydrophobic solvent,
For example, petroleum solvents such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added. The compounding amount of these hydrophobic solvents can be generally up to 200 parts by mass, preferably 100 parts by mass or less, per 100 parts by mass of the resin solid component.

The preparation of the visible light-curable resin composition as an electrodeposition paint can be carried out by a conventionally known method. For example, a photocurable resin (A), a photoreaction initiator (B), a photosensitizer (C) having a specific structure, and a radical protecting agent (D) if necessary ), A solvent and other components are well mixed, and the mixture can be prepared by adding water.

The composition thus prepared is further diluted with water in a usual manner, for example, in a pH range of 4 to 9 and a bath concentration (solid concentration) of 3 to 25% by mass, preferably Can be an electrodeposition paint (or an electrodeposition bath) in the range of 5 to 15% by mass.

The electrodeposition paint prepared as described above is
The coating can be performed on the surface of the conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is adjusted to 15 to 40 ° C, preferably 1 to 40 ° C.
Control at 5-30 ° C. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. An appropriate energization time is 10 seconds to 5 minutes.

Further, in this electrodeposition coating method, a method of coating an object to be coated with an electrodeposition coating material having a low glass transition temperature, then washing with water or washing and drying, and further applying an electrodeposition coating material having a glass transition temperature of 20 ° C. or more. (See JP-A-2-20873), that is, double-coat electrodeposition coating can also be performed.

The obtained film thickness is a dry film thickness, generally 0.1
５０50 μm, preferably 1 to 15 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then moisture and the like contained in the electrodeposition coating film are dried and removed with hot air or the like.

As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material in which these are fixed to the surface of plastic or glass by lamination, plating or the like can be used.

A cover coat layer may be provided on the surface of the electrodeposition coating film before being exposed to visible light and cured. Examples of the cover coat layer include those described above. This cover coat layer is preferably removed before the electrodeposition coating film is developed. The cover coat layer using a water-soluble polysaccharide polymer or an aqueous resin can be removed with a solvent such as water, an acidic aqueous solution, or a basic aqueous solution that dissolves or disperses these resins.

The visible light resist material formed on the conductor surface as described above, and the visible light resist electrodeposition coating film obtained by electrodeposition coating are exposed to visible light according to an image and cured. An image can be formed by removing the non-exposed portion by a developing process.

As a light source for curing the composition for visible light-sensitive material of the present invention, a conventionally known light source of visible light can be used without any particular limitation as long as it cures the composition. Examples of the light source that emits visible light include ultrahigh-pressure, high-pressure, medium-pressure, and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, and tungsten lamps. Further, among these light sources, various lasers having an oscillation line in a visible region where ultraviolet rays are cut by an ultraviolet cut filter can be used. Among them, GaN laser (405 nm), He
-Cd laser (430 nm), argon laser (4
88 nm) or YAG-SHG laser (532 nm)
Are preferred.

The development treatment is carried out by rinsing with an aqueous alkali solution when the non-exposed film is anionic, and with an aqueous acid solution having a pH of 5 or less when the film is cationic. Alkaline aqueous solutions that can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc., to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used.

Further, in the case of a photosensitive resin having no ionic group, development processing is performed by dissolving an unexposed portion using a solvent such as 1,1,1-trichloroethane, trichloroethylene, methyl ethyl ketone, or methylene chloride. . The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. If necessary, the printed circuit board can be manufactured by performing etching to remove the exposed conductor portion, and then removing the resist film.

The composition for a visible light-sensitive material of the present invention may be, for example, coated on a transparent resin film such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin to be a cover film layer. The composition of the present invention is applied using a roll coater, blade coater, curtain flow coater, etc., and dried to form a resist film (dry film thickness: about 0.1 to 5 μm). It can be used as a dry film resist having a protective film attached to the surface of the coating.

Such a dry film resist can be formed by peeling off the protective film and then bonding the resist film to a support by thermocompression bonding so that the resist film is in contact with the resist film to form a resist film. The resist film can be exposed to visible light, cured and developed according to the image in the same manner as the above-mentioned electrodeposition coating film to form an image. Further, in the dry film resist, a cover coat layer can be provided as necessary as described above. The cover coat layer may be formed by painting on the resist film, or may be formed by sticking on the resist film. The cover coat layer may or may not be removed before the development processing.

[0207]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. In the examples and comparative examples, “parts” indicates “parts by mass”. Regarding mass spectrometry, electron impact ionization mass spectrometry (EI-MS) was manufactured by JEOL Ltd. AX-505W.
A, Field desorption ionization mass spectrometry (FD-MS) was measured using SX-102A manufactured by JEOL Ltd.

Synthesis Example 1 Synthesis of Exemplified Compound (1-1)

[0209]

Embedded image

(1) Synthesis of compound a 27.5 g (0.157 mol) of quinaldine, 100 ml of dehydrated ethanol and 31.4 g of ethyl bromoacetate
(0.188 mol), and the mixture was heated to 83 ° C. and kept under reflux for 4 hours. After concentrating while replacing the reaction mass solvent with acetone, the mixture was filtered and dried to obtain 23.8 g (0.077 mol) of N- (ethoxycarbonylmethyl) -2-methylquinolinium bromide (compound a).

(2) Synthesis of Compound b 23.3 g (75.0 mmol) of compound a, 16.2 g of diethyl ethoxymethylenemalonate (75.0 mmol)
l), 248.8 g (1.8 mol) of potassium carbonate and 500 g of dehydrated ethanol were mixed and stirred at room temperature for 3 hours. After discharging the reaction mass into 3 L of water, extraction and liquid separation were performed using toluene, and the toluene organic layer was dried over sodium sulfate. After filtering off sodium sulfate, the filtrate is concentrated,
Recrystallization from toluene gives 3-ethoxycarbonyl-2H
-Pyrano [2,3-b] -benzo [1,2-h] indolizin-2-one (compound b) 2.90 g (9.82 m
mol).

(3) Synthesis of Exemplified Compound (1-1) Compound b 0.31 g (1.01 mmol), Lawson's reagent (manufactured by Wako Pure Chemical Industries, Ltd.) 0.45 g (1.11 mol) and toluene 30 ml were mixed. Refluxed for hours. The reaction mass was concentrated and purified by silica gel column chromatography (developing solvent: chloroform). After concentrating the preparative mass, the residue was recrystallized from methanol to give 3-ethoxycarbonyl-2-thia-2H-pyrano [2,3-b] -benzo [1,2-h] indolizine (exemplified compound (1-
1)) 0.15 g (red-brown crystals, 0.464 mmol)
I got

[0213]

[Table 1]

[Mass spectrometry] Using EI-MS. m / z: 250 (base peak) 323 (parent ion peak) [Absorption spectrum] (in chloroform) (first peak) λ _max = 489.0 nm (second peak) λ _max = 521.5 nm (third peak) λ _max = 430.6 nm

Synthesis Example 2 Synthesis of exemplified compound (1-19)

[0216]

Embedded image

(1) Synthesis of Compound c 24.8 g (0.266 mol) of α-picoline and 125 g of dehydrated ethanol were mixed, and 44.4 g (0.266 mol) of ethyl bromoacetate was added dropwise. 80
C., and kept at room temperature for 2 hours and then cooled to room temperature. After concentrating the reaction mass, 100 g of acetone was charged and shaken to form crystals. After cooling using an ice-water bath, the mixture was filtered and dried, and 60.2 g of N- (ethoxycarbonylmethyl) -2-methylpyridinium bromide (compound c) was added.
31 mol).

(2) Synthesis of Exemplified Compound (1-19) 27.1 g (0.104 mol) of compound c, 22.5 g (0.104 mol) of diethyl ethoxymethylenemalonate
l), potassium carbonate (345.0 g, 2.50 mol) and dehydrated ethanol (500 g) were mixed, and the mixture was stirred at room temperature for 3 days. The reaction mass was filtered off, and the filtrate was discharged into 3 L of water. Extraction and liquid separation were performed using toluene, and the obtained organic layer was dried over sodium sulfate. After drying, the mixture was filtered and the filtrate was concentrated. The main component of the concentrated mass was collected by silica gel column chromatography (developing solution: chloroform / ethyl acetate = 95/5). The collected solution was concentrated, recrystallized from chloroform, and 0.18 g (0.700 mmol) of 3-ethoxycarbonyl-2H-pyrano [2,3-b] indolizin-2-one (exemplary compound (1-19)). ) Got.

[0219]

[Table 2]

[Mass spectrometry] Using FD-MS.

M / z: 257 (peak of parent ion) [Absorption spectrum] (in toluene) (first peak) λ _max = 448.0 nm [toluene] (second peak) λ _max = 424.5 nm [toluene]

Example 1 As a photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20/10 //
100 parts by mass of a mixture of 20 (mass ratio), 55 parts of trimethylolpropane triacrylate,
-1) 1.5 parts of a photosensitizer and a photoreaction initiator represented by the following formula (α)

[0223]

Embedded image

A photosensitive solution was prepared using 20 parts of the titanocene compound and 160 parts of methyl cellosolve as a solvent.

The photosensitive solution obtained as described above was coated with a plate having a thickness of 2 mm and a size of 350
A 460 mm copper-clad glass fiber reinforced epoxy substrate was applied using a spinner and dried at 60 ° C. for 10 minutes to prepare a substrate having a resist film with a dry film thickness of 5 μm. Next, when the substrate having the resist coating was irradiated with light from a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm), the resin was quickly cured (to a 1% aqueous sodium carbonate solution (developer) at 30 ° C.). Immersion for 1 minute and development processing to prevent dissolution).

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above. Was done.

Examples 2 to 18 In Example 1, the exemplified compound (1-
A photosensitive solution was prepared in the same manner as in Example 1 except that 2) to (1-18) were used. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cut the ultraviolet wavelength region) and an Ar laser (488 nm) were used.
When the substrate having the above-mentioned resist film is irradiated with the light of m), the resin is quickly cured (immersed in a 1% aqueous solution of sodium carbonate (developing solution) at 30 ° C. for 1 minute, developed and not dissolved). confirmed.

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above. Was done.

Example 19 Instead of 20 parts of the titanocene compound of the formula (α) in Example 1, 20 parts of 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone was used as a photoreaction initiator. And the same photosensitive solution as in Example 1 was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were irradiated with light on the substrate having the resist film. It was confirmed that the resin was cured (immersed in a 1% aqueous sodium carbonate solution (developer) at 30 ° C. for 1 minute, developed and not dissolved).

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above, and it was confirmed that the resin was quickly cured. Was done.

Example 20 The same procedure as in Example 1 was carried out except that 20 parts of di-t-butyldiperoxyisophthalate was used as a photoreaction initiator instead of 20 parts of the titanocene compound of the formula (α) in Example 1. A photosensitive solution was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were applied to the substrate having the resist film at an intensity of 5 mJ / cm ² . Upon irradiation with light, it was confirmed that the resin was quickly cured (immersed in a 1% aqueous solution of sodium carbonate (developing solution) at 30 ° C. for 1 minute, developed and not dissolved).

After leaving the unexposed substrate at room temperature for 6 months, a 5 mJ / cm ² intensity xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (4
(88 nm), it was confirmed that the resin was quickly cured.

Example 21 Instead of the Ar laser (488 nm) of Example 1, Y
Except that the second harmonic (532 nm) of the AG laser was used, the substrate having the resist film was irradiated with light in the same manner as in Example 1, and the resin was quickly cured (1% of 30 ° C.).
Immersion in an aqueous solution of sodium carbonate (developer) for 1 minute to develop and not dissolve).

After leaving the unexposed substrate at room temperature for 6 months, the xenon lamp (cutting the ultraviolet wavelength region) and the second harmonic (532 n
m), it was confirmed that the resin was quickly cured.

Examples 22 to 23 The same procedures as in Example 1 were carried out except that Exemplified Compounds (1-19) and (1-20) were used instead of Exemplified Compound (1-1) used in Example 1. Similarly, a photosensitive solution was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and a He-Cd laser (430 nm) were irradiated on the substrate having the resist film with light. It was confirmed that the resin was quickly cured (immersed in a 1% aqueous solution of sodium carbonate (developing solution) at 30 ° C. for 1 minute, developed and not dissolved).

After leaving the unexposed substrate at room temperature for 6 months, the substrate was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and a He-Cd laser (430 nm) in the same manner as described above. Was confirmed.

Example 24 In Example 1, methyl acrylate / styrene / acrylic acid = 60/10 instead of 100 parts of acrylic resin.
/ 30 radical copolymer (acid value about 233) and 35 parts of glycidyl methacrylate obtained by addition reaction (acid value about 70, degree of unsaturation 1.83 mol / kg)
A photosensitive solution having the same composition as in Example 1 was prepared using 100 parts. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were irradiated with light on the substrate having the resist film. The resin hardens (30% 1% aqueous sodium carbonate solution (developer)
Immersed in water for 1 minute to develop and not dissolve).

After leaving the unexposed substrate at room temperature for 6 months, irradiation with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above confirmed that the resin was quickly cured. Was done.

Example 25 In Example 1, a mixture of 50 parts of the acrylic resin and 50 parts of the photocurable resin used in Example 24 was used instead of 100 parts of the acrylic resin, and the same composition as in Example 1 was used. Was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cut the ultraviolet wavelength region) and an Ar laser (488 nm)
Was irradiated onto the substrate having the above resist film, and it was confirmed that the resin was quickly cured (immersed in a 1% aqueous sodium carbonate solution (developer) at 30 ° C. for 1 minute, developed and not dissolved). Was.

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above. Was done.

Example 26 The same composition as in Example 1 was used, except that 155 parts of the photocurable resin used in Example 24 was used instead of 100 parts of the acrylic resin and 55 parts of trimethylolpropane triacrylate. Was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1,
Xenon lamp (cut UV wavelength region) and Ar
When a laser (488 nm) was irradiated on the substrate having the resist coating with light, the resin was quickly cured (30 ° C.).
Immersed in a 1% aqueous sodium carbonate solution (developer) for 1 minute to develop and not dissolve).

When the unexposed substrate was left at room temperature for 6 months and then irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above, it was confirmed that the resin was quickly cured. Was done.

Example 27 The procedure of Example 1 was repeated, except that 55 parts of trimethylolpropane triacrylate and 20 parts of the titanocene compound were used.
Equation (β)

[0244]

Embedded image

An oxetane compound represented by the formula (γ):

[0246]

Embedded image

A photosensitive solution having the same composition as in Example 1 was prepared using 10 parts of the compound represented by the formula (1). Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were irradiated with light on the substrate having the resist film. Resin hardens (1% of 30 ℃)
Immersion in an aqueous solution of sodium carbonate (developer) for 1 minute to develop and not dissolve).

After leaving the unexposed substrate at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above. Was done.

Example 28 100 parts (solid content) of the photosensitive solution obtained in Example 24 was mixed and stirred with 7 parts of triethylamine, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%). Was.

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, washed with water, and dried at 80 ° C. for 5 minutes. Was carried out to obtain an electrocoating photosensitive layer. When a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were applied to the photosensitive layer using the photosensitive layer in the same manner as in Example 1, the resin was quickly cured (30).
Immersion in a 1% aqueous solution of sodium carbonate (developer) at 1 ° C. for 1 minute to develop and not dissolve).

After the photosensitive layer was allowed to stand at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above, and it was confirmed that the resin was quickly cured. Was.

Example 29 Methyl acrylate / styrene / butyl acrylate /
Photocurable resin obtained by adding 15 parts of acrylic acid to a radical copolymer of glycidyl methacrylate / dimethylaminoethyl methacrylate = 20/10/22/30/18 (amine value: about 56, degree of unsaturation: 1.83) (Mol / kg) 100 parts, a photosensitive liquid 100 obtained by mixing 1.5 parts of the compound 1-1 in Table 1, 55 parts of trimethylolpropane triacrylate, and 20 parts of the same titanocene compound used in Example 1. (Solid content) was mixed with 3 parts of acetic acid, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%).

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, cationic electrodeposition coating was performed using a laminated copper plate as a cathode to a dry film thickness of 5 μm, washed with water, and dried at 80 ° C. for 5 minutes. Was carried out to obtain an electrocoating photosensitive layer. When the above photosensitive layer was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) using the photosensitive layer, the resin was quickly cured (2.38% tetramethyl ammonium hydrochloride at 30 ° C.). It was confirmed that the film was immersed in an aqueous solution of an oxide (developer) for 1 minute, developed and not dissolved.

After the photosensitive layer was allowed to stand at room temperature for 6 months and then irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above, it was confirmed that the resin was quickly cured. Was.

Example 30 In Example 1, N, N-
A photosensitive solution was prepared in the same manner as in Example 1 except that 3 parts of dimethylaniline was used. Using this, a photosensitive solution having the same composition as in Example 1 was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1,
Xenon lamp (cut UV wavelength region) and Ar
When a laser (488 nm) was irradiated on the substrate having the resist coating with light, the resin was quickly cured (30 ° C.).
Immersed in a 1% aqueous sodium carbonate solution (developer) for 1 minute to develop and not dissolve).

Further, after the unexposed substrate was left at room temperature for 6 months, irradiation with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above confirmed that the resin was quickly cured. Was done.

Examples 31 to 47 Photosensitive liquids were prepared in the same manner as in Examples 2 to 90 except that 3 parts of N, N-dimethylaniline was used as the radical protecting compound. . Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) were irradiated with light on the substrate having the resist film. It was confirmed that the resin was cured (immersed in a 1% aqueous sodium carbonate solution (developer) at 30 ° C. for 1 minute, developed and not dissolved).

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) in the same manner as described above. Was done.

Example 48 A photosensitive solution was prepared in the same manner as in Example 1, except that 5 parts of triethyl phosphite was used as the radical protecting compound. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (48) were used.
When the substrate having the above resist film is irradiated with light (8 nm), the resin is quickly cured (immersed in a 1% aqueous solution of sodium carbonate (developing solution) at 30 ° C. for 1 minute, developed and not dissolved). confirmed.

After leaving the unexposed substrate at room temperature for 6 months, irradiation with a xenon lamp (cutting the ultraviolet wavelength region) and an Ar laser (488 nm) as described above confirmed that the resin was quickly cured. Was done.

Examples 49 to 50 Photosensitive liquids were prepared in the same manner as in Examples 22 to 23 except that 3 parts of N, N-dimethylaniline was used as the radical protecting compound. Using this, a photosensitive solution having the same composition as in Example 1 was prepared. Using this, a resist film was formed on the substrate in the same manner as in Example 1, and a xenon lamp (cutting the ultraviolet wavelength region) and a He-Cd laser (430 nm) were irradiated on the substrate having the resist film with light. It was confirmed that the resin was quickly cured (immersed in a 1% aqueous solution of sodium carbonate (developing solution) at 30 ° C. for 1 minute, developed and not dissolved).

After the unexposed substrate was left at room temperature for 6 months, it was irradiated with a xenon lamp (cutting the ultraviolet wavelength region) and a He-Cd laser (430 nm) in the same manner as described above. Was confirmed.

Example 51 The photosensitive solution obtained in Example 1 was dried on a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater to a dry film thickness of 5%.
It was coated to a thickness of μm and dried at 60 ° C. for 10 minutes to produce a substrate having a resist film.

Next, the surface of the substrate having the resist film obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Then
After heating this at 120 ° C for 30 seconds in a dark room,
The resist film was completely dissolved in the aqueous sodium carbonate solution as a result of immersion in a 30% aqueous solution of sodium carbonate as a developing solution at 30 ° C. for 1 minute.

The photosensitive solution was applied to a transparent polyethylene terephthalate sheet with a bar coater so as to have a thickness of 5 μm, and dried at 60 ° C. for 10 minutes, and the absorbance of the unphotosensitive film was measured. As a result, in the range of 550 to 630 nm, which is the range of ± 30 nm or more of the maximum wavelength of the safe light in FIG. 1, the absorbance of the unexposed film is 0.5 or less, and the safe light does not adversely affect the photosensitive solution. It can be confirmed that the safety light is bright light from the relative luminous efficiency curve of FIG.

Examples 52 to 69 The photosensitive liquids obtained in Examples 2 to 18 were applied to a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater so that the dry film thickness was 5 μm. After drying for 10 minutes, a substrate having a resist film was prepared.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity was 40 lux. Then, in a dark room at 120 ° C. for 30 minutes.
After heating for 2 seconds, the resist film was completely dissolved in the aqueous solution of sodium carbonate as a result of immersion for 1 minute at 30 ° C. using a 1% aqueous solution of sodium carbonate as a developing solution. .

Examples 70 to 71 The photosensitive liquids obtained in Examples 22 to 23 were applied to a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater so as to have a dry film thickness of 5 μm. After drying for 10 minutes, a substrate having a resist film was prepared.

Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity was 40 lux. Then, in a dark room at 120 ° C. for 30 minutes.
After heating for 2 seconds, the resist film was completely dissolved in the aqueous solution of sodium carbonate as a result of immersion for 1 minute at 30 ° C. using a 1% aqueous solution of sodium carbonate as a developing solution. .

Comparative Examples 1 to 20 Substrates having a resist coating were produced in the same manner as in Examples 52 to 71 except that fluorescent lamps were used in place of the sodium lamp. Further, the obtained substrate was immersed in a 1% aqueous solution of sodium carbonate in the same manner as in Example 1. As a result, the resist film was not dissolved in the aqueous solution of sodium carbonate and was poor.

FIG. 4 shows the spectral distribution of the fluorescence and the like used in Comparative Examples 1 to 20.

[0272]

According to the present invention, a visible light curable resin composition containing a specific compound as a photosensitizer is a composition having extremely high practical utility. Conventionally, in the field of information recording using photocuring reaction, the method of directly outputting and recording the original electronically edited by a computer using a laser as it is, the stability of the photosensitive layer over time is low, and the sensitivity is low. , Solubility and storage stability.

However, the visible light curable resin composition of the present invention has a very good compatibility between the photocurable resin and the photosensitizer, is dissolved in a general-purpose coating solution, and is uniform on a support. ,
A coated surface excellent in storage stability over time can be obtained.

The indolizine compound photosensitizer having a unique structure used in the present invention has a He-Cd laser having a stable oscillation line at 430 nm, and has a stable oscillation line at 488 nm and 514.5 nm. Argon laser or YA with emission line at 532 nm as second harmonic
Since it has extremely high sensitivity to general-purpose visible lasers such as G lasers, the photosensitive material obtained using the visible light-curable resin composition of the present invention can be subjected to high-speed scanning exposure with such lasers. is there. When an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

The visible light curable resin composition of the present invention can be coated and printed under bright environmental conditions without increasing the viscosity of the composition under the environmental conditions of safe light irradiation.
It exerts a remarkable effect that is excellent in safety workability, work efficiency, product quality stability and the like.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a spectral distribution of a discharge lamp containing sodium as a main component of safety light that can be used in the present invention.

FIG. 2 is a graph showing a spectral distribution obtained by filtering a sodium discharge lamp.

FIG. 3 is a graph showing a relative luminosity curve.

FIG. 4 is a graph showing a spectral distribution of a fluorescent lamp.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 7/028 7/028 (72) Inventor Kazuhiro Kiyono Mayor of Sodegaura, Chiba Prefecture Takuji Ura 580 No. 32 Inside Mitsui Chemicals Co., Ltd. 580-2, Takuji No. 580 32 F-term in Mitsui Chemicals, Inc. SA63 SA64 SA78 SA88 TA08 TA10 UA01 WA01

Claims (10)

[Claims] 1. A compound of the general formula (1) In the formula, ring A represents an indolizine ring which may have a substituent, X is a hydrogen atom, a cyano group, a carboxyl group, and a compound represented by the following formula (2): [Wherein, Q is each independently an optionally substituted alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group, an alkylthio group, an aralkylthio group, an arylthio group, an alkenylthio group, or Formula (3) (In the formula, L ¹ and L ² each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group, an aryl group, or an alkenyl group.) Y represents a carboxyl group, a carbonyl group or a heterocyclic group represented by the formula (2); Z represents an oxygen atom, a sulfur atom, and a compound represented by the following formula (4) ) [Wherein T ¹ and T ² are each independently a hydrogen atom, a cyano group, a carbonyl group represented by the formula (2), or a compound represented by the following formula (5)] (In the formula, M ^{1 to} M ³ represent an alkyl group which may be substituted, G represents an oxygen atom or a dicyanomethylidenyl group, and * represents a bonding position.) ] A photosensitizer comprising at least one indolizine compound represented by (1). 2. The indolizine compound represented by the general formula (1) is represented by the following general formula (6): 中 wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently
Hydrogen atom, cyano group, hydroxyl group, halogen atom,
An alkyl group which may have a substituent, an aralkyl group,
Aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, acyl group, acyloxy group, heteroaryl group, heteroaryloxy group, A heteroarylthio group represented by the following formula (7): [In the formula, Q represents the same group as Q in the general formula (2). ]
Or a carbonyl group represented by the following formula (8): [In the formula, L ¹ and L ² represent the same group as Q in the general formula (3). Wherein the groups adjacent to each other in R ^{1 to} R ⁵ may be bonded to each other to form an alicyclic or aromatic ring which may be substituted, and X, Y and Z are represented by the general formula It represents the same group as X, Y and Z in (1). 2. An indolizine compound represented by｝.
3. The photosensitizer according to 1.). 3. A visible light curable resin composition comprising a photocurable resin (A), a photoreaction initiator (B) and a photosensitizer (C), wherein the photosensitizer (C) is used. Claim 1
Or a visible light curable resin composition containing the photosensitizer according to any one of the above. 4. The visible light-curable resin composition according to claim 3, wherein the visible light-curable resin composition contains a radical protecting agent (D). 5. The radical protecting compound (D) is at least one radical protecting compound selected from a phosphite compound and an aromatic compound having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring. The visible light-curable resin composition according to claim 3, wherein the resin composition comprises: 6. A visible light curable resin composition used in an environment of irradiation of a safety light having a maximum wavelength selected from the range of 500 to 620 nm and high relative luminous efficiency, and is formed from the composition. The visible light curable resin composition according to any one of claims 3 to 5, wherein the absorbance of the photosensitive film is 0.5 or less in a range of the maximum wavelength of the safety light ± 30 nm. 7. A discharge lamp mainly composed of sodium as a safety light (mainly a D line having a light wavelength of 589 nm).
The visible light curable resin composition according to claim 6, wherein 8. A visible light curable material composition comprising the visible light curable resin composition according to claim 3 and a solvent. 9. A visible light curable material comprising the visible light curable resin composition according to claim 3 on a substrate. 10. An indolizine compound represented by the following formula (9). Embedded image [Wherein R ⁵ and R ⁶ are both hydrogen atoms or are bonded to represent a condensed benzene ring, and Y ′ is COOR ″ (R ″ is an alkyl group or an aralkyl group which may have a substituent) Represents ]