JPH11322744A - Photosensitizer, visible light curable resin composition using the same and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitizer capable of exhibiting high sensitivity to laser beam of a long wavelength in a visible light range and excellent storage stability by making a specific benzopyrromethene-based compound as active ingredient. SOLUTION: This photosensitizer uses at least one benzopyrromethene-based compound of formula I (R1 to R3 and R5 to R9 are each H, a halogen, nitro, cyano, hydroxyl or the like; R4 is H, cyano, an alkyl or the like; R10 and R11 are each a halogen, an alkyl, an aralkyl or the like). The compound of formula I is obtained, for example, by reacting a compound of formula II with a compound formula III in the presence of an acid catalyst to give a compound, reacting the compound with a boron trihalide to give a compound of formula IV (X is a halogen) and, in the case in which at least one substituent group of R10 and R11 is not a halogen, substituting a part or the whole halogens of the compound of formula IV. A visible light curable resin composition having high sensitivity is obtained by using the photosensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitizer using a benzopyrromethene compound having a specific structure, and a visible light exhibiting high sensitivity to light rays in the visible light region by containing the photosensitizer. The present invention relates to a curable resin composition.

[0002]

2. Description of the Related Art In recent years, in the field of information using a photopolymerization reaction or image recording, instead of a conventional recording method using ultraviolet light using a film original or the like, a manuscript electronically edited by a computer is directly output at a high output. 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.

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
An argon laser having a stable oscillation line at 4.5 nm, or a YAG having a bright line at 532 nm as the second harmonic
Lasers and the like are widely used. Therefore, compounds having high sensitivity to these wavelengths have been desired, but conventionally used ultraviolet light-sensitive agents cannot be used due to low sensitivity in the visible region. Although the addition of a pyrylium salt or a thiopyrylium salt can improve the sensitivity in the visible region, the storage stability of the photosensitive layer is low and it has been difficult to use the photosensitive layer.

[0004]

As compounds having photosensitivity in the visible region, for example, 7-diethylamino-3-
Benzothiazoyl coumarin (common name: coumarin-6),
Or bis [3- (7-diethylaminocoumaryl)]
Ketones (common name: ketocoumarin) are known, but these have a maximum absorption wavelength of around 450 nm.
The wavelength is shorter than 488 nm of the argon laser, and the sensitivity is insufficient. Further, the 4-substituted-3-benzothiazoyl coumarin compound described in Japanese Patent Application Laid-Open No. 4-18088 has high photosensitivity at 488 nm of an argon laser, but at 514.5 nm or a second harmonic of a YAG laser. There was almost no absorption at 532 nm, leaving room for improvement in sensitivity.

Japanese Patent Application Laid-Open No. 7-5885 describes a photocurable composition containing a sensitizer containing a substituted or unsubstituted heterocyclic residue. No effect is described.

The present invention relates to a laser beam having a long wavelength of 514.5 nm, which is an argon laser, which is a high-power and stable laser light source, or a long-wavelength laser beam, such as 532 nm, which is a second harmonic of a YAG laser. High sensitivity to
An object of the present invention is to provide a visible light curable resin composition containing a photosensitizer having excellent storage stability.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a compound represented by the general formula (1):

[0008]

Embedded image

[Wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₇ ,
R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom,
Nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, alkyl group, halogenoalkyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aminocarbonyl Group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group, aralkyl group, aryl group, heteroaryl group, alkylthio group, arylthio group, alkenyloxy Carbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, mono (hydroxyalkyl) aminocar Group, di (hydroxyalkyl) aminocarbonyl group, mono (alkoxyalkyl)
R ₄ represents an aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group, an alkenyl group, an alkylamino group, a dialkylamino group, a mono (hydroxyalkyl) amino group or a di (hydroxyalkyl) amino group;
Represents a hydrogen atom, a cyano group, an alkyl group, an aralkyl group, an aryl group, a heteroaryl group or an alkenyl group, and R ₁₀ and R ₁₁ each independently represent a halogen atom, an alkyl group, an aralkyl group, an aryl group or a heteroaryl group. , An alkoxy group or an alkoxyalkoxy group. And a visible light-curable resin composition containing the photosensitizer using at least one benzopyrromethene compound represented by the formula (1).

[0010] The present invention further relates to an ink for a visible light curable material containing the composition and a solvent, and a visible light-sensitive material having the composition on a substrate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable resin composition of the present invention comprises
It contains a photosensitizer using the benzopyrromethene compound of the general formula (1).

It has been found that a photosensitizer using a benzopyrromethene compound represented by the general formula (1) of the present invention is extremely useful. The benzopyrromethene compound represented by the general formula (1) used in the present invention has an extremely large absorption at the wavelengths of argon laser light and YAG laser harmonic light, and has extremely high sensitivity to such light. And a photocurable resin (for example, a photopolymerizable or photocrosslinkable compound having at least one ethylenically unsaturated bond in a molecule) and a photosensitizer applicable to photocuring using a photoreaction initiator. It is a very useful material.

Further, the sensitivity of the conventional photosensitizer greatly fluctuates due to the difference in the coating method, but the photosensitizer of the present invention shows stable sensitivity in any method.

The "ink for a visible light curable material" referred to in the present invention means a photosensitive liquid for a visible light sensitive material, a paint for electrodeposition coating and the like as described later. In addition, “visible light curable material” means visible light sensitive material, photosensitive material for electrodeposition coating,
It means a dry film resist or the like.

Hereinafter, the present invention will be described in more detail. In the compound represented by the general formula (1) of the present invention, specific examples of R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ include a hydrogen atom; a nitro group; Cyano group; hydroxy group; amino group; carboxyl group; sulfonic acid group; halogen atom such as fluorine atom, chlorine atom, and bromine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group, alkyl group such as decalyl group and itacosanyl group A halogeno such as a chloromethyl group, a dichloromethyl group, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 1,1,1,3,3,3-hexafluoro-2-propyl group and a nonafluorobutyl group; Alkyl group; alkoxyalkyl group such as methoxyethyl group, ethoxyethyl group, isopropyloxyethyl group, 3-methoxypropyl group and 2-methoxybutyl group;

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, n-decyloxy, cyclopentyloxy, Alkoxy groups such as cyclohexyloxy group and 4-methylcyclohexyloxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3-methoxypropoxy group and 3- (isopropyloxy) propoxy group; phenoxy group and 2-methylphenoxy Aryloxy groups such as a group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group and 4-isopropylphenoxy group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropyl Carbonyl group, Acyl groups such as a sobutylcarbonyl group, a t-butylcarbonyl group, an isopentylcarbonyl group and a benzylcarbonyl group; a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, an n-hexyloxycarbonyl group, and an n-octyloxycarbonyl An alkoxycarbonyl group such as a group, an n-decyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 4-methylcyclohexyloxycarbonyl group;

Aminocarbonyl group; alkylaminocarbonyl group such as methylaminocarbonyl group, n-butylaminocarbonyl group, n-hexylaminocarbonyl group, cyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group; dimethylaminocarbonyl group; Dialkylaminocarbonyl groups such as diethylaminocarbonyl group, di-n-butylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-octylaminocarbonyl group, N-isoamyl-N-methylaminocarbonyl group; acetylamino Alkylcarbonylamino groups such as a group, an ethylcarbonylamino group and an isobutylcarbonylamino group; a phenylcarbonylamino group;
Arylcarbonylamino groups such as 4-ethylphenylcarbonylamino group, 3-isopropylphenylcarbonylamino group and 2-methoxyphenylcarbonylamino group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group and 2-methoxyphenylaminocarbonyl group , An arylaminocarbonyl group such as 4-n-propylphenylaminocarbonyl group; a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 3-methylphenoxycarbonyl group, a 2-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group ,
2,6-dimethylphenoxycarbonyl group, 2,4,6
Aryloxycarbonyl groups such as -trimethylphenoxycarbonyl group, 4-phenylphenoxycarbonyl group;

Aralkyl groups such as benzyl and phenethyl; phenyl, 3-nitrophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 2-methylphenyl, 3,5-dimethylphenyl, Trifluoromethylphenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group,
Aryl groups such as naphthyl group, biphenyl group and fluorenyl group; pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group,
Heteroaryl groups such as thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl, benzoimidazoyl, benzofuranyl and indo-3-yl;

Alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, 3,5,5-trimethylhexylthio; phenylthio; Arylthio groups such as 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group, and naphthylthio group; allyloxycarbonyl group;
Alkenyloxycarbonyl groups such as 2-butenoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group, 4-methylbenzyloxycarbonyl group and phenethyloxycarbonyl group; methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group; alkoxycarbonylalkoxycarbonyl groups such as n-propoxycarbonylmethoxycarbonyl group and isopropoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxycarbonyl groups such as methylcarbonylmethoxycarbonyl group and ethylcarbonylmethoxycarbonyl group;

A hydroxyethylaminocarbonyl group, 2
Mono (hydroxyalkyl) aminocarbonyl groups such as -hydroxypropylaminocarbonyl group and 3-hydroxypropylaminocarbonyl group; di (hydroxyethyl) aminocarbonyl group, di (2-hydroxypropyl) aminocarbonyl group, di (3-hydroxy Di (hydroxyalkyl) such as propyl) aminocarbonyl group
Aminocarbonyl group; methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group, ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group such as propoxyethylaminocarbonyl group; di (methoxymethyl) amino Di (alkoxyalkyl) aminocarbonyl groups such as carbonyl group, di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group, di (propoxyethyl) aminocarbonyl group;

Vinyl group, propenyl group, 1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-methyl-1-butenyl group, 2,2-dicyanovinyl group,
Alkenyl groups such as 2,2-tricyanovinyl group, methylamino group, n-butylamino group, n-hexylamino group,
Alkylamino groups such as cyclohexylamino group and 4-methylcyclohexylamino group; dimethylamino group, diethylamino group, di-n-butylamino group, di-n-hexylamino group, di-n-octylamino group, N-isoamyl A dialkylamino group such as -N-methylamino group; a hydroxymethylamino group, a hydroxyethylamino group,
A mono (hydroxyalkyl) amino group such as a 2-hydroxypropylamino group or a 3-hydroxypropylamino group; a di (hydroxymethyl) amino group, a di (hydroxyethyl) amino group, a di (2-hydroxypropyl) amino group, And a di (hydroxyalkyl) amino group such as a (3-hydroxypropyl) amino group.

Specific examples of R ₄ include a hydrogen atom; a cyano group; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group,
-Pentyl group, isopentyl group, n-hexyl group, n-
Alkyl groups such as octyl group, 2-ethylhexyl group, cyclohexyl group, decalyl group and itacosanyl group; aralkyl groups such as benzyl group, 2-methylbenzyl group, 4-ethylbenzyl group and phenethyl group; phenyl group;
Nitrophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, 2-methylphenyl group, 3,5-dimethylphenyl group, 3-trifluoromethylphenyl group,
4-chlorophenyl group, 4-methoxyphenyl group, 4-
Aryl groups such as (dimethylamino) phenyl, naphthyl, biphenyl and fluorenyl;

Pyrrolyl group, N-methylpyrrolyl group, N-
Ethylpyrrolyl, N-propylpyrrolyl, N-butylpyrrolyl, N-isobutylpyrrolyl, N-isopentylpyrrolyl, N-octylpyrrolyl, N-methoxymethylpyrrolyl, N-methoxyethylpyrrolyl Group, N-ethoxymethylpyrrolyl group, N-ethoxyethylpyrrolyl group, N-methoxycarbonylmethylpyrrolyl group, N-methoxycarbonylethylpyrrolyl group, N-ethoxycarbonylmethylpyrrolyl group, N-ethoxycarbonyl Ethylpyrrolyl group, N-benzylpyrrolyl group, N
-Phenylpyrrolyl group, N-tolylpyrrolyl group, N-allylpyrrolyl group, N-butenylpyrrolyl group, N-pentenylpyrrolyl group, thienyl group, furyl group, pyridyl group,
Quinolyl group, isoquinolyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, thiadiazoyl group, imidazoyl group, benzothiazoyl group, benzoxazoyl group, benzimidazoyl group, benzofuryl group,
A heteroaryl group such as an ind-3-yl group; a vinyl group;
Propenyl group, 1-butenyl group, 1-pentenyl group, 2
-Pentenyl group, 3-methyl-1-butenyl group, 2,2
And alkenyl groups such as -dicyanovinyl group and 1,2,2-tricyanovinyl group.

Specific examples of R ₁₀ and R ₁₁ include halogen atoms such as fluorine, chlorine and bromine; methyl, ethyl and n-
Propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, 2-ethylhexyl, cyclohexyl, decalyl An alkyl group such as an itacosanyl group; a benzyl group;
Aralkyl groups such as 2-methylbenzyl group, 4-ethylbenzyl group and phenethyl group;

Phenyl group, 3-nitrophenyl group, 4-
Cyanophenyl group, 4-hydroxyphenyl group, 2-methylphenyl group, 3,5-dimethylphenyl group, 3-trifluoromethylphenyl group, 4-chlorophenyl group,
Aryl groups such as 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, naphthyl group, biphenyl group and fluorenyl group; pyrrolyl group, N-methylpyrrolyl group,
N-ethylpyrrolyl group, N-propylpyrrolyl group, N-
Butylpyrrolyl group, N-isobutylpyrrolyl group, N-isopentylpyrrolyl group, N-octylpyrrolyl group, N-
Methoxymethylpyrrolyl group, N-methoxyethylpyrrolyl group, N-ethoxymethylpyrrolyl group, N-ethoxyethylpyrrolyl group, N-methoxycarbonylmethylpyrrolyl group, N-methoxycarbonylethylpyrrolyl group, N-
Ethoxycarbonylmethylpyrrolyl group, N-ethoxycarbonylethylpyrrolyl group, N-benzylpyrrolyl group,
N-phenylpyrrolyl group, N-tolylpyrrolyl group, N-
Allylpyrrolyl group, N-butenylpyrrolyl group, N-pentenylpyrrolyl group, thienyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, thiadiazoyl group, imidazoyl group, benzothiazoyl group, Heteroaryl groups such as a benzoxazoyl group, a benzimidazoyl group, a benzofuryl group and an indo-3-yl group;

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, n-decyloxy, cyclopentyloxy, An alkoxy group such as a cyclohexyloxy group and a 4-methylcyclohexyloxy group; and an alkoxyalkoxy group such as a methoxyethoxy group, an ethoxyethoxy group, a 3-methoxypropoxy group, and a 3- (isopropyloxy) propoxy group.

The following Table 1 shows specific examples of the benzopyrromethene compound represented by the general formula (1), but the present invention is not limited only to these examples.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

The benzopyrromethene compound represented by the general formula (1) according to the present invention can be produced by the following method. That is, typically, first, a compound represented by the general formula (2) and a compound represented by the general formula (3) or a compound represented by the general formula (4) in the presence of an acid catalyst such as hydrobromic acid or hydrogen chloride. The compound represented by the general formula (6) can be obtained by reacting the compound represented by the general formula (5) with the compound represented by the general formula (5). Next, the compound represented by the general formula (7) can be obtained by reacting the compound represented by the general formula (6) with boron trihalide. When at least one of them is a substituent of R ₁₀ and R ₁₁ which is not a halogen atom, a benzopyrromethene compound represented by the general formula (1) is obtained by substituting a part or all of the halogen atoms of the compound of the general formula (7). A compound can be obtained.

[0033]

Embedded image (In the formula, R _{4 to} R ₉ are the same as described above.)

[0034]

Embedded image (In the formula, R _{1 to} R ₃ are the same as described above.)

[0035]

Embedded image (In the formula, R _{5 to} R ₉ are the same as described above.)

[0036]

Embedded image (In the formula, R _{1 to} R ₄ are the same as described above.)

[0037]

Embedded image (In the formula, R _{1 to} R ₉ are the same as described above.)

[0038]

Embedded image (In the formula, R _{1 to} R ₉ are the same as described above, and X represents a halogen atom.)

The visible light-curable resin composition of the present invention is a benzopyrromethene-based photocurable resin composition comprising a photocurable resin, a photosensitizer, and a photoreaction initiator. A photocurable resin, a photoreaction initiator (eg, a photoradical polymerization initiator, a photoacid generator, a photobase generator, etc.) containing the photosensitizer of the present invention using a compound, and the present invention. Obtained by mixing a photosensitizer and the like.

The photocurable resin used in the present invention is not particularly limited as long as it is a generally used photocurable resin having a photosensitive group which can be crosslinked or polymerized by light irradiation. A compound having an ethylenically unsaturated double bond of a monomer, a prepolymer,
Oligomers such as oligomers and trimers, mixtures thereof, and copolymers thereof. Monofunctional and polyfunctional (meth) acrylates are generally used.
JP-A-223759, page 2, lower right column, line 6 to page 6, lower left column, line 16, anionic photocurable resin containing a (meth) acryloyl group as a photosensitive group, and a cinnamoyl group as a photosensitive group And a photocurable resin containing an allyl group as a photosensitive group. The resin is preferably used in combination with the following photoradical polymerization initiator. These photocurable resins may be used alone or as a mixture.

In the above-mentioned JP-A-3-223759, as specific examples of the esterified product of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid described in the ethylenically unsaturated compound of the photocurable resin component (a2), Molecular weight 300
Up to 1000 polyethylene glycol di (meth) acrylates can also be used.

In addition to the above-mentioned photocurable resin, a polymerization reaction, an etherification reaction, a pinacol transfer, a silanol dehydration reaction, an intramolecular dehydration condensation reaction, a hydrolysis condensation reaction can be carried out using an acid generated from a photoacid generator as a catalyst. A compound that cures (insolubilizes) by such a 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, and trimethylolpropane diglycidyl ether;
Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, dicyclopentadienedioxide, epoxycyclohexenecarboxylic acid ethylene glycol diester, 1,3-bis [2- {3 (7
-Oxabicyclo [4.1.0] heptyl) @ethyl]
Tetramethyldisiloxane (J.Polym. Sci.: Part
A: see Polym. Chem. 28, 479, 1990), alicyclic epoxy compounds, butylene glycol divinyl ether, trimethylolpropanedi (1-propenyl) methyl ether, trimethylolpropanedi (1-propenyl) butylether, Trimethylolpropanedi (1-
(Propenyl) octyl ether, trimethylolpropanedi (1-propenyl) phenyl ether, trimethylolpropanedi (1-propenyl) ether acetate, trimethylolpropanedi (1-propenyl) ether acrylate, trimethylolpropanedi (1-propenyl) Vinyl ether compounds such as -N-butyl carbonate (J. Polym. Sci .: Part A: Polym. Chem.
34, 2051, 1996), dodecyl arene (DA), diethylene glycol dialene (DEGA), triethylene glycol dialene (TEGA), 1-tetrahydrofurfuryl arene ether (THFA), N-hexyloxy-1,2-propadiene (HA), 1,4-di-N
-Butoxy-1,2-butadiene (DBB), 1,4-
Alkoxyallene compounds such as diethoxy-1,2-butadiene and N-hexylpropadyl ether (HPE) (J. Polym. Sci .: Part A: Polym. Chem. 33, 249)
3, 1995)), oxetane compounds such as 3-ethyl-3-phenoxymethyl oxetane, phenoxymethyl oxetane, methoxymethyl oxetane, and 3-methyl-3-methoxymethyl oxetane (J. Polym. Sci .: Part
A: Polym. Chem. 33, 1807, 1995), 2-propylidene-4,5-dimethyl-1,3-dioxolane, 2
-Propylidene-4-methyl-1,3-dioxolan,
Ketene acetal compounds such as 3,9-dibutylidene-2,4,8,10-tetraoxaspiro [5.5] undecane (J. Polym. Sci .: Part A: Polym. Chem. 3)
4, 3091, 1996), 1-phenyl-4-methyl-
Bicyclo orthoester compounds such as 2,6,7-trioxabicyclo [2.2.2] octane (J. Polym. S
ci .: Polym. Lett. Ed. 23, 359, 1985), propiolactone, butyrolactone, γ-valerolactone, γ
-Caprolactone, γ-caprylolactone, γ-laurylolactone, lactone compounds such as coumarin, aromatic vinyl compounds such as methoxy-α-methylstyrene, heterocyclic vinyl compounds such as vinylcarbazole, hexamethylolmelamine, Examples thereof include melamine compounds such as hexamethoxymelamine, 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 a 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, a photobase generator or a photoradical generator, if necessary, a conventionally known acrylic resin, vinyl resin, A polyester resin, an epoxy resin, a phenol resin, a rubber, a urethane resin, and the like can be blended.

The benzopyrromethene compound represented by the general formula (1) used as a photosensitizer in the present invention is 400
-700 nm light in the visible region, especially 400-600
It is a compound that is excited by absorbing light of nm and has an interaction with a photocurable resin or a photoreaction initiator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited compound of the present invention to the photocurable resin or photoreaction initiator. Therefore, the compound of the present invention is a very useful compound as a photosensitizer.

In the present invention, the photosensitizer contains at least one benzopyrromethene compound represented by the general formula (1), and may be used in combination with other known photosensitizers. Good. The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer. Ketocoumarin, coumarin-6 and JP-A-4-18
Coumarin compounds described in JP-A-088 / 88.

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

In the visible light curable resin composition of the present invention, the amount of the benzopyrromethene compound used as the photosensitizer of the present invention depends on the type of the benzopyrromethene compound represented by the general formula (1), Although it depends on the type of the photocurable resin component to be interacted with, usually, the photocurable resin component 1
The amount of the benzopyrromethene compound used is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight. If the amount of the benzopyrromethene compound is less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease. If the amount exceeds 10 parts by weight, the composition is kept in a uniform state from the viewpoint of solubility. Tend to be difficult to maintain.

As the photoreaction initiator used in the present invention, a photoradical polymerization initiator, a photoacid generator and a photobase generator can be used. The photo-radical polymerization initiator is not particularly limited as long as it is a commonly used photo-radical polymerization initiator.Examples include aromatic carbonyls such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone, and anthraquinone. Compound; acetophenone,
Acetophenones such as propiophenone, α-hydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone; benzoyl peroxide, t-butylperoxybenzoate, t-butyl Such as peroxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyl diperoxyisophthalate, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; Organic peroxides; diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; organic halides such as carbon tetrachloride, carbon tetrabromide, chloroform and iodoform; 3-phenyl-5-isoxazolone; 6-Tris ( Rikuroromechiru) -1,
Heterocyclic and polycyclic compounds such as 3,5-triazinebenzanthrone; 2,2′-azo (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 ′ Azo compounds such as -azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2-methylbutyronitrile); iron-arene complexes (Iron-Arene
Complex: see EP 152377);
Titanocene compounds (see JP-A-63-221110); bisimidazole compounds; N-arylglycine compounds; acridine compounds; combinations of aromatic ketones / aromatic amines;
-321895) and the like. Among the above radical photopolymerization initiators, di-t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra (t
-Butylperoxycarbonyl) benzophenone, iron-
Allene complexes and titanocene compounds are preferred compounds because of their high activity against crosslinking or polymerization.

The photoacid generator is a compound which generates an acid upon exposure to light and cures the above-mentioned compound using the generated acid as a catalyst. Although not particularly limited, for example, sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, onium salts such as selenium salts, iron-allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, Sulfonic esters, sulfonic imide esters, and the like can be used. Further, in addition to the above, JP-A-7-17-1
No. 46552 and Japanese Patent Application No. 9-289218 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. The photobase generator may be a commonly used photobase generator. For example, although not particularly limited, for example, nitrobenzyl carbamate compounds such as [(o-nitrobenzyl) oxy] carbonylcyclohexylamine (J. Am. Chem. Soc., Vol. 113, No. 11,
4305, 1991), N-{[1- (3,5-dimethoxyphenyl) -1-methylethoxy] carbonyl} cyclohexylamine, N-{[1- (3,5-dimethoxyphenyl) -1-methylethoxy). ] Photofunctional urethane compounds such as carbonyl-pyridine (J. Org. Chem., Vo
l.55, No.23, 5919, 1990) etc. can be used.

The amount of the photoreaction initiator to be used is not critical and can be varied in a wide range depending on the type and the like. , 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight.
When used in a large amount exceeding 25 parts by weight, the stability of the resulting composition tends to decrease.

In the visible light curable resin composition of the present invention, if necessary, an adhesion promoter, 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; It may contain various pigments such as pigments, metal oxides such as cobalt oxide, and plasticizers such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, polyethylene glycol, and polypropylene glycol.

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

Next, applications of the visible light curable resin composition of the present invention will be described. The visible light curable resin composition of the present invention can be handled in the same manner as a commonly used known photosensitive material. That is, the visible light curable resin composition containing the photosensitizer of the present invention is dispersed or dissolved in a solvent or water (when a pigment is used as a colorant, the pigment is finely dispersed) to prepare a photosensitive liquid. This can be used as a visible light-sensitive material by a method of applying it on a support using a coating device such as a roller, a roll coater, a spin coater, or a spray, and drying.

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 to block oxygen in the air to prevent radicals generated by exposure from being deactivated by oxygen, and to smoothly cure the coating by exposure.

As the cover coat, for example, a resin film (thickness: 1 to 70 μm) such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin is coated on the surface of the coating film. Alcohol, partially saponified polyvinyl acetate, polyvinyl alcohol-vinyl acetate copolymer, partially saponified polyvinyl acetate-vinyl acetate copolymer, polyvinylpyrrolidone, water-soluble polysaccharide polymers such as pullulan, basic group, Acrylic resin containing acidic group or base, polyester resin, vinyl resin,
An aqueous liquid in which an aqueous resin such as an epoxy resin is dissolved or dispersed in water is applied to the surface of the coating film (dry film thickness of about 0.5 to 5
μm) and dried to form a cover coat layer. The 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 that dissolves or disperses these resins.

Examples of the solvent to be used include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc.), ethers (tetrahydrofuran, dioxane, etc.). Dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, cumene, etc.), halogenated hydrocarbons (chloroform, trichloroethylene, dichloromethane, etc.), alcohols (methanol, ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, N-methyl) Pyrrolidone, 1,3-dimethylimidazolidin-2
-One, dimethylsulfoxide, etc.).

The support may be, for example, a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing them, a printed circuit board whose surface is treated with these metals, or a plastic. , Glass or silicon wafers, carbon and the like.

The visible light curable composition of the present invention can be handled in the same manner as a usual photosensitive material for electrodeposition coating, and can also be used as a coating for electrodeposition coating.

In this case, first, the photocurable resin composition is made into a water dispersion or an aqueous solution. Water-dispersion or water-solubility of the photocurable resin composition may be neutralized with an alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the photocurable resin composition, Alternatively, when a cationic group such as an amino group is introduced, the reaction is carried out by neutralization with an acid (neutralizing agent).

Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkyls such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine. Amines; alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia;

Examples of the acid neutralizing agent include formic acid,
Monocarboxylic acids such as acetic acid, lactic acid, and butyric acid are exemplified. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent to be used is generally 0.2 to 1.0 equivalent, particularly preferably 0.3 to 1 equivalent of the ionic group contained in the photocurable resin composition.
A range of -0.8 equivalents is desirable.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, if necessary, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol may be added to the above visible light curable resin composition. ,
t-Butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent to be used can be generally up to 300 parts by weight, preferably up to 100 parts by weight, per 100 parts by weight of the resin solid component.

In order to increase the amount of coating on the object to be coated, a hydrophobic solvent such as a petroleum solvent such as toluene or xylene; methyl ethyl ketone or methyl isobutyl ketone is added to the above visible light curable resin composition. Ketones such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol; The amount of these hydrophobic solvents is usually 20 parts by weight per 100 parts by weight of the resin solid component.
It can be up to 0 parts by weight, preferably 100 parts by weight or less.

The preparation of the visible light curable resin composition as an electrodeposition coating composition can be carried out by a conventionally known method. For example, the photocurable resin water-solubilized by the neutralization, the photosensitizer of the present invention, the photoreaction initiator, and, if necessary, a nitrogen-containing compound, a solvent and other components are thoroughly mixed, and water is added. It can be prepared by adding.

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 content concentration) of 3 to 25% by weight, preferably Is an electrodeposition paint (or electrodeposition bath) in the range of 5 to 15% by weight
It can be.

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 the 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, the conductor to be coated is immersed in the electrodeposition coating bath controlled as described above, as an anode when the electrodeposition coating is anionic, or as a cathode when the coating is cationic. , 5 to 200 V DC. An appropriate energization time is 10 seconds to 5 minutes. Further, in the electrodeposition coating method, a method of applying an electrodeposition coating material having a low glass transition temperature to an object to be coated, then washing with water or washing and drying, and further applying an electrodeposition coating material having a glass transition temperature of 20 ° C. or higher (Japanese Patent Laid-Open No. 2-
No. 20873), that is, double-coat electrodeposition coating can be performed.

The obtained film thickness is a dry film thickness, generally 0.5
５０50 μm, preferably 1 to 15 μm.

After the electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then the 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.

The visible light curable material formed on the conductor surface as described above, and the visible light-sensitive electrodeposited 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.

Further, a cover coat layer can be provided in advance 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. The 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 by a solvent such as water, an acidic aqueous solution, or a basic aqueous solution which dissolves or disperses these resins.

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

Light sources for exposure include ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight and the like. Among the light sources used, there can be used light rays in the visible region in which ultraviolet rays are cut by an ultraviolet cut filter, various lasers having oscillation lines in the visible region, and the like. As a high power and stable laser light source,
An argon laser or a second harmonic of a YAG laser is preferred.

The development treatment is carried out by washing with an aqueous alkali solution when the non-exposed portion film is anionic, and with an aqueous acid solution having a pH of 5 or less when the non-exposed film is cationic. Alkaline aqueous solution is usually caustic soda,
Sodium carbonate, caustic potash, ammonia water, and the like that can be imparted with water solubility by neutralizing with a free carboxylic acid contained in a coating film, and acetic acid, formic acid, lactic acid, and the like can be used as the acid aqueous solution.

Further, in the case of a photocurable resin having no ionic group, the developing treatment is performed by 1,1,1-trichloroethane,
The unexposed portion is dissolved by using a solvent such as trichlene, methyl ethyl ketone, or methylene chloride.

The developed coating film is washed with water, dried with hot air or the like, and an intended 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 of the present invention can be applied to a wide range of uses such as a photoresist, a plate-making material for flat plates or letterpress, a PS plate for offset printing, an information recording material, and a relief image forming material.

The visible light-curable resin composition of the present invention may be used, for example, 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, a blade coater, a curtain flow coater, or the like, and is dried to form a resist film (dry film thickness of about 0.5 to 5 μm), which is then protected on the surface of the film. It can be used as a dry film resist with a film attached. Such a dry film resist can be formed by peeling off the protective film and then bonding the resist film to a support by a method such as thermocompression bonding so that the resist film is in contact with the resist film. The resist film is exposed to visible light and cured according to the image in the same manner as the electrodeposition coating described above,
By performing the development processing, an image can be formed. Further, in the dry film resist, a cover coat layer can be provided as necessary similarly to the 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.

[0082]

EXAMPLES The present invention will be described below with reference to specific examples, but these are illustrative, and the present invention is not limited to these examples. Parts in Examples are parts by weight, and% means% by weight.

Example 1 5 parts of the compound 1-1 in Table 1 was used as a photosensitizer, and methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20 as an acrylic resin (polymer binder). / 10 /
A photosensitive solution was prepared using 100 parts of a polymer of the mixture of No. 20, 55 parts of trimethylolpropane triacrylate, 20 parts of a titanocene compound of the following formula (a) as a photoreaction initiator, and 160 parts of methylcellosolve as a solvent. . This photosensitive solution was applied on a laminated copper plate using a spinner so as to have a dry film thickness of 3.5 g / m ² to form a photosensitive layer. Next, a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532
nm) was applied to the photosensitive layer to obtain 1 mJ / cm
It was confirmed that the resin was rapidly cured at ² strengths (30 ° C., 1 minute development treatment with 1% aqueous sodium carbonate solution, not dissolved).

[0084]

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After the photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Example 2 A photosensitive solution having the same composition as in Example 1 was prepared by using 5 parts of the compound of 1-2 in Table 1 as a photosensitizer. Using this, a photosensitive layer was formed in the same manner as in Example 1, and the above-mentioned photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. / Cm ² strength quickly cures the resin (3
0 ° C., 1 minute development with 1% aqueous sodium carbonate solution, not dissolved).

Further, after the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned photosensitive sensitivity.

Example 3 A photosensitive solution having the same composition as in Example 1 was prepared by using 5 parts of the compound of 1-3 in Table 1 as a photosensitizer. Using this, a photosensitive layer was formed in the same manner as in Example 1, and the above-mentioned photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. / Cm ² strength quickly cures the resin (3
0 ° C., 1 minute development with 1% aqueous sodium carbonate solution, not dissolved).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Examples 4 to 50 In the same manner as in Example 1, compounds 1-4 to 1-50 shown in Table 1 were obtained.
As a result of evaluation of the photosensitive layer produced by using the same method, as in Example 1, all of them showed extremely high sensitivity.

After the respective photosensitive layers were allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the photosensitive sensitivity.

Example 51 Instead of 20 parts of the titanocene compound of the formula (a) in Example 1, 20 parts of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone was added to a photoinitiator. And a photosensitive solution having the same composition as in Example 1 was prepared. Using this, a photosensitive layer was formed in the same manner as in Example 1,
Xenon lamp (cuts the wavelength in the ultraviolet region) and Y
When the above-mentioned photosensitive layer was irradiated with the second harmonic (532 nm) of an AG laser, the resin was quickly cured at an intensity of 1 mJ / cm ² (30 ° C., developed with 1% aqueous solution of sodium carbonate for 1 minute, and did not dissolve) ) It was confirmed that.

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned sensitivity.

Example 52 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 (a) in Example 1. A photosensitive solution having the composition was prepared. Using this, a photosensitive layer was formed in the same manner as in Example 1, and a second harmonic (532n) of a xenon lamp (cutting a wavelength in an ultraviolet region) and a YAG laser was used.
m), the above-mentioned photosensitive layer was irradiated with light.
It was confirmed that the resin was rapidly cured at ² strengths (30 ° C., 1 minute development treatment with 1% aqueous sodium carbonate solution, not dissolved).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned photosensitive sensitivity.

Example 53 Instead of using 5 parts of the compound (1-1) in Table 1 of Example 1, 3 parts of the compound (1-9) in Table 1 and the compound (1-48) in Table 1 were used. Three parts were used to prepare a photosensitive solution having the same composition as in Example 1. Using this, a photosensitive layer was formed in the same manner as in Example 1, and a second harmonic (532n) of a xenon lamp (cutting a wavelength in an ultraviolet region) and a YAG laser was used.
m), the above-mentioned photosensitive layer was irradiated with light.
It was confirmed that the resin was rapidly cured at ² strengths (30 ° C., 1 minute development treatment with 1% aqueous sodium carbonate solution, not dissolved).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Example 54 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 photosensitive layer was formed in the same manner as in Example 1, and the above-mentioned photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. It was confirmed that the resin quickly cured at 30 ° C./cm ² strength (not dissolved by developing at 30 ° C. for 1 minute with a 1% aqueous sodium carbonate solution).

After the above-mentioned photosensitive layer was left at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned sensitivity.

Example 55 In Example 1, a mixture of 50 parts of the acrylic resin and 50 parts of the photocurable resin used in Example 54 was used instead of 100 parts of the acrylic resin. A photosensitive solution having the composition was prepared. Using this, a photosensitive layer was formed in the same manner as in Example 1, and a second harmonic (532n) of a xenon lamp (cutting a wavelength in an ultraviolet region) and a YAG laser was used.
m), the above-mentioned photosensitive layer was irradiated with light.
It was confirmed that the resin was rapidly cured at ² strengths (30 ° C., 1 minute development treatment with 1% aqueous sodium carbonate solution, not dissolved).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Example 56 The same composition as in Example 1 was used, except that 155 parts of the photocurable resin used in Example 54 was used instead of 100 parts of the acrylic resin and 55 parts of trimethylolpropane triacrylate. Was prepared. Using this,
A photosensitive layer was formed in the same manner as in Example 1, and a xenon lamp (cutting the wavelength in the ultraviolet region) and a second YAG laser were used.
When the above-mentioned photosensitive layer was irradiated with light at a harmonic (532 nm), the resin was rapidly cured at an intensity of 1 mJ / cm ² (30 nm).
At 1 ° C. for 1 minute with a 1% aqueous solution of sodium carbonate and not dissolved).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Example 57 In Example 1, an okitacene compound of the formula (b) was used in place of 55 parts of trimethylolpropane triacrylate and 20 parts of the titanocene compound, and the compound 10 of the formula (c) was used as a photoacid generator. Using the same parts, a photosensitive solution having the same composition as in Example 1 was prepared.

[0105]

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[0106]

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Using this, a photosensitive layer was formed in the same manner as in Example 1, and a xenon lamp (cutting the wavelength in the ultraviolet region)
When the photosensitive layer was irradiated with the second harmonic (532 nm) of YAG laser and light, the resin was quickly cured at an intensity of 1 mJ / cm ² (30 ° C., developed with 1% aqueous solution of sodium carbonate for 1 minute and dissolved). No) was confirmed (excellent effects can be confirmed by comparison with Comparative Example 3).

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed. As a result, no change was found in the above-mentioned sensitivity.

Example 58 To 100 parts (solid content) of the photosensitive solution obtained in Example 54, 7 parts of triethylamine was mixed and stirred, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%). Obtained.

The obtained aqueous dispersion resin solution was used as an electrodeposition coating bath, an anion electrodeposition coating was performed so that the dry film thickness was 3.5 g / m ^{2 using} the laminated copper plate as an anode.
Drying was performed at 5 ° C. for 5 minutes to obtain an electrocoating photosensitive layer.

Using this photosensitive layer, a xenon lamp (cutting the wavelength in the ultraviolet region) and YA were used in the same manner as in Example 1.
When the above-mentioned photosensitive layer was irradiated with the second harmonic (532 nm) of a G laser, the resin was rapidly cured at 1 mJ / cm ² intensity (at 30 ° C., developed with 1% aqueous solution of sodium carbonate for 1 minute and did not dissolve). ) It was confirmed that.

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned sensitivity.

Example 59 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, 100 parts of a photosensitive solution obtained by mixing 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. The 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 resulting water-dispersed resin solution was used as an electrodeposition coating bath, and the laminated copper plate was used as a cathode. Cationic electrodeposition was performed so that the dry film thickness was 3.5 g / m ^2.
Drying was performed at 5 ° C. for 5 minutes to obtain an electrocoating photosensitive layer.

Using this photosensitive layer, a xenon lamp (cutting the wavelength in the ultraviolet region) and YA were used in the same manner as in Example 1.
When the above-mentioned photosensitive layer was irradiated with the second harmonic (532 nm) of the G laser, the resin was rapidly cured at an intensity of 3 mJ / cm ² (at 30 ° C., developed with 1% aqueous lactic acid solution for 1 minute and did not dissolve). It was confirmed that.

After the above-mentioned photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out. As a result, no change was found in the above-mentioned photosensitive sensitivity.

Comparative Example 1 A photosensitive solution having the same composition as in Example 1 was prepared by using 5 parts of the compound of the following formula (d) as a photosensitizer. Using this, a photosensitive layer was formed in the same manner as in Example 1, and the above photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. At the same strength as in Example 1, the resin is cured (30
At a temperature of 4.5 mJ / cm ² , and the resin was hardened at 4.5 mJ / cm ² strength.

[0118]

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Further, when the photosensitive layer was left at room temperature for 6 months, the uniformity of the photosensitive layer was impaired due to the precipitation of crystals, and the photosensitive sensitivity was remarkably deteriorated.

Comparative Example 2 A photosensitive solution having the same composition as in Example 1 was prepared by using 5 parts of the compound represented by the following formula (e) as a photosensitizer. Using this, a photosensitive layer was formed in the same manner as in Example 1, and the above photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. At the same strength as in Example 1, the resin is cured (30
At 1 ° C. for 1 minute with an aqueous solution of sodium carbonate for 1 minute, and the resin was cured at a strength of 5.0 mJ / cm ² .

[0121]

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When the photosensitive layer was left at room temperature for 6 months, the uniformity of the photosensitive layer was impaired due to the precipitation of crystals, and the photosensitive sensitivity was significantly deteriorated.

Comparative Example 3 A photosensitive solution having the same composition as in Example 57 was prepared by using 5 parts of the compound represented by the following formula (f) as a photosensitizer. Using this, a photosensitive layer was formed in the same manner as in Example 57, and the above-described photosensitive layer was irradiated with a xenon lamp (cutting the wavelength in the ultraviolet region) and the second harmonic (532 nm) of a YAG laser. At the same strength as in Example 57, the resin was not cured (not developed and dissolved in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute), and the resin was cured at a strength of 30 mJ / cm ² .

[0124]

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When the photosensitive layer was left at room temperature for 6 months, the uniformity of the photosensitive layer was impaired due to the precipitation of crystals, and the photosensitive sensitivity was remarkably deteriorated.

[0126]

Conventionally, in the field of information recording using a photopolymerization reaction, a manuscript electronically edited by a computer is used.
In the method of directly outputting and recording using a laser as it is, there are problems such as low temporal stability of the photosensitive layer, low sensitivity, solubility, and storage stability.

On the other hand, the benzopyrromethene compound according to the present invention is applicable to general-purpose visible lasers such as an argon laser having a stable oscillation line at 488 nm and 514.5 nm and a YAG laser having an emission line at 532 nm as a second harmonic. On the other hand, since it has very high sensitivity, the photosensitizer of the present invention using the compound exhibits high sensitivity to light in the visible light region. Therefore, the photosensitive material obtained by using the visible light curable resin composition of the present invention containing the photosensitizer can be subjected to high-speed scanning exposure with the above laser. When an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

Further, the visible light curable resin composition of the present invention has extremely good compatibility between the basic resin and the photosensitizer, and
It is a composition which is dissolved in a general-purpose coating solution, can obtain a coated surface which is uniform on a support and has excellent storage stability over time, and is extremely excellent in practical use.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 201/00 C09D 201/00 G03F 7/029 G03F 7/029 // C07D 207/44 C07D 207/44 (72) Inventor Akira Ogiso Kanagawa 1190 Kasama-cho, Sakae-ku, Yokohama Mitsui Chemical Co., Ltd. Within Chemical Co., Ltd. (72) Inventor Genji Imai 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Paint Inside (72) Inventor Hideo Kogure 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Paint Kansai Paint Inside the corporation

Claims (4)

[Claims] 1. A compound of the general formula (1) [Wherein, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, Carboxyl group, sulfonic acid group, alkyl group, halogenoalkyl group, alkoxyalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, Alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group, aralkyl group, aryl group, heteroaryl group, alkylthio group, arylthio group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxy Aryloxycarbonyl group, an alkylcarbonyl alkoxycarbonyl group, mono (hydroxyalkyl) aminocarbonyl group, di (hydroxyalkyl) aminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group, di (alkoxyalkyl) aminocarbonyl group,
Represents an alkenyl group, an alkylamino group, a dialkylamino group, a mono (hydroxyalkyl) amino group or a di (hydroxyalkyl) amino group, wherein R ₄ is a hydrogen atom,
Cyano group, an alkyl group, an aralkyl group, an aryl group, a heteroaryl group or an alkenyl group, R _10, R ₁₁
Each independently represents a halogen atom, an alkyl group, an aralkyl group, an aryl group, a heteroaryl group, an alkoxy group or an alkoxyalkoxy group. ] A photosensitizer comprising at least one benzopyrromethene compound represented by the formula: 2. A photocurable resin composition comprising a photocurable resin, a photosensitizer and a photoreaction initiator, wherein the photocurable resin composition according to claim 1 is contained. Photocurable resin composition. 3. An ink for a visible light curable material, comprising the visible light curable resin composition according to claim 2 and a solvent. 4. A visible light curable material comprising the visible light curable resin composition according to claim 2 on a substrate.