JPH11100408A - Visible light-curable resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a photosensitizer, highly sensitive to laser beams having large wavelengths in the visible light region, and excellent in storage stability by including an organic boron compound having a specific structure as the photosensitizer. SOLUTION: This composition contains a compound of formula I [R1 -R3 , R5 -R9 are each H, a halogen, nitro, cyano, OH, amino, sulfone, a (halogeno) alkyl, a (alkoxy)alkoxy, an aryloxy, an acyl or the like; R4 is H, cyano, an alkyl, an aralkyl, an aryl or the like; R10 , R11 are each a halogen, an alkyl, an aralkyl, a (hetero)aryl or the like] as a photosensitizer. The compound of formula I is obtained e.g. by reacting a compound of formula II with a boron trihalide and, if necessary, substituting a part or all of the halogen atoms of the obtained compound of formula III by other groups. The photosensitizer is mixed with a photocurable resin and a photoreactive initiator to obtain the visible light-curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a visible light curable resin composition containing an organic boron compound having a specific structure as a photosensitizer and having high sensitivity to light in the visible light region, and its use. .

[0002]

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, a document that has been electronically edited on a computer has been used instead of a conventional method of recording a film document or the like on a photosensitive layer by using a mask as a mask. Is directly studied on the photosensitive layer by using a high-power laser to record. 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 wavelengths of 488 nm and 514.
An argon laser having a stable oscillation line at 5 nm, a YAG laser having a bright line at 532 nm as a second harmonic, 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 it.

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

Further, European Patent Publication No. 0619 is disclosed.
No. 520 discloses a bispyrromethene-based boron compound. When this compound is used, it exhibits high sensitivity to the above laser beam, but has a problem in storage stability of a photosensitive layer, and improvement is strongly demanded. I was

[0006]

SUMMARY OF THE INVENTION The present invention relates to an argon laser 514.5 which is a high power and stable laser light source.
Visible light containing a photosensitizer with high sensitivity and excellent storage stability to long-wavelength laser light such as 532 nm which is the second harmonic of a YAG laser or a second harmonic of a YAG laser. A curable resin composition is provided.

[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 an organic boron compound represented by the following general formula (1) as a photosensitizer.

[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, alkoxy group, alkoxyalkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aminocarbonyl group, alkylamino Carbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxycarbonyl group, aralkyl group, aryl group, heteroaryl group, alkylthio group,
Arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) aminocarbonyl, di (hydroxyalkyl) aminocarbonyl, mono (alkoxyalkyl) aminocarbonyl Group,
Represents a di (alkoxyalkyl) aminocarbonyl group or an alkenyl group, R ₄ represents a hydrogen atom, a cyano group, an alkyl group, an aralkyl group, an aryl group, a heteroaryl group or an alkenyl group, R ₁₀ and R ₁₁ represent a halogen atom, Represents an alkyl group, an aralkyl group, an aryl group, a heteroaryl group, an alkoxy group or an alkoxyalkoxy group. And a visible light curable resin composition.

[0010] The present invention also relates to an ink for a visible light curable material, comprising the visible light curable resin composition and a solvent.

[0011] The present invention further relates to a visible light-sensitive material comprising the composition on a substrate. As used herein, the term "ink for a visible light curable material" as used herein means a photosensitive liquid for a visible light sensitive material, a paint for electrodeposition coating, and the like. The term "visible light curable material" means a visible light sensitive material, a photosensitive material for electrodeposition coating, a dry film resist, and the like.

It has been found that the compound represented by the general formula (1) of the present invention is a very useful compound as a photosensitizer. This compound has an extremely large absorption at the wavelength of the argon laser light or the YAG laser harmonic light, is very sensitive to such light, and is a light-curing resin (for example, an ethylenically unsaturated bond is a molecular compound). A photopolymerizable or photocrosslinkable compound having at least one compound in the compound)
It is also a very useful compound applicable to photocuring using a photopolymerization initiator. Further, the sensitivity of the conventional photosensitizer greatly fluctuates due to the difference in the coating method, but the compound represented by the general formula (1) of the present invention shows a stable sensitivity in any method. is there.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION 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; Nitro group; cyano group; hydroxy group; amino group; carboxyl group; sulfonic acid group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n
Alkyl groups such as -butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group; chloromethyl group, dichloromethyl group, Halogenoalkyl groups such as fluoromethyl group, trifluoromethyl group, pentafluoroethyl group and nonafluorobutyl group;
Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, isopropyloxyethyl group, 3-methoxypropyl group and 2-methoxybutyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n- Alkoxy groups such as pentyloxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group; methoxyethoxy group, ethoxyethoxy group, 3- Alkoxyalkoxy groups such as methoxypropoxy and 3- (isopropyloxy) propoxy; phenoxy, 2-methylphenoxy, 4-methylphenoxy, 4-t-butylphenoxy, 2-methoxyphenoxy, 4-isopropyl Fenoki An aryloxy group such as a group;

Acyl groups such as formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, isobutylcarbonyl group, t-butylcarbonyl group, isopentylcarbonyl group and benzylcarbonyl group; methoxycarbonyl group; Ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group,
n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4
An alkoxycarbonyl group such as -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 phenylaminocarbonyl group;
Arylaminocarbonyl groups such as 4-methylphenylaminocarbonyl group, 2-methoxyphenylaminocarbonyl group, 4-n-propylphenylaminocarbonyl group; phenylcarbonylamino group, 4-ethylphenylcarbonylamino group, 3-isopropylphenylcarbonyl Arylcarbonylamino groups such as amino group and 2-methoxyphenylcarbonylamino group; phenoxycarbonyl group, 4-methylphenoxycarbonyl group, 3-methylphenoxycarbonyl group, 2-methylphenoxycarbonyl group, 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; pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, thiadiazoyl group, imidazoyl group, benzothiazoyl group, benzoxazoyl group,
Benzimidazoyl group, benzofuranyl group, indo-3
-A heteroaryl group such as an yl group;

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, isopropoxycarbonylmethoxycarbonyl group;

A methylcarbonylmethoxycarbonyl group,
Alkylcarbonylalkoxycarbonyl groups such as ethylcarbonylmethoxycarbonyl group; mono (hydroxyalkyl) aminocarbonyl groups such as hydroxyethylaminocarbonyl group, 2-hydroxypropylaminocarbonyl group and 3-hydroxypropylaminocarbonyl group;
Di (hydroxyethyl) aminocarbonyl group, di (2-
Di (hydroxyalkyl) aminocarbonyl groups such as hydroxypropyl) aminocarbonyl group and di (3-hydroxypropyl) aminocarbonyl group; methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group, ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl Mono (alkoxyalkyl) aminocarbonyl groups such as a group, propoxyethylaminocarbonyl group; di (methoxymethyl) aminocarbonyl group, di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) Di (alkoxyalkyl) aminocarbonyl groups such as aminocarbonyl group and di (propoxyethyl) aminocarbonyl group; vinyl group, propenyl group, 1-butenyl group, 1-
Examples thereof include alkenyl groups such as a pentenyl group, a 2-pentenyl group, a 3-methyl-1-butenyl group, a 2,2-dicyanovinyl group, and a 1,2,2-tricyanovinyl 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 and cyclohexyl group; aralkyl groups such as benzyl group and phenethyl group; phenyl group, 3-nitrophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group and 2-methylphenyl Group, 3,5-dimethylphenyl group, 3-trifluoromethylphenyl group, 4-chlorophenyl group, 4-
Aryl groups such as methoxyphenyl group, 4- (dimethylamino) phenyl group and naphthyl group; pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, thiadiazoyl group, imidazoyl group, benzothiazoyl group, benzoyl group An oxazoyl group,
Benzimidazoyl group, benzofuranyl group, indo-3
Heteroaryl groups such as -yl group; vinyl group, propenyl group, 1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-methyl-1-butenyl group, 2,2-dicyanovinyl group, 1,2 And alkenyl groups such as 2-tricyanovinyl group.

Specific examples of R ₁₀ and R ₁₁ include halogen atoms such as fluorine, chlorine and bromine; methyl, ethyl and n-
Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group and cyclohexyl group; benzyl An aralkyl group such as a phenethyl group; a 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 and naphthyl; pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl,
Heteroaryl groups such as thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl, benzoimidazoyl, benzofuranyl, indo-3-yl; methoxy, ethoxy, n-propoxy and isopropoxy , N-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n
-Alkoxy groups such as decyloxy group, cyclopentyloxy group, cyclohexyloxy group and 4-methylcyclohexyloxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3-methoxypropoxy group and 3- (isopropyloxy) propoxy group Can be mentioned.

Table 1 below shows specific examples of the organic boron compound represented by the general formula (1), but the present invention is not limited to these examples.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

The organic boron compound represented by the general formula (1) of the present invention can be produced by the following method. That is,
Known methods (for example, Journal of Chemical Society, C
The compound represented by the general formula (3) can be obtained by reacting a compound represented by the general formula (2) synthesized according to Chemical Communication, 1994, 1129-1130) with boron trihalide. Further, when at least one of them is a substituent of R ₁₀ and R ₁₁ which is not a halogen atom, a part or all of the halogen atoms of the compound of the general formula (3) are substituted to obtain an organic boron compound represented by the general formula (1). Obtainable.

[0030]

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

[0031]

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

The compound represented by the general formula (1) of the present invention can be used in the visible light range of 400 to 700 nm, particularly 40.
A compound which is excited by absorbing light of 0 to 600 nm and has an interaction with a photocurable resin or a photoreaction initiator (for example, a photoradical polymerization initiator, a photoacid generator, a photobase generator, etc.). is there. 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.

The photosensitizer of the present invention contains at least one kind of the organic boron compound represented by the general formula (1), and may be used in combination with other known photosensitizers.

The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer, and examples thereof include ketocoumarin, coumarin-6, and coumarin compounds described in JP-A-4-18088. No.

In this case, the content of the organic boron compound represented by the general formula (1) in the photosensitizer is not particularly limited. The content of the organic boron compound represented by the general formula (1) in the sensitizer is preferably 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% by weight or more. , 50% by weight or more is particularly preferred.

The visible light curable resin composition of the present invention is obtained by mixing the photosensitizer of the present invention, a photocurable resin, a photoreactive initiator and the like.

In the visible light curable resin composition of the present invention, the amount of the photosensitizer of the present invention used depends on the type of the organic boron compound represented by the general formula (1) contained in the photosensitizer. The amount of the organoboron compound of the present invention is usually 0.1 to 10 parts by weight, preferably 100 to 10 parts by weight, preferably 100 to 100 parts by weight of the photocurable resin component. A range of 0.3 to 5 parts by weight is suitable. If the amount of the present compound is less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease,
If the amount is more than 0 parts by weight, it tends to be difficult to keep the composition in a uniform state from the viewpoint of solubility.

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,
You may mix and use.

In the above 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.

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
: Polym. Chem. 28, 479, 1990), 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, trimethylolpropanedi (1-propenyl) ether acetate, trimethylolpropanedi (1-propenyl) ether acrylate, Vinyl ether compounds such as trimethylolpropane di (1-propenyl) -N-butyl carbonate (J. Polym. Sci .: Part A: Polym. Chem. 34, 2)
051, 1996), dodecyl allene (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-diethoxy-1,2-butadiene, N-hexylpropadyl ether (HPE) and the like Alkoxy allene compounds (J.
Polym. Sci .: Part A: Polym. Chem. 33, 2493, 1995
Oxetane compounds such as 3-ethyl-3-phenoxymethyloxetane, phenoxymethyloxetane, methoxymethyloxetane, 3-methyl-3-methoxymethyloxetane (see J. Polym. Sci .: Part A: P
olym. Chem. 33, 1807, 1995), 2-propylidene-4,5-dimethyl-1,3-dioxolan, 2-propylidene-4-methyl-1,3-dioxolan, 3,9
Ketene acetal compounds such as -dibutylidene-2,4,8,10-tetraoxaspiro [5.5] undecane (J. Polym. Sci .: Part A: Polym. Chem. 34, 309)
1, 1996), 1-phenyl-4-ethyl-2,6,
Bicyclo orthoester compounds such as 7-trioxabicyclo [2.2.2] octane (J. Polym. Sci .: Po
lym. Lett. Ed. 23, 359, 1985), lactone compounds such as propiolactone, butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprylolactone, γ-laurylolactone, coumarin and the like, 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 can be cured by acid protons.

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 having 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 or base generator, if necessary, conventionally known acrylic resins, vinyl resins, polyester resins, epoxy resins, phenol resins, Rubber, urethane resin and the like can be blended.

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-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyl diperoxyisophthalate, 3,3 ′, 4,4′-tetra ( organic peroxides such as t-butylperoxycarbonyl) benzophenone;
Diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; organic halides such as carbon tetrachloride, carbon tetrabromide, chloroform and iodoform; 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloro) Methyl) -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 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. 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 which generates a base upon exposure to light, and is a compound which cures the above-mentioned compound by using the generated base as a catalyst, and 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-methyl-ethoxy] carbonyl] cyclohexylamine, N-[[1- (3,5-dimethoxyphenyl) -1-methyl -Ethoxy] carbonyl] pyridine and other photofunctional urethane compounds (J. Org. Chem., V
ol. 55, No. 23, 5919, 1990).

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, the use 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 commonly used known photosensitive materials. That is, the visible light curable resin composition containing the compound 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),
A photosensitive liquid is prepared, applied to a support using a coating device such as a roller, a roll coater, a spin coater or the like, and dried, to be used as a visible light photosensitive material.

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 layer, for example, a resin film (thickness: about 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. , 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 Aqueous liquid in which aqueous resins such as acrylic resin, polyester resin, vinyl resin, epoxy resin or the like containing a group, an acidic group, or a base are dissolved or dispersed in water is applied to the coating film surface (dry film thickness: about 0.5
５5 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 the resin.

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, etc.), halogenated hydrocarbons (chloroform,
Trichloroethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), and others (dimethylformamide, dimethyl sulfoxide, etc.).

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 silicon wafers, carbon and the like.

The visible light curable resin composition of the present invention can be handled in the same manner as a usual photosensitive material for electrodeposition coating, and can be used as a coating for electrodeposition coating.
In that case, the visible light-curable resin composition is first made into a water-dispersed product or a water-soluble product.

The water-dispersible or water-soluble visible light curable resin composition is prepared by (1) alkali (neutralization) when an anionic group such as a carboxyl group is introduced into the visible light curable resin composition. (2) neutralization with an acid (neutralizing agent) when a cationic group such as an amino group is introduced. Examples of the alkali neutralizer used at that time include, for example, 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 is generally 0.2 to 1 equivalent of the ionic group contained in the visible light curable resin composition.
The range is preferably from 1.0 to 1.0 equivalent, particularly preferably from 0.3 to 0.8 equivalent.

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 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,
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 weight, preferably 100 parts by weight or less, per 100 parts by weight 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,
The water-soluble photocurable resin 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 mixed well, and water is added. Can be prepared.

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

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 15 to 40 ° C.
Control at ~ 30 ° C. Then, 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 electrodeposition coating is of the cationic type. Apply DC current. An appropriate energizing time is 30 seconds to 5 minutes.

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, followed by 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 film thickness obtained 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 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, and tin oxide, or a material obtained by fixing these materials to the surface of plastic or glass by lamination, plating, or the like can be used.

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 an image and cured. An image can be formed by removing the non-exposed portion by a developing process.

As the light source for exposure, light sources such as ultra-high pressure, high pressure, medium pressure and low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like are used. 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 developing 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 solutions are generally capable of imparting water solubility by neutralizing the free carboxylic acids present in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc. Etc. can be used.

Further, in the case of a photocurable resin having no ionic group, the developing treatment is performed with 1,1,1-trichloroethane,
The unexposed portion is dissolved by using a solvent such as trichlene, methyl ethyl ketone, or methylene chloride. After the developed coating film is washed with water and dried with hot air or the like, 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 photoresists, plate making materials for flat plates and letterpresses, PS plates for offset printing, information recording materials, and relief image forming materials.

The visible light-curable resin composition of the present invention may be used, in addition to the above, 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 base 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 resulting resist film is peeled or not peeled of the base film layer, in the same manner as the above-mentioned electrodeposition coating, according to the image, exposed to visible light, cured, and when there is a base film layer In this case, an image can be formed by peeling this off, and if not, developing it from above. In the dry film resist, if necessary, a cover coat layer similar to the above can be provided between the base film layer and the resist film. 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.

[0072]

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. The parts in the examples are parts by weight,
% Indicates% by weight.

Example 1 Using 5 parts of the compound 1-1 in Table 1 as a photosensitizer,
As the photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20/10
A photosensitive solution was prepared by using 100 parts of a polymer of a mixture of / 20, 55 parts of trimethylolpropane triacrylate, 20 parts of a titanocene compound of the following formula (a) as a polymerization 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 . Next, when the above-mentioned photosensitive layer was irradiated with light by an argon laser having an intensity of 1 mJ / cm ² , it was confirmed that the resin was quickly cured. Similar results were obtained by irradiation with a second harmonic (532 nm) of a xenon lamp and a YAG laser.

[0074]

Embedded image

Example 2 Using 5 parts of the compound 1-2 in Table 1 as a photosensitizer,
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, and when the above-mentioned photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was quickly cured. Similar results were obtained by irradiation with a second harmonic (532 nm) of a xenon lamp and a YAG laser.

Example 3 Using 5 parts of the compound of 1-3 in Table 1 as a photosensitizer,
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, and when the above-mentioned photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was quickly cured. Similar results were obtained by irradiation with a second harmonic (532 nm) of a xenon lamp and a YAG laser.

Example 4 Using 5 parts of the compound of 1-4 in Table 1 as a photosensitizer,
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, and when the above-mentioned photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was quickly cured. Similar results were obtained by irradiation with a second harmonic (532 nm) of a xenon lamp and a YAG laser.

Examples 5 to 56 In the same manner as in Example 1, the organic boron compounds 1-
As a result of evaluating the photosensitive layer prepared using 5-1 to 56,
As in Example 1, all exhibited extremely high photosensitivity.

[0079]

The visible light curable resin composition containing the organoboron compound of the present invention as a photosensitizer is a composition having extremely high practical utility. Conventionally, in the field of information recording using a photopolymerization reaction, the method of directly outputting and recording an original electronically edited by a computer directly using a laser in the field of information recording using photopolymerization reaction, the temporal stability of the photosensitive layer is low, and the sensitivity is low. , Solubility and storage stability. But,
The visible light curable resin composition of the present invention has extremely good compatibility between the base resin and the photosensitizer, and can be dissolved in a general-purpose coating solution to obtain a uniform and smooth coated surface on the support. it can.

The organic boron compound used in the present invention can be used for 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 a bright line at 532 nm as a second harmonic. Since it has very high sensitivity, 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 a laser. When an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Kenichi Sugimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals ( 72) Inventor Tsukahara U 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. (72) Inventor Takeshi Takeda 1190 Kasama-cho, Sakae-ku, Yokohama-shi Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. Kansai Paint Co., Ltd. (72) Inventor Hideo Kogure 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref.

Claims (3)

[Claims] 1. A visible light curable resin composition comprising a compound represented by the general formula (1) as a photosensitizer. Embedded image [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, 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, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) aminocarbonyl, di (hydroxyalkyl) aminocarbonyl, mono (alkoxyalkyl) aminocarbonyl, (Alkoxyalkyl) represents an aminocarbonyl group or an alkenyl group;
₄ is a hydrogen atom, a cyano group, an alkyl group, an aralkyl group,
Represents an aryl group, a heteroaryl group or an alkenyl group, and R ₁₀ and R ₁₁ represent a halogen atom, an alkyl group, an aralkyl group, an aryl group, a heteroaryl group, an alkoxy group or an alkoxyalkoxy group. ] 2. An ink for a visible light curable material, comprising the visible light curable resin composition according to claim 1 and a solvent. 3. A visible light curable material comprising the visible light curable resin composition according to claim 1 on a substrate.