JP2000019729A - Visible light setting resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing a photosensitizer high in sensitivity and excellent in preservation stability by containing the photosensitizer containing a specific benzopyrromethene boron compound. SOLUTION: This visible light setting resin composition contains a photopolymerizable resin, a photo-reaction initiator, at least one kind of radical protective compound selected from an ester phosphite compound and an aromatic compound with N,N-dimethylamino group bonded to a carbon atom forming an aromatic ring, and a photosensitizer containing at least one kind of benzopyrromethene boron compound expressed by a formula. In the formula, R1-R3 and R5-R9 independently represent hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group or carboxyl group; R4 represents hydrogen atom, cyano group, alkyl group or aryl group; and R10, R11 independently represent halogen atom, alkyl group, aralkyl group, aryl group or heteroaryl group.

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 having improved curability inhibition by oxygen and exhibiting high sensitivity to light in the visible light region and having excellent curability.

[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
Argon laser with stable oscillation line at 4.5 nm or YAG with emission line at 532 nm as 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.

As compounds having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazoylcoumarin (common name: coumarin-6) or bis [3
-(7-diethylaminocoumaryl)] ketone (common name:
Ketocoumarin) is known, but since these have a maximum absorption wavelength of about 450 nm, they have a shorter wavelength than 488 nm of an argon laser and have insufficient sensitivity. Further, the 4-substituted-3-benzothiazoyl coumarin compound described in JP-A-4-18088 has high sensitivity at 488 nm of an argon laser,
At 4.5 nm or at 532 nm, which is the second harmonic of the YAG laser, there was almost no absorption, leaving room for improvement in sensitivity.

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

Conventionally, in order to form a conductor circuit such as a printed wiring board, a resist pattern is formed on a substrate coated with a photosensitive resist by exposure / development.
Unnecessary portions are removed by etching.

As an exposure method, there are a method of exposing through a photomask and a method of directly drawing a resist with a laser. The method of exposing through a photomask has problems that a considerable amount of time is required for positioning the photomask, and that if the resist surface is sticky, it is difficult to position the photomask.

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

[0009]

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 curing that contains a photosensitizer that is highly sensitive 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 and has excellent storage stability. The present invention provides a conductive resin composition.

In addition, the present inventors have proposed a method for directly drawing a resist with a visible light laser without using a photomask, in which active radicals generated in the resist by laser irradiation are deactivated by oxygen in the air. An object of the present invention is to provide a resist which is difficult and can maintain high sensitivity.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, completed the present invention by using a specific radical protecting compound and a photosensitizer. . That is, the present invention relates to: 1, the following components (A) a photopolymerizable resin, (B) a photoreaction initiator, (C) a phosphite compound and N, N-dimethylamino bonded to a carbon atom forming an aromatic ring. Characterized in that it contains at least one radical protecting compound selected from aromatic compounds having a group and (D) a photosensitizer containing at least one benzopyrromethene-based boron compound represented by the following general formula (1). Visible light curable resin composition,

[0012]

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, 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. ]

(2) a composition for a visible light curable material comprising the above visible light curable resin composition and a solvent; (3) a composition comprising the above visible light curable resin composition on a substrate It relates to a visible light curable material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The visible light curable resin composition of the present invention contains a photosensitizer containing at least one benzopyrromethene-based boron compound represented by the general formula (1).

It has been found that the photosensitizer using the benzopyrromethene-based boron compound represented by the general formula (1) of the present invention is extremely useful. General formula (1) used in the present invention
The benzopyrromethene-based boron compound represented by has a very large absorption at the wavelength of argon laser light or YAG laser high-wavelength light, and is very sensitive to such light, and requires a resin and a photoreaction initiator. It is a material useful as a photosensitizer applicable to the visible light curable resin composition to be used.

In the present invention, the term "composition for visible light curable material" includes, for example, paints, inks, adhesives, printing materials, resist materials, and non-photosensitive coating materials formed from these materials. Is meant.

The visible light curable resin composition of the present invention comprises a photocurable resin (A), a photoreaction initiator (B) (for example, a photoradical polymerization initiator), (C) a phosphite compound and an aromatic ring. Containing at least one radical protecting compound selected from aromatic compounds having an N, N-dimethylamino group bonded to a carbon atom forming (B) and (D) a benzopyrromethene-based boron compound represented by the general formula (1). A composition.

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

In the photocurable resin (A), monofunctional and polyfunctional (meth) acrylates are generally used,
For example, JP-A-3-223759, 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, photosensitive resin Examples thereof include a photocurable resin containing a cinnamoyl group as a group and a photocurable resin containing an allyl group as a photosensitive group. The photocurable resin (A) is preferably used in combination with the following photoradical polymerization initiator. These photocurable resins (A) may be used alone or may be mixed. In the publication, a 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.

If necessary, a resin containing no unsaturated group such as an acrylic resin, a vinyl resin, a polyester resin, an alkyd resin, an epoxy resin, a phenol resin, a rubber, and a urethane resin, which are conventionally known, is added. be able to.

As the photoreaction initiator (B) used in the present invention, a photoradical polymerization initiator 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 thereof include benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone and anthraquinone. Aromatic carbonyl compounds; acetophenone, propiophenone, α-hydroxyisobutylphenone, α,
α'-dichloro-4-phenoxyacetophenone, 1-
Acetophenones such as hydroxy-1-cyclohexylacetophenone and diacetylacetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di-t-butyldiperoxyisophthalate, 3 ,
Organic peroxides such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; diphenylhalonium salts such as diphenyliodobromide and diphenyliodonium chloride; organic such as carbon tetrabromide, chloroform and iodoform. Halides; heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone and 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzathrone; 2,2′-azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile) Azo compounds such as iron;
Allene complexes (see EP 152377); titanocene compounds (see JP-A-63-221110); bisimidazole compounds; N-arylglycidyl compounds; acridine compounds; a combination of aromatic ketone / aromatic amine; And peroxyketal (see JP-A-6-321895). Among the above photoradical polymerization initiators, di-t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, an iron-allene complex and a titanocene compound are It is preferable to use this one because of its high activity against crosslinking or polymerization.

The mixing ratio of the photoreaction initiator is not critical, and can be varied in a wide range depending on the type of the photoreaction initiator. Generally, 100 parts by weight (solid content) of the photocurable resin is used.
0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight
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 radical protecting compound (C) used in the present invention, radicals generated when a resist film formed from a visible light curable resin composition is cured by irradiation with a visible light laser are inactivated by oxygen. Which can provide good sensitivity to the resist even in the presence of oxygen, in the present invention,
At least one compound selected from a phosphite compound and an aromatic compound having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring is used.

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

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

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

Of these, aromatic compounds having an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring and having a molecular weight of from 120 to 400 are considered to be compatible with the resin of the resist and the resulting resist film. It is particularly preferable in terms of sensitivity to visible light.

The amount of the specific radical protecting compound (C) is not strictly limited, and can be changed according to the type and amount of the photoreaction initiator (B) to be used. , Solid content of visible light curable resin composition 100
The amount is preferably in the range of 0.1 to 30 parts by weight, and particularly preferably in the range of 1 to 10 parts by weight, from the viewpoint of the photosensitivity of the resist film, the film strength and the like. .

The benzopyrromethene-based boron compound represented by the general formula (1) as the photosensitizer (D) of the present invention is:
Light in the visible light range of 400 to 700 nm, particularly the wavelength of the argon laser light or the YAG laser harmonic light (400
The compound is excited by absorbing light (up to 600 nm) and interacts with the photocurable resin (A) and the photoreaction initiator (B). The term "interaction" as used herein refers to energy transfer or electron transfer from the excited benzopyrromethene-based boron compound represented by the general formula (1) to the photocurable resin (A) or photoreaction initiator (B). Included. For this reason, the benzopyrromethene-based boron compound represented by the general formula (1) used here is a very useful compound as a photosensitizer.

Further, the conventional visible light curable resin composition comprises:
Although there was a problem in storage stability, the visible light-curable resin composition of the present invention can withstand long-term storage and has excellent storage stability over time.

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, neopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group, decalyl group, and icosanyl group Groups; chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, nonafluorobutyl and the like A halogenoalkyl group; an alkoxyalkyl group such as a methoxyethyl group, an ethoxyethyl group, an isopropyloxyethyl group, a 3-methoxypropyl group, and a 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; methylaminocarbonyl group, n-butylaminocarbonyl group, n-hexylaminocarbonyl group, cyclohexylaminocarbonyl group, alkylaminocarbonyl group such as 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, 3- 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;

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, propenyl, 1-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2,2-dicyanovinyl, 1,
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 icosanyl group; benzyl group, 2-methylbenzyl group, 4-ethylbenzyl group,
Aralkyl groups such as phenethyl group; phenyl group, 3-nitrophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, 2-methylphenyl group, 3,5-dimethylphenyl group, 3-trifluoromethylphenyl group, 4-
Aryl groups such as chlorophenyl group, 4-methoxyphenyl group, 4- (dimethylamino) phenyl group, naphthyl group, biphenyl group and fluorenyl group;

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 icosanyl group; a benzyl group;
Aralkyl groups such as -methylbenzyl group, 4-ethylbenzyl group and phenethyl group;

Phenyl, 3-nitrophenyl, 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.

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

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

The benzopyrromethene boron 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 boron compound can be obtained.

[0050]

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

[0051]

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

[0052]

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

[0053]

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

[0054]

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

[0055]

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

The photosensitizer (D) of the present invention has the general formula (1)
And at least one kind of a benzopyrromethene-based boron compound represented by the formula (1), and other known photosensitizers may be used in combination.

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. Is mentioned.

In this case, the content of the benzopyrromethene-based boron compound represented by the general formula (1) in the photosensitizer (D) is not particularly limited, however, in order to obtain a desired effect in the present invention. The content of the benzopyrromethene-based boron 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 still more preferably 30% by weight or more. % Or more, and a photosensitizer containing 50% by weight or more is particularly preferable.

The amount of the photosensitizer (D) used depends on the type and amount of the photosensitizer (D) and the photocurable resin (A) to be interacted with.
Depending on the type of component, usually, the photocurable resin (A)
The amount of the photosensitizer (D) to be used is in the range of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the component. If the amount of the photosensitizer (D) is less than 0.1 part by weight, the photosensitivity of the film to be formed tends to decrease. Tend to be difficult to maintain in a uniform state.

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

The above-mentioned other photopolymerizable unsaturated compound is preferably in the range of about 0 to 80% by weight, particularly about 5 to 50% by weight, based on the total weight (solid content) of the composition.

The visible light curable resin composition of the present invention may further comprise, if necessary, an adhesion promoter; a photopolymerization initiator or a sensitizer effective against ultraviolet rays; hydroquinone, 2,6-di-t.
Polymerization inhibitors such as -butyl-p-cresol (BHT) and N, N-diphenyl-p-phenylenediamine; various pigments such as organic resin fine particles, coloring pigments and extender pigments; metal oxides such as cobalt oxide; Plasticizers such as dibutyl acid, dioctyl phthalate, tricresyl phosphate, polyethylene glycol and polypropylene glycol; and organic solvents.

The above-mentioned adhesion promoter is compounded to improve the adhesion of the resist 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.

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

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

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

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

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

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

The water-dispersible or water-soluble visible light curable resin composition may be alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the photocurable resin.
Or when a cationic group such as an amino group is introduced, neutralization with an acid (neutralizing agent). Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Further, examples of the acid neutralizing agent include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent 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 flowability of the water-soluble or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol, t- -Butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used is generally
Up to 300 parts by weight per 100 parts by weight of resin solid component,
Preferably it can be up to 100 parts by weight.

Further, 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, methyl isobutyl ketone or the like is added to the photocurable resin composition. Ketones; 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 is
The amount 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 coating composition can be carried out by a conventionally known method. For example, the photocurable resin (A), the photoreaction initiator (B), the radical protection compound (C), the photosensitizer (D), and the solvent and the Can be prepared by thoroughly mixing the components and adding water.

The visible light curable resin composition thus prepared is further diluted with water by a usual method, for example, when the pH is in the range of 4 to 9, the bath concentration (solids concentration) is 3 to 3.
Electrodeposition paint (or electrodeposition bath) can be in the range of 25% by weight, preferably 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 1
Control at 5-30 ° C. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. An appropriate energization time is 10 seconds to 5 minutes.

In the electrodeposition coating method, the object to be coated is coated with an electrodeposition coating material having a low glass transition temperature, then washed with water or washed and dried, and further coated with 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 1-20 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then moisture and the like contained in the electrodeposition coating film are dried and removed with hot air or the like.

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

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

As the light source for exposure, light sources such as ultrahigh 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 can be 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 rinsing 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 that can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc., to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used.

In the case of the photocurable resin (A) having no ionic group, the unexposed portion is dissolved by using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, or methylene chloride. Do by doing. The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. If necessary, the printed circuit board can be manufactured by performing etching to remove the exposed conductor portion, and then removing the resist film.

[0083]

EXAMPLES The present invention will be described more specifically with reference to examples. Hereinafter, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Example 1 As photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20/10 //
100 parts of a polymer of the mixture of No. 20, 55 parts of trimethylolpropane triacrylate, 5 parts of a photosensitizer of the compound of 1-1 in Table 1, 20 parts of a titanocene compound of the following formula (a) as a photoreaction initiator, N, N as radical protecting compounds
A photosensitive solution was prepared using 3 parts of dimethylaniline and 160 parts of methyl cellosolve as a solvent.

[0085]

Embedded image

The photosensitive solution obtained as described above was applied to a plate having a thickness of 2 mm and a size of 350 mm with a copper layer having a thickness of 18 μm on the surface.
A 460 mm copper-clad glass fiber reinforced epoxy substrate was coated with a bar coater and dried at 60 ° C. for 10 minutes to obtain a resist film having a dry film thickness of 5 μm.

A 21-step step is formed on the resist film forming substrate.
Through a tablet film, the wavelength of 488 nm
Exposure 3mJ /
cm ^TwoVisible light laser by scanning method so that
Irradiated in air. Next, formation of a resist film after the above exposure
After heating the substrate at 60 ° C. for 10 minutes, 30% of 1% carbon dioxide
Immerse in a soda aqueous solution (developer) for 1 minute to develop and
The uncured part of the dist film was removed. After development of resist
The step tablet sensitivity was 7 steps. Here,
Tablet sensitivity is a stepwise change in light transmittance.
Film (here a 21-step tablet)
Good registration when exposed and developed using
The number of steps with the lowest light transmittance that indicates the strike pattern (curability)
To taste. The greater the number of steps, the lower the light transmittance of the film
The higher the number of steps showing a good resist pattern, the better
Indicates good sensitivity. Xenon lamp (ultraviolet wave
Long region cut) and the second harmonic of YAG laser (5
32 nm), the resist film was irradiated with light.
Light intensity is 3mJ / cm^TwoStep of resist after development
The bullet sensitivity was good at 7 steps.

The same evaluation was performed after the unexposed resist film-formed substrate was left at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Examples 2 to 50 In Example 1, 1-2 to 1 of Table 1 were used as photosensitizers.
A resist film was formed and evaluated in the same manner as in Example 1 except that -50 was used. The step tablet sensitivity of the resist after development was all good at 7 steps.

The same evaluation was performed after the unexposed resist film-formed substrate was left at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Example 51 In Example 1, methyl acrylate / styrene / acrylic acid = 60/10 in place of 100 parts of the acrylic resin.
/ 30 radical copolymer (acid value about 233) and 35 parts of glycidyl methacrylate obtained by addition reaction (acid value about 70, degree of unsaturation 1.83 mol / kg)
A photosensitive solution having the same composition as in Example 1 was prepared using 100 parts. Using this, a resist film was formed and evaluated in the same manner as in Example 1. The step tablet sensitivity of the developed resist was good at 7 steps.

The same evaluation was performed after leaving the unexposed resist film-formed substrate at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Example 52 In Example 1, a mixture of 50 parts of the acrylic resin and 50 parts of the photocurable resin used in Example 51 was used instead of 100 parts of the acrylic resin, and the same composition as in Example 1 was used. Was prepared. Using this, a resist film was formed and evaluated in the same manner as in Example 1. The step tablet sensitivity of the developed resist was good at 7 steps.

Further, after the unexposed resist film forming substrate was left at room temperature for 6 months, the same evaluation was performed.
No change was found in the photosensitive sensitivity.

Example 53 The same composition as in Example 1 was used, except that 155 parts of the photocurable resin used in Example 51 were used instead of 100 parts of the acrylic resin and 55 parts of trimethylolpropane triacrylate. Was prepared. Using this, a resist film was formed and evaluated in the same manner as in Example 1. The step tablet sensitivity of the developed resist was good at 7 steps.

Further, after the unexposed resist film forming substrate was left at room temperature for 6 months, the same evaluation was performed.
No change was found in the photosensitive sensitivity.

Example 54 100 parts (solid content) of the photosensitive solution obtained in Example 51 was mixed and stirred with 7 parts of triethylamine, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%). Was.

The obtained aqueous dispersion resin solution was used as an electrodeposition coating bath, anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, washed with water, and dried at 80 ° C. for 5 minutes. Was carried out to obtain an electrocoating photosensitive layer. Evaluation was performed in the same manner as in Example 1 using this photosensitive layer. The step tablet sensitivity of the developed resist was good at 7 steps.

Further, the unexposed electrodeposition coating photosensitive layer was coated at room temperature for 6 hours.
After having been left for a month, the same evaluation was performed. As a result, no change was found in the photosensitive sensitivity.

Example 55 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, 5 parts of compound 1-1 in Table 1, 55 parts of trimethylolpropane triacrylate, Example 1
100 parts (solid content) of the photosensitive solution obtained by mixing 20 parts of the titanocene compound used in the above was mixed with 3 parts of acetic acid, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%).
I got

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, a cationic copper electrodeposition coating was performed using a laminated copper plate as a cathode to a dry film thickness of 5 μm, followed by washing with water and drying at 80 ° C. for 5 minutes. Was carried out to obtain an electrocoating photosensitive layer. Evaluation was performed in the same manner as in Example 1 using this photosensitive layer. The step tablet sensitivity of the developed resist was good at 7 steps.

Further, the unexposed electrodeposition coating photosensitive layer was cured at room temperature for 6 hours.
After having been left for a month, the same evaluation was performed. As a result, no change was found in the photosensitive sensitivity. As a developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used instead of the 1% aqueous solution of sodium carbonate.

Example 56 A photosensitive solution was prepared in the same manner as in Example 1 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of the N, N-dimethylaniline radical protecting compound. Prepared. Using this, a resist film was formed and tested in the same manner as in Example 1. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

The same evaluation was performed after leaving the unexposed resist film-formed substrate at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Example 57 A photosensitive solution was prepared in the same manner as in Example 51 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of N, N-dimethylaniline as the radical protecting compound. Prepared. Using this, a resist film was formed and tested in the same manner as in Example 1. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

The same evaluation was performed after leaving the unexposed resist film-formed substrate at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Example 58 A photosensitive solution was prepared in the same manner as in Example 52 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of N, N-dimethylaniline as the radical protecting compound. Prepared. Using this, a resist film was formed and tested in the same manner as in Example 1. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

The same evaluation was performed after leaving the unexposed resist film-formed substrate at room temperature for 6 months.
No change was found in the photosensitive sensitivity.

Example 59 A photosensitive solution was prepared in the same manner as in Example 53 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of the radical protecting compound N, N-dimethylaniline. Prepared. Using this, a resist film was formed and tested in the same manner as in Example 1. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

Further, after the unexposed resist film forming substrate was left at room temperature for 6 months, the same evaluation was performed.
No change was found in the photosensitive sensitivity.

Example 60 A photosensitive solution was prepared in the same manner as in Example 54 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of N, N-dimethylaniline as the radical protecting compound. Prepared. Using this, the formation and test of an electrocoating photosensitive layer were carried out in the same manner as in Example 54. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

The photosensitive layer of the undeposited electrodeposition coating film
After having been left for a month, the same evaluation was performed. As a result, no change was found in the photosensitive sensitivity.

Example 61 A photosensitive solution was prepared in the same manner as in Example 55 except that 5 parts of triethylphosphorous acid was used instead of 3 parts of the N, N-dimethylaniline radical protecting compound. Prepared. Using this, the formation and test of an electrocoating photosensitive layer were performed in the same manner as in Example 55. As a result, the step tablet sensitivity of the developed resist was good at 7 steps.

The photosensitive layer of the undeposited electrodeposition coating film was coated at room temperature for 6 hours.
After having been left for a month, the same evaluation was performed. As a result, no change was found in the photosensitive sensitivity.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the compound of the following formula was used as the photosensitizer, and that 3 parts of N, N-dimethylaniline which was a radical protecting compound was not used. A photosensitive solution having the composition was prepared. Using this, formation and evaluation of the resist film were performed in the same manner as in Example 1. The step tablet sensitivity of the developed resist was poor at three steps.

[0116]

Embedded image

Further, after the unexposed resist film-formed substrate was left at room temperature for 6 months, the same evaluation was performed.
The above-mentioned sensitivity was poor at three steps.

[0118]

According to the present invention, a visible light curable resin composition containing a specific compound as a photosensitizer is a composition having extremely high practical utility. Conventionally, in the field of printed circuit boards using a photo-curing reaction as a resist material, a method of directly outputting and recording a printed circuit diagram using a laser as it is, the temporal stability of the photosensitive layer is low, and the sensitivity is low, There were problems such as solubility and storage stability.

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

The photosensitizer used in the present invention is 48
It has a very high sensitivity to general-purpose visible lasers such as an argon laser having stable oscillation lines at 8 nm and 514.5 nm and a YAG laser having an emission line at 532 nm as a second harmonic. The resist material obtained using the conductive resin composition 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.

Since the resist film obtained from the visible light curable resin composition of the present invention contains a specific radical protecting compound (C), radicals generated in the resist film by irradiation with a visible light laser are converted to oxygen. Thus, it is possible to prevent the resist film from being deactivated and the curing of the resist film from being inhibited.
That is, when the visible light curable resin composition of the present invention is used, a resist film having good sensitivity can be formed.

In general, when the curing is inhibited by oxygen, the degree of curing becomes insufficient near the surface of the resist film, so that the cross-sectional shape of the formed resist pattern becomes uneven, but the visible light curable resin composition of the present invention is Since the curing inhibition by oxygen can be prevented, a resist pattern having a rectangular cross section can be formed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Kogure 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Kansai Paint Co., Ltd. (72) Akira Ogiso 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Within the company (72) Inventor Denmi Misawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Corporation (72) U Tsukahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref. Mitsui Chemicals Co., Ltd. CA39 CC01 CC03 4F100 AB17A AH03B AH07B AK01B AK25B AT00A BA02 BA10A BA10B CA30B CC01B GB90 JB14B JL01 JN17 4J011 QC09 RA19 SA21 SA31 SA41 SA63 SA64 SA78 SA84 SA86 TA07 TA08 UA02 VA01 WA01

Claims (3)

[Claims] 1. Component (A) having a photocurable resin, (B) a photoreaction initiator, (C) a phosphite compound and an N, N-dimethylamino group bonded to a carbon atom forming an aromatic ring. Visible light comprising at least one radical protecting compound selected from aromatic compounds and (D) a photosensitizer containing at least one benzopyrromethene-based boron compound represented by the following general formula (1). Curable resin composition. 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, 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, R ₄ represents 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. ] 2. A visible light curable material composition 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.