JP2000029213A - Positive type visible light sensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type visible light sensitive resin compsn. having satisfactory sensitivity in the visible light region, particularly to second harmonics of argon laser and YAG laser, excellent in shelf stability and forming a superior photosensitive layer for visible light laser. SOLUTION: The visible light sensitive resin compsn. contains a positive type visible light sensitive resin and an organoboron compd. represented by the formula as a photosensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type visible-light-sensitive resin composition containing an organoboron compound having a specific structure as a photosensitizer and exhibiting high sensitivity to light in the visible light region and its use. Related to

[0002]

2. Description of the Related Art In recent years, in the field of information using light reaction or image recording, instead of the conventional recording method using ultraviolet light using a film original or the like, an electronically edited original by a computer is directly used as a high output laser. A method of directly outputting and recording the data by using 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 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 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.

[0005]

SUMMARY OF THE INVENTION The present invention relates to an argon laser 514.5 which is a high power and stable laser light source.
Positive-type visible light containing a photosensitizer that is highly sensitive to laser light having a long wavelength in the visible light region such as 532 nm, which is the second harmonic of a YAG laser, or 532 nm, which is the second harmonic of a YAG laser, and has excellent storage stability. A photosensitive resin composition is provided.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a positive-type visible light using an organoboron compound having a peculiar structure as a photosensitizer. The present inventors have found that a photosensitive resin composition solves the conventional problems, and have completed the present invention.

That is, the present invention relates to a positive visible light-sensitive resin composition comprising a positive visible light-sensitive resin and a photosensitizer, wherein the photosensitizer is represented by the general formula (1): Positive visible light-sensitive resin composition, characterized by containing an organic boron compound represented,

Embedded image[Wherein, R₁, R_Two, R_Three, R_Five, R₆, R₇Are independent
Are hydrogen, halogen, nitro, cyano,
Droxy group, amino group, carboxyl group, sulfonic acid
Group, alkyl group, halogenoalkyl group, alkoxyal
Kill group, alkoxy group, alkoxyalkoxy group,
Oxyalkoxyalkoxy group, aryloxy group,
Aralkyloxy group, acyl group, alkoxycarbonyl
Group, aminocarbonyl group, alkylaminocarbonyl
Group, dialkylaminocarbonyl group, alkyl carbonyl
Ruamino group, arylcarbonylamino group, aryla
Minocarbonyl group, aryloxycarbonyl group, ara
Alkyl, aryl, heteroaryl, alkylthio
O group, arylthio group, alkenyloxycarbonyl
Group, aralkyloxycarbonyl group, alkoxycarbo
Nylalkoxycarbonyl group, alkylcarbonylalkyl
Coxycarbonyl group, mono (hydroxyalkyl) amido
Nocarbonyl group, di (hydroxyalkyl) aminocar
Bonyl group, mono (alkoxyalkyl) aminocarboni
And di (alkoxyalkyl) aminocarbonyl groups
Or an alkenyl group;₁, R_Two, R_Three, R_Five, R₆,
R₇At least one of which is an alkoxy group or an alcohol
Xyalkoxy, aryloxy or aralkyl
An oxy group;_FourIs hydrogen atom, cyano group, alkyl
Group, aralkyl group, aryl group, heteroaryl group or
Represents an alkenyl group;₈, R₉Is a halogen atom, al
Kill group, aralkyl group, aryl group, heteroaryl
Group, alkoxy group, alkoxyalkoxy group, alkoxy
Alkoxyalkoxy group, halogenoalkyl group, al
A thioalkyl group, a dialkylaminoalkyl group,
Alkylthioalkoxy group, dialkylaminoalkoxy
Group, dialkylaminoalkoxyalkoxy group, alkyl
Luthio group, alkoxyalkylthio group, alkylthioa
Alkylthio, dialkylaminoalkylthio, ara
Alkyloxy group, aryloxy group, arylthio group,
A heteroaryloxy group or a heteroarylthio group
Represent. Where R₈And R₉Are both halogen atoms,
R₁, R_Two, R _Three, R_Five, R₆, R₇Are all alkenyl groups
Will not be. ]

[0008] 2. The positive visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and the exposed portion of the resin is dissolved in an organic solvent or an aqueous developer by irradiation with visible light. And the non-irradiated portion is a resin that does not dissolve in an organic solvent or an aqueous developing solution, wherein the positive-type visible light-sensitive resin composition; The present invention relates to a composition for a positive visible light-sensitive material containing a solvent, and 4, a positive resist material containing the above-mentioned positive visible light-sensitive resin composition on a substrate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The positive visible light-sensitive resin composition of the present invention contains a photosensitizer of an organic boron compound represented by the general formula (1).

It has been found that the photosensitizer using the organic boron compound represented by the general formula (1) of the present invention is extremely useful. The organic boron compound represented by the general formula (1) used in the present invention has an extremely large absorption at the wavelength of argon laser light or YAG laser high-wavelength light, and
It is a very useful material as a photosensitizer, having a very high sensitivity to such light and applicable to a positive photosensitive resin composition using a resin and a photoacid generator.

The "composition for positive-type visible light-sensitive material" referred to in the present invention includes, for example, paints, inks, adhesives,
It means a printing plate material, a resist material, and a non-photosensitive film formed from these materials.

Hereinafter, the present invention will be described in more detail. The photosensitizer of the organoboron compound represented by the general formula (1) emits light in the visible light region of 400 to 700 nm,
A compound that is excited by absorbing light having a wavelength of 400 to 600 nm and has an interaction with a resin or a photoacid generator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited photosensitizer to the resin or photoacid generator. For this reason, the photosensitizer used here is an extremely useful compound as a photosensitizer.

In the compound represented by formula (1) of the present invention, specific examples of R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R ₇ include a hydrogen atom; a nitro group; a cyano group; Hydroxy group; amino group; carboxyl group; sulfonic acid group;
Halogen atoms such as chlorine atom and bromine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-
An alkyl group such as an ethylhexyl group and a cyclohexyl group;
Chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group,
A halogenoalkyl group such as a nonafluorobutyl 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, isobutoxy, tert-butoxy, sec-butoxy, n-
Pentyloxy group, isopentyloxy group, tert-
Pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3-
Methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,1,2- Trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1-ethyl-2-
Methylpropoxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, 1-
Methylhexyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 4-methylhexyloxy group, 5-methylhexyloxy group, 1,1-dimethylpentyloxy group, 1,2-dimethylpentyloxy group 1,3-dimethylpentyloxy group, 1,4-dimethylpentyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethylpentyloxy group, 2,4-
Dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 1-ethylpentyloxy group, 2-ethylpentyloxy group,
3-ethylpentyloxy group, 1,1,2-trimethylbutoxy group, 1,1,3-trimethylbutoxy group, 1,
2,3-trimethylbutoxy group, 1,2,2-trimethylbutoxy group, 1,3,3-trimethylbutoxy group,
2,3,3-trimethylbutoxy group, 1-ethyl-1-
Methylbutoxy group, 1-ethyl-2-methylbutoxy group, 1-ethyl-3-methylbutoxy group, 2-ethyl-
1-methylbutoxy group, 2-ethyl-3-methylbutoxy group, 1-n-propylbutoxy group, 1-isopropylbutoxy group, 1-isopropyl-2-methylpropoxy group, methylcyclohexyloxy group, n-octyloxy group , 1-methylheptyloxy group, 2-methylheptyloxy group, 3-methylheptyloxy group, 4-methylheptyloxy group, 5-methylheptyloxy group, 6-
Methylheptyloxy group, 1,1-dimethylhexyloxy group, 1,2-dimethylhexyloxy group, 1,3-
Dimethylhexyloxy group, 1,4-dimethylhexyloxy group, 1,5-dimethylhexyloxy group, 2,2
-Dimethylhexyloxy group, 2,3-dimethylhexyloxy group, 2,4-dimethylhexyloxy group, 2,
5-dimethylhexyloxy group, 3,3-dimethylhexyloxy group, 3,4-dimethylhexyloxy group,
3,5-dimethylhexyloxy group, 4,4-dimethylhexyloxy group, 4,5-dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxy group A 1-n-propylpentyloxy group,
2-n-propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyloxy group, 1-ethyl-2-methylpentyloxy group, 1-ethyl-3 −
Methylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2-ethyl-3-methylpentyloxy group, 2 -Ethyl-4-
Methylpentyloxy group, 3-ethyl-1-methylpentyloxy group, 3-ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3-ethyl-4-methylpentyloxy group, 1 1,1,2-trimethylpentyloxy group, 1,1,3-trimethylpentyloxy group, 1,1,4-trimethylpentyloxy group, 1,2,2-trimethylpentyloxy group, 1,
2,3-trimethylpentyloxy group, 1,2,4-trimethylpentyloxy group, 1,3,4-trimethylpentyloxy group, 2,2,3-trimethylpentyloxy group, 2,2,4-trimethylpentyl Oxy group, 2,
3,4-trimethylpentyloxy group, 1,3,3-trimethylpentyloxy group, 2,3,3-trimethylpentyloxy group, 3,3,4-trimethylpentyloxy group, 1,4,4-trimethylpentyl Oxy group, 2,
4,4-trimethylpentyloxy group, 3,4,4-trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-te
rt-butylbutoxy group, 1-n-propyl-1-methylbutoxy group, 1-n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-isopropyl-1-methylbutoxy Group, 1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy group, 1,1-diethylbutoxy group, 1,2-
Diethyl butoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group,
1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethylbutoxy group, 2-ethyl-1,2-
Dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2-ethyl-2,3-dimethylbutoxy group,
1,2-dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group, 1,4-dimethylcyclohexyloxy group, ethylcyclohexyloxy group,
n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-pentadecanyloxy group, icosanyloxy group, 2-decalinoxy group, 4-
1 to 1 carbon atoms such as a (t-butyl) cyclohexyloxy group
20 linear alkoxy groups, or branched or cyclic alkoxy groups having 1 to 10 carbon atoms;

Alkoxyalkoxy groups such as methoxyethoxy, ethoxyethoxy, 3-methoxypropoxy and 3- (isopropyloxy) propoxy; phenoxy, 2-methylphenoxy, 4-methylphenoxy, 4-t- Aryloxy groups such as butylphenoxy group, 2-methoxyphenoxy group and 4-isopropylphenoxy group; benzyloxy group, phenethyloxy group,
3-phenylpropoxy group, 1-naphthylmethoxy group,
2-naphthylmethoxy group, 2-naphthylethoxy group, biphenylmethoxy group, 2-anthraquinoylmethoxy group, 4-ethylphenylmethoxy group, 4-p-isopropylphenylmethoxy group, 4-t-butylphenylmethoxy group, p -Isopropylphenylethoxy group, t-butylphenylethoxy group, 4-t-butylphenylethoxy group, tolylmethoxy group, tolylethoxy group, 2,3
-Dimethylphenylmethoxy group, 2,4-dimethylphenylmethoxy group, 2,5-dimethylphenylmethoxy group, 2,6-dimethylphenylmethoxy group, 2,4,6
-Trimethylphenylmethoxy, 2-chlorophenylmethoxy, 3-chlorophenylmethoxy, 4-chlorophenylmethoxy, 2-bromophenylmethoxy, 3-bromophenylmethoxy, 4-bromophenylmethoxy, 2-fluorophenylmethoxy Group, 3-
Fluorophenylmethoxy group, 4-fluorophenylmethoxy group, 2-methoxyphenylmethoxy group, 3-methoxyphenylmethoxy group, 4-methoxyphenylmethoxy group, 2-ethoxyphenylmethoxy group, 3-ethoxyphenylmethoxy group, 4-ethoxy Phenylmethoxy group, 2-n-propoxyphenylmethoxy group, 3-n-
Propoxyphenylmethoxy group, 4-n-propoxyphenylmethoxy group, 2-isopropoxyphenylmethoxy group, 3-isopropoxyphenylmethoxy group, 4-isopropoxyphenylmethoxy group, 2-n-butoxyphenylmethoxy group, 3-n -Butoxyphenylmethoxy group, 4-n-butoxyphenylmethoxy group, 2-isobutoxyphenylmethoxy group, 3-isobutoxyphenylmethoxy group, 4-isobutoxyphenylmethoxy group, 2
-T-butoxyphenylmethoxy group, 3-t-butoxyphenylmethoxy group, 4-t-butoxyphenylmethoxy group, 2,3-dimethylphenylethoxy group, 2,4-
Dimethylphenylethoxy group, 2,5-dimethylphenylethoxy group, 2,6-dimethylphenylethoxy group,
2,4,6-trimethylphenylethoxy group, 2-chlorophenylethoxy group, 3-chlorophenylethoxy group, 4-chlorophenylethoxy group, 2-bromophenylethoxy group, 3-bromophenylethoxy group, 4-bromophenylethoxy group, 2-fluorophenylethoxy group, 3-fluorophenylethoxy group, 4-fluorophenylethoxy group, 2-methoxyphenylethoxy group, 3-methoxyphenylethoxy group, 4-methoxyphenylethoxy group, 2-ethoxyphenylethoxy group,
3-ethoxyphenylethoxy group, 4-ethoxyphenylethoxy group, 2-n-propoxyphenylethoxy group, 3-n-propoxyphenylethoxy group, 4-n-
Propoxyphenylethoxy group, 2-isopropoxyphenylethoxy group, 3-isopropoxyphenylethoxy group, 4-isopropoxyphenylethoxy group, 2-n
-Butoxyphenylethoxy group, 3-n-butoxyphenylethoxy group, 4-n-butoxyphenylethoxy group, 2-isobutoxyphenylethoxy group, 3-isobutoxyphenylethoxy group, 4-isobutoxyphenylethoxy group, 2- t-butoxyphenylethoxy group, 3
-T-butoxyphenylethoxy group, 4-t-butoxyphenylethoxy group, fluoren-9-yloxy group,
9-methylfluoren-9-yloxy group, 9-ethylfluoren-9-yloxy group, 9-propylfluoren-9-yloxy group, 9-butylfluoren-9-yloxy group, 4-nitrobenzyloxy group, 4-cyano Benzyloxy group, 4-acetylbenzyloxy group,
2,4-dimethylbenzyloxy group, 2,3-dimethylbenzyloxy group, 2,5-dimethylbenzyloxy group, 2,6-dimethylbenzyloxy group, 3,5-dimethylbenzyloxy group, 2,4,6 An aralkyloxy group having 1 to 20 carbon atoms such as a trimethylbenzyloxy 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; an aminocarbonyl group; an alkyl group such as a methylaminocarbonyl group, an n-butylaminocarbonyl group, an n-hexylaminocarbonyl group, a cyclohexylaminocarbonyl group, a 4-methylcyclohexylaminocarbonyl group. An aminocarbonyl group;

Dimethylaminocarbonyl, diethylaminocarbonyl, di-n-butylaminocarbonyl, di-n-hexylaminocarbonyl, di-n-octylaminocarbonyl, N-isoamyl-N-methylaminocarbonyl, etc. Dialkylaminocarbonyl group; acetylamino group, ethylcarbonylamino group, alkylcarbonylamino group such as isobutylcarbonylamino group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group, 2-methoxyphenylaminocarbonyl group, 4-n Arylaminocarbonyl groups such as -propylphenylaminocarbonyl group; phenylcarbonylamino group, 4-ethylphenylcarbonylamino group, 3-isopropylphenylcarbonylamino group, 2
Arylcarbonylamino groups such as -methoxyphenylcarbonylamino group; phenoxycarbonyl group, 4-methylphenoxycarbonyl group, 3-methylphenoxycarbonyl group, 2-methylphenoxycarbonyl group, 2,4
Aryloxycarbonyl groups such as -dimethylphenoxycarbonyl group, 2,6-dimethylphenoxycarbonyl group, 2,4,6-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 groups; pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl,
Benzimidazoyl group, benzofuranyl group, indo-3
A heteroaryl group such as -yl group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n
Alkylthio groups such as -butylthio group, isobutylthio group, t-butylthio group, 3,5,5-trimethylhexylthio group; phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butyl Arylthio groups such as phenylthio group and naphthylthio group; alkenyloxycarbonyl groups such as allyloxycarbonyl group and 2-butenoxycarbonyl group; aralkyl groups such as benzyloxycarbonyl group, 4-methylbenzyloxycarbonyl group and phenethyloxycarbonyl group An oxycarbonyl group;

Alkoxycarbonylalkoxycarbonyl groups such as methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, isopropoxycarbonylmethoxycarbonyl group; methylcarbonylmethoxycarbonyl group, ethylcarbonylmethoxycarbonyl group and the like; Alkylcarbonylalkoxycarbonyl group; mono (hydroxyalkyl) aminocarbonyl group such as hydroxyethylaminocarbonyl group, 2-hydroxypropylaminocarbonyl group, 3-hydroxypropylaminocarbonyl group; di (hydroxyethyl) aminocarbonyl group, di (2 -(Hydroxypropyl) aminocarbonyl group, di (3-hydroxypropyl) aminocarbonyl group, etc. Mono (alkoxyalkyl) aminocarbonyl groups such as methoxymethylaminocarbonyl, methoxyethylaminocarbonyl, ethoxymethylaminocarbonyl, ethoxyethylaminocarbonyl, and propoxyethylaminocarbonyl; di (methoxymethyl) ) Di (alkoxyalkyl) aminocarbonyl groups such as aminocarbonyl group, di (methoxyethyl) aminocarbonyl group, di (ethoxymethyl) aminocarbonyl group, di (ethoxyethyl) aminocarbonyl group and di (propoxyethyl) aminocarbonyl group A vinyl group, a propenyl group,
Alkenyl groups such as 1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-methyl-1-butenyl group, 2,2-dicyanovinyl group, 1,2,2-tricyanovinyl group and the like are mentioned. Can be.

At least one of R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R ₇ represents an alkoxy group, an alkoxyalkoxy group, an aryloxy group, or an aralkyloxy 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 an alkenyl group such as a 2-tricyanovinyl group.

Specific examples of R ₈ and R ₉ 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 phenyl group or a phenethyl 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 and indo-3-yl;

The above alkoxy groups; methoxyethoxy groups, ethoxyethoxy groups, 3-methoxypropoxy groups,
Alkoxyalkoxy groups such as 3- (isopropyloxy) propoxy group; examples of alkoxyalkoxyalkoxy groups include methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propoxymethoxymethoxy group, butoxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxy group; Methoxy group, propoxyethoxymethoxy group, butoxyethoxymethoxy group, methoxypropoxymethoxy group, ethoxypropoxymethoxy group,
Propoxypropoxymethoxy group, butoxypropoxymethoxy group, methoxybutoxymethoxy group, ethoxybutoxymethoxy group, propoxybutoxymethoxy group, butoxybutoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propoxymethoxyethoxy group, butoxymethoxyethoxy group, Methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, butoxyethoxyethoxy, methoxypropoxyethoxy, ethoxypropoxyethoxy, propoxypropoxyethoxy, butoxypropoxyethoxy, methoxybutoxyethoxy, methoxybutoxyethoxy, methoxybutoxyethoxy Propoxybutoxyethoxy, butoxybutoxyethoxy, methoxymethoxypropoxy , Ethoxy methoxypropoxy group,
Propoxymethoxypropoxy, butoxymethoxypropoxy, methoxyethoxypropoxy, ethoxyethoxypropoxy, propoxyethoxypropoxy, butoxyethoxypropoxy, methoxypropoxypropoxy, ethoxypropoxypropoxy, propoxypropoxy, butoxypropoxy, butoxypropoxy Methoxybutoxypropoxy group, ethoxybutoxypropoxy group, propoxybutoxypropoxy group, butoxybutoxypropoxy group, methoxymethoxybutoxy group, ethoxymethoxybutoxy group, propoxymethoxybutoxy group, butoxymethoxybutoxy group,
Methoxyethoxybutoxy group, ethoxyethoxybutoxy group, propoxyciethoxybutoxy group, butoxyethoxybutoxygo, methoxypropoxybutoxy group, ethoxypropoxybutoxy group, propoxypropoxybutoxy group, butoxypropoxybutoxy group, methoxybutoxybutoxy group, methoxybutoxybutoxy group A propoxybutoxybutoxy group, a butoxybutoxybutoxy group, a 4-ethylcyclohexyloxyethoxyethoxy group, a (2-ethyl-1-hexyloxy) ethoxypropoxy group, a 4- (3,5,5-trimethylhexyloxybutoxyethoxy group, A linear, branched or cyclic C1-C20 alkoxyalkoxyalkoxy group such as 6- (2- (2-decalyloxy) butoxy) n-hexyloxy group;

Halogenoalkyl groups such as chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group and nonafluorobutyl group; 2-methylthioethyl group, 2-ethylthioethyl group, n-propylthioethyl group, 2-iso-propylthioethyl group, 2-n-butylthioethyl group, 2-
alkylthioalkyl groups such as iso-butylthioethyl group; 2-dimethylaminoethyl group, 2- (2-dimethylaminoethoxy) ethyl group, 4-dimethylaminobutyl group, 1-dimethylaminopropan-2-yl group, 3 Dialkylaminoalkyl groups such as -dimethylaminopropyl group, 2-di-iso-propylaminoethyl group, 2-di-n-butylaminoethyl group; 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n -Propylthioethoxy group, 2-iso-propylthioethoxy group, 2
Alkylthioalkoxy groups such as -n-butylthioethoxy group and 2-iso-butylthioethoxy group;

A 2-dimethylaminoethoxy group, 2- (2
-Dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropane-2-
Yloxy group, 3-dimethylaminopropoxy group, 2-
Dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2- (2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1
Dialkylaminoalkoxy groups such as -diethylaminopropoxy group, 2-di-iso-propylaminoethoxy group, 2-di-n-butylaminoaminoethoxy group; dimethylaminoethoxyethoxy group, dimethylaminoethoxypropoxy group, diethylaminoethoxypropoxy group Dialkylaminoalkoxyalkoxy groups such as;

The above-mentioned aralkyloxy groups; aryloxy groups such as phenoxy, 2-methylphenoxy, 4-methylphenoxy, 4-t-butylphenoxy, 2-methoxyphenoxy and 4-iso-propylphenoxy; A methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, an iso-butylthio group, a sec-butylthio group, t
-Butylthio group, n-pentylthio group, iso-pentylthio group, 1,2-dimethylpropylthio group, 1,1-
Alkylthio groups such as dimethylpropylthio group; alkoxyalkylthio groups such as methoxymethylthio group, methoxyethylthio group and ethoxyethylthio group; alkylthioalkylthio groups such as methylthiomethylthio group, methylthioethylthio group and ethylthioethylthio group; Dialkylaminoalkylthio groups such as dimethylaminoethylthio group and 4-dimethylaminobutylthio group; phenylthio group, 2-methylphenylthio group, 4-methylphenylthio group, 4-t-butylphenylthio group and 2-methoxyphenyl Arylthio groups such as thio group and 4-t-butylphenylthio group; heteroaryloxy groups such as pyrrolyloxy group, thienyloxy group, furanyloxy group and oxazoyloxy group; pyrrolylthio group, thienylthio group, furanylthio group, oxa group It can be exemplified heteroarylthio groups such as a ylthio group.

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

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

The organoboron compound represented by the general formula (1) of the present invention can be produced by the following method. That is,
Known methods (eg, Aust. J. Chem., 1965, 11, 1835)
-45, Liebigs Ann. Chem., 1973, 146-60), the compound represented by the following general formula (2) is reacted with boron trihalide to thereby form the compound represented by the following general formula (3). After obtaining the compound, a halogen atom is finally substituted to obtain an organic boron compound represented by the general formula (1).

[0033]

Embedded image

[0034]

Embedded image (In the above formula, R _{1 to} R ₇ are the same as described above, and X represents a halogen atom.)

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

The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer, 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 organic boron compound represented by the general formula (1) in the photosensitizer is as follows:
Although there is no particular limitation, in order to obtain a desired effect in the present invention, the content of the organic boron compound represented by the general formula (1) in the photosensitizer is 10% by weight or more. Is more preferably 20% by weight or more, further preferably 30% by weight or more, and a photosensitizer containing 50% by weight or more is particularly preferable.

The amount of the organic boron compound photosensitizer used is
Although it depends on the type and amount of the photosensitizer of the organoboron compound represented by the general formula (1) contained in the photosensitizer and the type of the resin component to be interacted with, it is usually 100 parts by weight of the resin component. The amount of the organic boron compound photosensitizer represented by the general formula (1) is preferably 0.1 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight. If the amount of the organic boron compound photosensitizer is less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease, and
When 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 positive-type visible light-sensitive resin composition of the present invention comprises a conventionally known positive-type visible light-sensitive resin composition (for example, paint , An ink, an adhesive, a printing plate material, a resist material for a printed wiring board) containing a photosensitizer of the organoboron compound represented by the general formula (1) as an essential component. .

Representative examples of the above-described conventionally known positive-type visible light-sensitive resin compositions are described below.

The positive visible light-sensitive resin in the composition includes, for example, a resin containing a photoacid generator, a resin containing a component other than the photoacid generator component (eg, a photobase generator, etc.), and the resin itself. Resins decomposed by light.
When these resins are decomposed by light, their properties, such as polarity and molecular weight, change, whereby the resins become soluble in substances such as a developer (aqueous solution, organic solvent, etc.). The resin may have a component such as a photoacid generator incorporated therein or may be a mixture of a component such as a photoacid generator and a resin having a group that is decomposed by an acid or the like. Further, other resins or the like for adjusting the solubility of the developing solution can be further added to these as required.

The resin containing the photoacid generator component will be described. The resin includes a resin in which a photoacid generator is incorporated in a resin skeleton (for example, a resin in which a resin generates an acid group upon exposure to light, thereby enabling alkali development) or a mixture of a photoacid generator and a resin [ The acid generated by the photoacid generator causes the resin to be cut to have a low molecular weight, an acid group to be added to the resin, or a change to a soluble substance (for example, (poly) P-hydroxystyrene). One that exhibits dispersibility or solubility in an organic solvent or an aqueous developer].

Examples of such a composition include a composition mainly composed of a resin in which quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group via a sulfonic acid ester bond (Japanese Patent Application Laid-Open No. 61-61980). -206293
JP-A-7-334449), that is, a naphthoquinonediazide photosensitive composition utilizing a reaction in which a quinonediazide group is photolyzed by irradiation light to form indenecarboxylic acid via ketene; A chemically amplified photosensitive material utilizing a change in solubility between irradiated and unirradiated parts by causing a elimination reaction in a base resin (polymer) in a chain using a photoacid generator that generates an acid group as a catalyst (particularly, Kaihei 4-2
No. 26461, U.S. Pat. No. 4,491,628, JP-A-59-45439, JP-A-63-2
No. 50642, Polymers in Electronics "Davidso
n T. Edit.ACS Symposium Series242, American Chemica
l Society, Washington DC, 1984, p. 11 ", N. Hayash
i, T. Ueno, M. Toriumi, etc, ACS Polym. materials
Sci. Eng., 61, 417 (1989), H. Ito, CG Wilson, AC
S Symp. Ser., 242, 11 (1984), etc.); forms a crosslinked film insoluble in a solvent or aqueous alkali solution by heating, and forms a crosslinked structure with a photoacid generator that generates an acid group by irradiation with light. Positive photosensitive compositions utilizing a mechanism in which the irradiated portion is cut and becomes soluble in a solvent or an aqueous alkaline solution (JP-A-6-295064, JP-A-6-295064)
308733, JP-A-6-313134,
JP-A-6-313135, JP-A-6-31313
No. 6, JP-A-7-146552, etc.) and the like.

In the above-mentioned compounds, a functional group (hydroxyl group, carboxyl group, etc.) which controls solubility in a developer in a resin is blocked (acid-labile group) to make it insoluble, and the block is formed by a photoacid generator. It dissociates and restores the solubility of the polymer. Examples of the acid labile group (R group of —OR) in which the hydroxyl group (—OH group) is blocked include, for example, t-butoxycarbonyl group (t-BOC group), t-butoxy group, t-butoxycarbonylmethyl group, Examples include a tetrahydropyranyl group, a trimethylsilyl group, an iso-propoxycarbonyl group, and the like. The resin having a hydroxyl group is not particularly limited as long as it exhibits the above-mentioned effects, but is usually a phenolic hydroxyl group. As the acid labile group, a t-BOC group and a t-butoxy group are particularly preferable, and examples thereof include poly (t-butoxycarbonyloxystyrene) and poly (t-butoxycarbonyloxy-α-styrene). , Poly (t-butoxystyrene) and copolymers of these monomers with other polymerizable monomers (eg, C1-24 alkyl or cycloalkyl esters of methyl (meth) acrylic acid, maleimide, sulfone, etc.) And the like. The t
The composition of poly (t-butoxycarbonyloxystyrene) containing a -BOC group is described, for example, as follows.
The acid generated by the photoacid generator decomposes the t-BOC group, evaporates isobutene and carbon dioxide to form polystyrene, and changes (increases) the polarity of the resin by changing the t-BOC group to a hydroxyl group. This makes use of the property of improving the solubility in a developing solution (aqueous alkaline solution). Examples of the acid labile group (R ′ group of —COOR ′) in which a carboxyl group (—COOH group) is blocked include carboxylic acid ester derivatives having a t-butyl group.

The components of the resin include a two-component system of a resin having an acid labile group and a photoacid generator, and a three-component system of a resin having an acid labile group, a photoacid generator, and other resins. Can be used as The other resin is
By using this, for example, the coating workability of the composition can be improved or the solubility in a developer can be changed.

The above resins contain a resin (a) containing a carboxyl group and / or a hydroxyphenyl group, an olefinically unsaturated compound containing an ether bond (b), and a photoacid generator that generates an acid group upon irradiation with light. Or a liquid or solid resin composition.

In the case where the resin (a) has both a carboxyl group and a hydroxyphenyl group, even if the resin has these groups in the same molecule, the resin containing one of these groups may be the same as the resin containing the other group. It does not matter even if it is a mixed resin of the resin containing.

Examples of the carboxyl group-containing resin (a-1) include acrylic resins and polyester resins.

The above resin (a-1) is generally used in an amount of about 500
It preferably has a number average molecular weight of from about 100,000, especially from about 1500 to 30,000, and the carboxyl group is preferably from about 0.5 to 10 mol, especially about 0.7 to 5 mol per kg of resin. .

Hydroxyphenyl group-containing resin (a-2)
As a condensate of a monofunctional or polyfunctional phenol compound, an alkylphenol compound, or a mixture thereof with a carbonyl compound such as formaldehyde and acetone; and a hydroxyphenyl group-containing unsaturated monomer such as P-hydroxystyrene. Depending on the above, copolymers with the above-mentioned other polymerizable unsaturated monomers can be used.

The above resin (a-2) is generally used in an amount of about 500
It preferably has a number average molecular weight of about 10000 to about 100000, particularly about 1500 to 30000, and the hydroxyphenyl group is preferably about 1.0 mol or more, more preferably about 2 to 8 mol per kg of resin.

When the resin (a-1) and the resin (a-2) are used as a mixture, the mixing ratio is 90/1.
It is preferable to mix them in a weight ratio of 0 to 10/90.

Examples of the resin (a-3) having a carboxyl group and a hydroxyphenyl group include a carboxyl group-containing polymerizable unsaturated monomer (such as (meth) acrylic acid) and a hydroxyphenyl group-containing polymerizable unsaturated monomer. (Hydroxystyrene, etc.) and, if necessary, other polymerizable unsaturated monomers (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) A) C1-C12 alkyl esters of acrylic acid such as acrylate, aromatic compounds such as styrene, (meth)
A copolymer with hydroxybenzoic acids, gallic acid, resorcinic acid, or a mixture thereof with phenol, naphthols, resorcinol, catechol, etc., with formaldehyde. And the like.

The above resin (a-3) is generally used in an amount of about 500.
It preferably has a number average molecular weight of from about 100,000, especially from about 1500 to 30,000, and the carboxyl group is preferably from about 0.5 to 10 mol, especially about 0.7 to 5 mol per kg of resin. . The hydroxyphenyl group is present in an amount of about 1.0 mol or more, preferably about 2 to 8
Molar is preferred.

The olefinically unsaturated compound (b) containing an ether bond includes, for example, about 1 to 4 unsaturated ether groups such as a vinyl ether group, a 1-propenyl ether group and a 1-butenyl ether group at the molecular terminal. To do. The compound (b) has the formula -R "-
OA [where A represents a vinyl group, a 1-propenyl group or an olefinically unsaturated group of 1-butenyl, and R "represents a linear or branched C1-C6 group such as ethylene, propylene or butylene. A chain alkylene group], and preferably at least one unsaturated ether group
A low or high molecular weight compound containing up to 4
For example, polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and phenolic resin; polyols such as ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, and pentaerythritol; and alkyl unsaturated halides such as chloroethyl vinyl ether. Condensates with ethers; reaction products of polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate with hydroxyalkyl unsaturated ethers such as hydroxyethyl vinyl ether.
In particular, a condensate of the above polyphenol compound and a halogenated alkyl unsaturated ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl unsaturated ether are preferable from the viewpoint of etching resistance, accuracy of a formed pattern, and the like. It is. The compound (b) is used in an amount of usually about 5 to 150 parts by weight, preferably about 10 to 100 parts by weight, based on 100 parts by weight of the resin (a).

The composition containing the components (a) and (b) is characterized in that the coating formed therefrom is crosslinked by heating and by the addition reaction of a carboxyl group and / or a hydroxyphenyl group with an unsaturated ether group to form a solvent. Or insoluble in aqueous alkali solution, then irradiate with active energy rays, and then heat after irradiation, the cross-linking structure is cut by the catalytic action of the generated acid, and the irradiated part becomes soluble again in solvent or aqueous alkali solution It is a positive photosensitive resin composition.

In the composition, an acid hydrolysis reaction is caused in an exposed portion by an acid generated when a film to be formed is exposed, but water must be present in order for the acid hydrolysis reaction to proceed smoothly. Is desirable. Therefore, in the composition of the present invention, by incorporating a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methylcellulose, and ethylcellulose, the water required for the above reaction can be easily incorporated into the formed coating film. You can do so. The amount of the hydrophilic resin to be added is generally 20 parts by weight or less, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.

Further, the photoacid generator described in the above,
It is a compound that generates an acid upon exposure and decomposes the resin using the generated acid as a catalyst. A conventionally known compound can be used. Examples thereof include sulfonium salts, ammonium salts, phosphonium salts, onium salts such as iodonium salts and selenium salts, iron-allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfones Acid esters, sulfonic imide esters, halogen compounds, and the like can be used.
Further, in addition to the above, JP-A-7-146552,
Photoacid generators described in Japanese Patent Application No. 9-289218 can also be used. This photoacid generator component may be a mixture with the above-mentioned resin or a compound bonded to the resin. The content of the photoacid generator is preferably about 0.1 to 40 parts by weight, particularly about 0.2 to 20 parts by weight, based on 100 parts by weight of the resin.

In the composition of the present invention, in addition to the above-mentioned resins, solubility in an organic solvent or an aqueous developer can be improved,
In addition, the above-mentioned other resins which are insoluble or dissolved (or dispersed) in water or an organic solvent, which can make the composition worse, can be added as necessary.
Specifically, for example, a phenolic resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, a silicone resin, a fluororesin, and a mixture or modified product of two or more of these resins Is mentioned.

In order to impart appropriate flexibility and non-adhesiveness to a film formed using the composition of the present invention, a plasticizer such as a phthalate ester is added to the composition of the present invention. A polyester resin, an acrylic resin, or the like can be added.

Further, the composition of the present invention may optionally contain a flow control agent, a plasticizer, a coloring agent such as a dye or a pigment, and the like.

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 plate and letterpress, 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 (for example, a general positive photosensitive resist material and a positive resist material for electrodeposition coating) of the visible light curable resin composition of the present invention will be described.

As a general positive photosensitive resist material, for example, the positive visible light-sensitive resin composition of the present invention is dispersed or dissolved in a solvent (including water). Pigment is finely dispersed) to prepare a photosensitive solution,
This can be used as a positive resist material by a method of applying it on a support using a coating device such as a roller, a roll coater, or a spin coater, and drying.

Solvents used for dissolving or dispersing the positive-type visible light photosensitive resin composition include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and esters (ethyl acetate, butyl acetate, benzoic acid) Methyl ether, 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, dimethylsulfoxide, etc.), water and the like. .

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

When used as a positive resist material for electrodeposition coating, the positive visible light-sensitive resin composition of the present invention is first made into a water-dispersed product or a water-soluble product.

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

In order to further improve the 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 30 per 100 parts by weight of the resin solid component.
It can be up to 0 parts by weight, preferably up to 100 parts by weight.

In order to increase the amount of coating on the object to be coated, a hydrophobic solvent such as a petroleum solvent such as toluene or xylene; methyl ethyl ketone or methyl isobutyl is added to the positive type visible light photosensitive resin composition. Ketones such as ketones; esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added. The amount of these hydrophobic solvents is usually 2 parts per 100 parts by weight of the resin solid component.
It can be up to 00 parts by weight, preferably 100 parts by weight or less.

The preparation of a positive-type visible light photosensitive resin composition as an electrodeposition paint can be carried out by a conventionally known method. For example, a resin or a resin mixture which has been made water-soluble by the above-described neutralization, a photosensitizer of an organic boron compound, and further, if necessary, a solvent and other components are well mixed, and the mixture can be prepared by adding water. .

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

The obtained film thickness 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 the moisture and the like contained in the electrodeposition coating film are dried and removed with hot air or the like (the compositions (a) and (b) are used). In this case, the coated substrate is subjected to temperature and time conditions under which a crosslinking reaction between the carboxyl group and / or hydroxyphenyl group-containing polymer and the vinyl ether group-containing compound substantially occurs, for example, about 60 to Heat at a temperature of about 150C for about 1 minute to about 30 minutes to crosslink and cure the coating).

As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material obtained by fixing these materials 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 decomposed. An image can be formed by removing the exposed portion by a developing process.

The light source for exposure is obtained from light sources such as ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps and sunlight. 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 (532 nm) of a YAG laser is preferable.

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

Further, in the case of a photosensitive resin having no ionic group, development processing is performed by dissolving the exposed portion using a solvent such as 1,1,1-trichloroethane, trichloroethylene, methyl ethyl ketone, or methylene chloride.
After development, the coating film is washed with water and then dried with hot air, etc.,
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.

When (a) and (b) are used as the composition, the cross-linked structure of the cured coating film is cut on the substrate irradiated with visible light in the presence of the acid generated by the irradiation. Under such temperature and time conditions, for example, heating is performed at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating film on the irradiated portion. At that time, preferably,
The substrate irradiated with visible light is brought into contact with water in advance. The contact with water facilitates the generation of an acid and facilitates the subsequent cleavage reaction of the crosslinked structure. The contact with water can be performed by immersing the substrate in room temperature water or hot water, or by spraying water vapor.

The positive-type visible light-sensitive resin composition of the present invention may further include, for example, a transparent resin film such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin, which is used as a cover film layer. On top, the composition of the present invention is roll-coated,
It is applied using a blade coater, curtain flow coater, etc., and dried to form a resist film (dry film thickness of about 0.5 to 5 μm).
After forming m), the film can be used as a dry film resist in which a protective film is attached to the surface of the film.

Such a dry film resist can be formed by peeling off the protective film and then bonding the resist film to a support by thermocompression bonding so that the resist film is in contact with the support film to form a resist film. The resist film can be exposed to visible light and developed according to the image in the same manner as the above-mentioned electrodeposition coating film to form an image.

[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. In the examples and comparative examples, “parts” indicates “parts by weight”.

Example 1 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
1 part and 3 parts of azobisisobutyronitrile are mixed with 1 part
The reaction product obtained by reacting at 00 ° C. for 2 hours is 1500 c
The resulting mixture was poured into a toluene solvent (c) to precipitate and separate the reaction product. The precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) was added to 100 parts of this, and NAI-
105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name)
10 parts and the compound of 1-1 in Table 1 as a photosensitizing dye.
Five parts of the mixture was dissolved in diethylene glycol dimethyl ether to adjust the solid content to 20% to obtain a photosensitive solution.

Next, this photosensitive liquid was applied to a copper-clad laminate using a spin coater so that the dry film thickness became 5 μm, and heated at 120 ° C. for 8 minutes to form a resist film. The substrate was irradiated with a 5 mJ / cm ² intensity argon laser through a positive pattern mask to light the above-mentioned photosensitive layer, heated at 120 ° C. for 10 minutes, and developed with a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and no reduction or swelling of the film in the unexposed portion was observed. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut off) and a second harmonic (532 nm) of a YAG laser.

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

Examples 2 to 42 Photosensitive liquids were prepared in the same manner as in Example 1 except that 1-2 to 1-42 in Table 1 were used as photosensitizers. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and an argon laser having an intensity of 5 mJ / cm ² was applied to the obtained substrate through a positive pattern mask to obtain the photosensitive layer. The layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after development with respect to the irradiation amount of visible light, a film having excellent contrast is formed,
No decrease or swelling of the film in the unexposed portion was observed. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut off) and a second harmonic (532 nm) of a YAG laser.

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

Example 43 22 parts of acrylic acid, 50 parts of styrene, 28 parts of n-butyl methacrylate, azobisisobutyronitrile (AI
BN) A mixture of 5 parts was dropped into 60 parts of methyl isobutyl ketone, which was heated to 80 ° C. and stirred, over 2 hours, and then kept at that temperature for 2 hours to obtain a solid content of about 62.5. %, A carboxyl group 3 mol / kg polymer was obtained.

80 parts of the carboxyl group-containing polymer (solid content: 62.5%) obtained above, 20 parts of a P-hydroxystyrene polymer (molecular weight: 1000), a divinyl ether compound (1 mol of a bisphenol compound and 2-chloroethyl 60 parts of a condensate with 2 mol of vinyl ether), 2 parts of polyethylene glycol (average molecular weight: 400), NAI-10
5 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) 10
Of a photosensitizer used in Example 1 was dissolved in diethylene glycol dimethyl ether to obtain a 20% by weight photosensitive solution.

Using this photosensitive liquid, a photosensitive layer was formed in the same manner as in Example 1, and heated at 120 ° C. for 8 minutes. The substrate obtained was irradiated with an argon laser having an intensity of 5 mJ / cm ² through a positive pattern mask. To the above photosensitive layer,
After heating at 10 ° C. for 10 minutes, development was performed using a 1% aqueous solution of sodium carbonate. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and the second harmonic (532 nm) of a YAG laser.

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

Example 43 P-hydroxystyrene polymer (molecular weight: 1000) 10
0 parts, a divinyl ether compound (condensate of 1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) 60 parts, polyethylene glycol (average molecular weight 4
A mixture of 2 parts, 10 parts of NAI-105 (photoacid generator, manufactured by Midori Chemical Co., Ltd., trade name) and 1.5 parts of the photosensitizer used in Example 1 was dissolved in diethylene glycol dimethyl ether. A photosensitive solution of 20% by weight was obtained.

Using this photosensitive solution, a photosensitive layer was formed in the same manner as in Example 1, and heated at 120 ° C. for 8 minutes. The substrate obtained was irradiated with an argon laser having an intensity of 5 mJ / cm ² through a positive pattern mask. To the above photosensitive layer,
After heating at 10 ° C. for 10 minutes, development was performed using a 1% aqueous solution of sodium carbonate. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and the second harmonic (532 nm) of a YAG laser.

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

Example 45 100 parts (solid content) of the photosensitive solution obtained in Example 1 was mixed with 0.8 equivalent of triethylamine with respect to the carboxyl group, stirred and then dispersed in deionized water to obtain a water-dispersed resin solution ( (Solid content 15%).

The obtained water-dispersed resin solution was used as an electrodeposition coating bath, anion electrodeposition coating was performed so that the dry film thickness was 5 μm using the laminated copper plate as an anode, washed with water, and washed at 120 ° C. for 8 hours.
The substrate was heated at 120 ° C. for 10 minutes by irradiating the photosensitive layer with a 5 mJ / cm ² intensity argon laser through a positive pattern mask.
% Aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and the second harmonic (532 nm) of a YAG laser.

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

Example 46 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 18 parts of dimethylaminoethyl methacrylate,
A reaction product obtained by reacting a mixture of 17 parts of n-butyl acrylate and 3 parts of azobisisobutyronitrile at 100 ° C. for 2 hours is poured into 1500 cc of a toluene solvent, and the reaction product is precipitated and separated. The product was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5000 and a hydroxyphenyl group content of 4.6 mol / kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) and 10 parts of NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd.) A mixture of 1.5 parts of the photosensitizer used in Example 1 was dissolved in diethylene glycol dimethyl ether and adjusted to a solid content of 60% to obtain a photosensitive solution.

100 parts of photosensitive solution obtained above (solid content)
After mixing and stirring 0.8 equivalents of acetic acid with respect to the amino group,
Disperse in deionized water to form a water-dispersed resin solution (solid content 15
%).

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, and a dry film thickness was 5 μm.
After heating for a minute, a photosensitive layer was formed. The photosensitive layer was irradiated with a 5 mJ / cm ² intensity argon laser through a positive pattern mask, heated at 120 ° C. for 10 minutes, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide. did. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Xenon lamp (a light beam whose ultraviolet wavelength region has been cut) and the second harmonic (532) of a YAG laser
nm), similar results were obtained.

After the photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was performed.

Example 47 50 parts of poly (t-butoxycarbonyloxystyrene) (molecular weight: 1000) were added to 1,000 parts of tetrahydrofuran,
50 parts of the following novolak phenolic resin, NAI-105
10 parts of a photoacid generator (trade name, manufactured by Midori Kagaku KK) and 1.5 parts of the photosensitizing dye used in Example 1 were blended to obtain a photosensitive solution having a solid content of 9%.

Production of novolak phenolic resin 1490 parts of o-cresol, 30% formalin 114
5 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 1% 15% hydrochloric acid
After adding 3.5 parts and heating under reflux for 40 minutes, 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. The aqueous layer was removed after neutralization by adding 35% sodium hydroxide solution, and 400 parts of deionized water was added.
After washing the resin at 5 ° C., the aqueous layer was removed and the same washing operation was repeated twice, followed by drying at about 120 ° C. under reduced pressure to obtain a novolak phenol resin having a molecular weight of 600.

Using the photosensitive solution obtained above, a photosensitive layer was formed in the same manner as in Example 1, and after evaporating the solvent, argon was applied to the substrate through a positive pattern mask at an intensity of 5 mJ / cm ^2. A laser is applied to the photosensitive layer to irradiate it with light.
After heating at 10 ° C. for 10 minutes, development was performed using a 1% aqueous solution of sodium carbonate. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and the second harmonic (532 nm) of a YAG laser.

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

Example 48 50 parts of poly (tetrahydropyranyl ether styrene) (molecular weight: 1000) was added to 1,000 parts of tetrahydrofuran,
50 parts of the novolak phenolic resin of Example 45, NAI
A photosensitive solution having a solid content of 9% was obtained by mixing 10 parts of -105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) and 1.5 parts of the photosensitizing dye used in Example 1.

Using this photosensitive solution, a photosensitive layer was formed in the same manner as in Example 1, and after the solvent was evaporated, a 5 mJ / cm ² intensity argon laser was applied to the substrate through a positive pattern mask. The photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with a xenon lamp (a light beam whose ultraviolet wavelength region was cut off) and the second harmonic (532 nm) of a YAG laser.

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

Comparative Example 1 In Example 1, NKX-1595 was used as a photosensitizer.
(Nippon Kogaku Dye Co., Ltd., trade name, coumarin-based compound
) The same feeling as in Example 1 except that 1.5 parts was used.
The light solution was prepared. Using this, the light was exposed in the same manner as in Example 1.
Form a layer, heat at 120 ° C. for 8 minutes, and apply
5mJ / cm through positive pattern mask ^TwoStrength
Irradiate the above photosensitive layer with a Lugon laser at 120 ° C
And then use 1% aqueous sodium carbonate solution
And developed. Residue of film after development for visible light dose
As a result of examining the existence, the coating was not dissolved and was bad.

The second harmonic (532n) of a xenon lamp (a light beam whose ultraviolet wavelength region is cut) and a YAG laser
The same result was not obtained by irradiation of m).

[0112]

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

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

The 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 a stable oscillation line at 8 nm and 514.5 nm and a YAG laser having a bright line at 532 nm as a second harmonic. The photosensitive material obtained using the photosensitive 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.

 ──────────────────────────────────────────────────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 Inside 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 Inc. U Tsukahara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 2H025 AA01 AB01 AB15 AB20 AC01 AC08 AD03 BE00 BG00 CA28 CB17 CB41 CB43 CB45 CC03 FA15 4H048 AA03 AB76 AB92 VA10 VA20 VA30 VA32 VA40 VA75 VB20 4J011 RA03 R A07 RA10 RA11 RA12 SA78 SA85 SA86 SA87 SA89 TA07 UA02 UA06 VA01 WA01 WA05 WA06

Claims (4)

[Claims] 1. A positive visible light-sensitive resin and a photosensitizer.
In the positive visible light-sensitive resin composition containing,
Organic Boron Compound Represented by General Formula (1) as Photosensitizer
-Type visible light-sensitive resin characterized by containing a substance
Composition. Embedded image[Wherein, R₁, R_Two, R_Three, R_Five, R₆, R₇Are independent
Are hydrogen, halogen, nitro, cyano,
Droxy group, amino group, carboxyl group, sulfonic acid
Group, alkyl group, halogenoalkyl group, alkoxyal
Kill group, alkoxy group, alkoxyalkoxy group,
Oxyalkoxyalkoxy group, aryloxy group,
Aralkyloxy group, acyl group, alkoxycarbonyl
Group, aminocarbonyl group, alkylaminocarbonyl
Group, dialkylaminocarbonyl group, alkyl carbonyl
Ruamino group, arylcarbonylamino group, aryla
Minocarbonyl group, aryloxycarbonyl group, ara
Alkyl, aryl, heteroaryl, alkylthio
O group, arylthio group, alkenyloxycarbonyl
Group, aralkyloxycarbonyl group, alkoxycarbo
Nylalkoxycarbonyl group, alkylcarbonylalkyl
Coxycarbonyl group, mono (hydroxyalkyl) amido
Nocarbonyl group, di (hydroxyalkyl) aminocar
Bonyl group, mono (alkoxyalkyl) aminocarboni
And di (alkoxyalkyl) aminocarbonyl groups
Or an alkenyl group;₁, R_Two, R_Three, R_Five, R₆,
R₇At least one of which is an alkoxy group or an alcohol
Xyalkoxy, aryloxy or aralkyl
An oxy group;_FourIs hydrogen atom, cyano group, alkyl
Group, aralkyl group, aryl group, heteroaryl group or
Represents an alkenyl group;₈, R₉Is a halogen atom, al
Kill group, aralkyl group, aryl group, heteroaryl
Group, alkoxy group, alkoxyalkoxy group, alkoxy
Alkoxyalkoxy group, halogenoalkyl group, al
A thioalkyl group, a dialkylaminoalkyl group,
Alkylthioalkoxy group, dialkylaminoalkoxy
Group, dialkylaminoalkoxyalkoxy group, alkyl
Luthio group, alkoxyalkylthio group, alkylthioa
Alkylthio, dialkylaminoalkylthio, ara
Alkyloxy group, aryloxy group, arylthio group,
A heteroaryloxy group or a heteroarylthio group
Represent. Where R₈And R₉Are both halogen atoms,
R₁, R_Two, R _Three, R_Five, R₆, R₇Are all alkenyl groups
Will not be. ] 2. The positive visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and an exposed portion of these resins exposed to visible light is dissolved in an organic solvent or an aqueous developer. 2. The positive-type visible light-sensitive resin composition according to claim 1, wherein the unexposed portion is a resin that does not dissolve in an organic solvent or an aqueous developer. 3. A composition for a positive-type visible light-sensitive material, comprising the positive-type visible light-sensitive resin composition according to claim 1 and a solvent. 4. A positive resist material comprising the positive visible light-sensitive resin composition according to claim 1 on a substrate.