JP2000019738A - Positive visible light sensitive resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing a photosensitizer excellent in preservation stability and high in sensitivity to laser beams of long wavelength by containing a specific dipyrromethene boron complex as the photosensitizer. SOLUTION: This composition contains a dipyrromethene boron complex expressed by a formula, as a photosensitizer. This photosensitizer is excited by absorbing light in a visible light area of 400-700 nm, particularly 400-600 nm, and interacts with resin and a photo-acid generating agent. In the formula, R1-R7 independently represent hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, alkyl group, halogenoalkyl group, alokoxyalkyl group or the like; R4 represents hydrogen atom, cyano group, alkyl group, aralkyl group, aryl group, heteroaryl group or the like; R8 represents alkyl group, aryl group or aralkyl group; and R9 represents halogen atom, alkoxy group, aryloxy group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive-type visible light-sensitive resin composition containing a dipyrromethene boron complex compound having a specific structure as a photosensitizer and exhibiting high sensitivity to light in the visible light region, and to the same. Related to the application.

[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]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a dipyrromethene boron complex compound having a unique structure is used as a photosensitizer. The inventors have found that a visible light-sensitive resin composition solves the conventional problems, and has 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 a dipyrromethene boron complex compound represented,

[0008]

Embedded image

[Wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group,
Cyano group, hydroxy group, amino group, carboxyl group,
Sulfonic acid group, alkyl group, halogenoalkyl group, alkoxyalkyl group, acyl group, alkoxycarbonyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group , Aryloxycarbonyl, aralkyl, aryl, heteroaryl, alkylthio, arylthio, alkenyloxycarbonyl, aralkyloxycarbonyl, alkoxycarbonylalkoxycarbonyl, alkylcarbonylalkoxycarbonyl, mono (hydroxyalkyl) amino Carbonyl group, di (hydroxyalkyl) aminocarbonyl group, mono (alkoxyalkyl) aminocarbonyl group, di (alkoxya) Kill) an amino group or an alkenyl group, R ₄ is a hydrogen atom, a cyano group,
Represents an alkyl group, an aralkyl group, an aryl group, a heteroaryl group or an alkenyl group, and R ₈ represents an alkyl group,
Represents an aryl group or an aralkyl group, and R ₉ represents a halogen atom, an alkoxy group, an aryloxy group or an aralkyloxy group. ]

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 developer, the positive-type visible light-sensitive resin composition described above, 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.

[0011]

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

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

The term "composition for positive-type visible light-sensitive material" used 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 dipyrromethene boron complex compound represented by the general formula (1) is excited by absorbing light in the visible light region of 400 to 700 nm, in particular, light of 400 to 600 nm, and generates resin or light. A compound that interacts with an acid 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 the general 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;
A halogen atom such as a chlorine atom and a bromine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, sec-pentyl group, cyclopentyl group, n
-Hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl Group, 2,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2
2-trimethylpropyl group, 1-ethylbutyl group, 2-
Ethylbutyl group, 1-ethyl-2-methylpropyl group,
Cyclohexyl group, methylcyclopentyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5
-Methylhexyl group, 1,1-dimethylpentyl group,
1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3, 3-dimethylpentyl group, 3,
4-dimethylpentyl group, 1-ethylpentyl group, 2-
Ethylpentyl group, 3-ethylpentyl group, 1,1,2
-Trimethylbutyl group, 1,1,3-trimethylbutyl group, 1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group,
2,3,3-trimethylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-
Ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1-n-
Propylbutyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, methylcyclohexyl group, n-octyl group, 1-methylheptyl group, 2-
Methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl Group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,
2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group Dimethylhexyl group, 4,4
-Dimethylhexyl group, 4,5-dimethylhexyl group,
1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-n-propylpentyl group, 1-isopropylpentyl group, 2-isopropylpentyl group,
1-ethyl-1-methylpentyl group, 1-ethyl-2-
Methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-
1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl- 2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1,1,2-trimethylpentyl group, 1,
1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 1,2,2-trimethylpentyl group,
1,2,3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,2,4-
Trimethylpentyl group, 2,3,4-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,3,3
-Trimethylpentyl group, 3,3,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 2,4
4-trimethylpentyl group, 3,4,4-trimethylpentyl group, 1-n-butylbutyl group, 1-isobutylbutyl group, 1-sec-butylbutyl group, 1-tert-
Butylbutyl group, 2-tert-butylbutyl group, 1-
n-propyl-1-methylbutyl group, 1-n-propyl-2-methylbutyl group, 1-n-propyl-3-methylbutyl group, 1-isopropyl-1-methylbutyl group, 1
-Isopropyl-2-methylbutyl group, 1-isopropyl-3-methylbutyl group, 1,1-diethylbutyl group,
1,2-diethylbutyl group, 1-ethyl-1,2-dimethylbutyl group, 1-ethyl-1,3-dimethylbutyl group, 1-ethyl-2,3-dimethylbutyl group, 2-ethyl-1, 1-dimethylbutyl group, 2-ethyl-1,2-
Dimethylbutyl group, 2-ethyl-1,3-dimethylbutyl group, 2-ethyl-2,3-dimethylbutyl group, 1,2
-Dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, ethylcyclohexyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-pentadecanyl group, decalyl group,
A linear alkyl group having 1 to 20 carbon atoms, such as an icosanyl group, or a branched or cyclic alkyl group having 1 to 10 carbon atoms;

Chloromethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 1,1,1,3,3,3-hexafluoro-
Halogenoalkyl groups such as 2-propyl group and nonafluorobutyl group; methoxyethyl group, ethoxyethyl group, isopropyloxyethyl group, 3-methoxypropyl group,
Alkoxyalkyl groups such as -methoxybutyl 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 A methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, an n-hexyloxycarbonyl group,
alkoxycarbonyl groups such as n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group;

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

Benzyl, phenethyl, 3-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl,
Biphenylmethyl group, 2-anthraquinoylmethyl group,
4-ethylphenylmethyl group, 4-p-isopropylphenylmethyl group, 4-t-butylphenylmethyl group, p
-Isopropylphenylethyl group, t-butylphenylethyl group, 4-t-butylphenylethyl group, tolylmethyl group, tolylethyl group, 2,3-dimethylphenylmethyl group, 2,4-dimethylphenylmethyl group, 2,5-
Dimethylphenylmethyl group, 2,6-dimethylphenylmethyl group, 2,4,6-trimethylphenylmethyl group,
2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3
-Fluorophenylmethyl group, 4-fluorophenylmethyl group, 2-methoxyphenylmethyl group, 3-methoxyphenylmethyl group, 4-methoxyphenylmethyl group, 2
-Ethoxyphenylmethyl group, 3-ethoxyphenylmethyl group, 4-ethoxyphenylmethyl group, 2-n-propoxyphenylmethyl group, 3-n-propoxyphenylmethyl group, 4-n-propoxyphenylmethyl group, 2-
Isopropoxyphenylmethyl group, 3-isopropoxyphenylmethyl group, 4-isopropoxyphenylmethyl group, 2-n-butoxyphenylmethyl group, 3-n-butoxyphenylmethyl group, 4-n-butoxyphenylmethyl group, 2 -Isobutoxyphenylmethyl group, 3-isobutoxyphenylmethyl group, 4-isobutoxyphenylmethyl group, 2-t-butoxyphenylmethyl group, 3-t-
Butoxyphenylmethyl group, 4-t-butoxyphenylmethyl group, 2,3-dimethylphenylethyl group, 2,4
-Dimethylphenylethyl group, 2,5-dimethylphenylethyl group, 2,6-dimethylphenylethyl group, 2,
4,6-trimethylphenylethyl group, 2-chlorophenylethyl group, 3-chlorophenylethyl group, 4-chlorophenylethyl group, 2-bromophenylethyl group, 3
-Bromophenylethyl group, 4-bromophenylethyl group, 2-fluorophenylethyl group, 3-fluorophenylethyl group, 4-fluorophenylethyl group, 2-methoxyphenylethyl group, 3-methoxyphenylethyl group, 4- Methoxyphenylethyl group, 2-ethoxyphenylethyl group, 3-ethoxyphenylethyl group, 4-ethoxyphenylethyl group, 2-n-propoxyphenylethyl group, 3-n-propoxyphenylethyl group, 4-
n-propoxyphenylethyl group, 2-isopropoxyphenylethyl group, 3-isopropoxyphenylethyl group, 4-isopropoxyphenylethyl group, 2-n-butoxyphenylethyl group, 3-n-butoxyphenylethyl group, 4 -N-butoxyphenylethyl group, 2-isobutoxyphenylethyl group, 3-isobutoxyphenylethyl group, 4-isobutoxyphenylethyl group, 2-t
-Butoxyphenylethyl group, 3-t-butoxyphenylethyl group, 4-t-butoxyphenylethyl group, fluoren-9-yl group, 9-methylfluoren-9-yl group, 9-ethylfluoren-9-yl group , 9-propylfluoren-9-yl group, 9-butyl-fluorene-9
An aralkyl group such as an yl group;

Phenyl, naphthyl, anthranyl, 2-methylphenyl, 3-methylphenyl,
-Methylphenyl group, 2,3-dimethylphenyl group,
2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2, 3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-
Trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, cyclohexylphenyl group, octylphenyl group,
2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-
Naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-
Methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-
An aryl group substituted by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as a 2-naphthyl group, an 8-methyl-2-naphthyl group, a 2-ethyl-1-naphthyl group, a 3-methoxyphenyl group A 4-methoxyphenyl group, a 2,3-dimethoxyphenyl group, a 2,4-dimethoxyphenyl group,
2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,6-dimethoxyphenyl group,
2,3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2,
4,6-trimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group, 2 -Methoxy-1-naphthyl group, 3
-Methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1-naphthyl group, 7-methoxy-1-naphthyl group, 8
-Methoxy-1-naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6
Linear, branched or cyclic alkoxy having 1 to 10 carbon atoms such as -methoxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1-naphthyl group, etc. Aryl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group,
Aryl groups substituted with halogen atoms such as bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, etc. Aryl groups, N-methylaminophenyl groups, N, N-dimethylaminophenyl groups, N,
N-diethylaminophenyl, N-phenyl-N-methylaminophenyl, N-tolyl-N-ethylaminophenyl, N-chlorophenyl-N-cyclohexylaminophenyl, N, N-ditolylaminophenyl and the like Substitution of an alkylthioaryl group such as an N-monosubstituted aminoaryl group, an N, N-disubstituted aminoaryl group, a methylthiophenyl group, an ethylthiophenyl group, a methylthionaphthyl group, a phenylthiophenyl group, an arylthioaryl group, or the like; An unsubstituted aryl group;

Pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl, benzoimidazoyl, benzofuranyl, indo-3-yl A heteroaryl group such as a group;

Alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, 3,5,5-trimethylhexylthio; phenylthio; Arylthio groups such as 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group, and naphthylthio group; allyloxycarbonyl group;
Alkenyloxycarbonyl groups such as 2-butenoxycarbonyl group; aralkyloxycarbonyl groups such as benzyloxycarbonyl group, 4-methylbenzyloxycarbonyl group and phenethyloxycarbonyl group; methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group; alkoxycarbonylalkoxycarbonyl groups such as n-propoxycarbonylmethoxycarbonyl group 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 Group, propenyl group, 1-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-methyl-1-butenyl group,
2,2-dicyanovinyl group, 1,2,2-tricyanovinyl group, 2-phenylvinyl group, 2-phenyl-2-cyanovinyl group, 2-cyano-2-ethoxycarbonylvinyl group, 2-cyano-2 -Methoxycarbonylvinyl group, 2-cyano-2-phenacylvinyl group, 2- (benzothiazol-2'-yl) vinyl group, 2- (benzoxazol-2'-yl) vinyl group, 2- [5 ' -Methyl-4 '-(dicyanomethylidene) pyran-2'-yl] alkenyl group such as a vinyl group.

Specific examples of R ₄ include a hydrogen atom; a cyano group; the above-mentioned alkyl group, aralkyl group, aryl 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-ethoxyethyl Pyrrolyl 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, furyl, pyridyl, quinolyl, isoquinolyl, oxazoyl, isoxazoyl, oxadiazoyl, thiadiazoyl, imidazoyl, benzothiazoyl, benzoxazoyl, benzimidazoyl, benzofuryl, indo- Heteroaryl groups such as 3-yl group; vinyl group, propenyl group, 1
-Butenyl group, 1-pentenyl group, 2-pentenyl group,
Examples thereof include alkenyl groups such as a 3-methyl-1-butenyl group, a 2,2-dicyanovinyl group, and a 1,2,2-tricyanovinyl group.

Examples of the alkyl group, aralkyl group and aryl group of R ₈ include the above-mentioned alkyl group, aralkyl group,
An aryl group.

Examples of the halogen atom for R ₉ include halogen atoms such as fluorine, chlorine and bromine.

Examples of the alkoxy group for R ₉ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, and 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-dimethyl Butoxy 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-dimethyl Pentyloxy group, 3,3-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 1-ethylpentyloxy group, 2-ethylpentyloxy group, 3-ethylpentyloxy group, 1,1,2-trimethyl Butoxy 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-dimethyl Hexyloxy group, 4,5-dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyloxy group, 3-
Ethylhexyloxy group, 4-ethylhexyloxy group, 1-n-propylpentyloxy group, 2-n-propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyl An oxy group, a 1-ethyl-2-methylpentyloxy group, a 1-ethyl-3-methylpentyloxy group, a 1-ethyl-4-methylpentyloxy group,
2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2-ethyl-3-methylpentyloxy group, 2-ethyl-4-methylpentyloxy group, 3-ethyl-1- Methylpentyloxy group,
3-ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3-ethyl-4-methylpentyloxy group, 1,1,2-trimethylpentyloxy group, 1,1,3- Trimethylpentyloxy group,
1,1,4-trimethylpentyloxy group, 1,2,2
A trimethylpentyloxy group, a 1,2,3-trimethylpentyloxy group, a 1,2,4-trimethylpentyloxy group, a 1,3,4-trimethylpentyloxy group,
2,2,3-trimethylpentyloxy group, 2,2,4
-Trimethylpentyloxy group, 2,3,4-trimethylpentyloxy group, 1,3,3-trimethylpentyloxy group, 2,3,3-trimethylpentyloxy group,
3,3,4-trimethylpentyloxy group, 1,4,4
-Trimethylpentyloxy group, 2,4,4-trimethylpentyloxy group, 3,4,4-trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-te
rt-butylbutoxy group, 2-tert-butylbutoxy group, 1-n-propyl-1-methylbutoxy group, 1-
n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-isopropyl-1-methylbutoxy group, 1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy Group, 1,
1-diethylbutoxy group, 1,2-diethylbutoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group, 1-ethyl-2,
3-dimethylbutoxy group, 2-ethyl-1,1-dimethylbutoxy group, 2-ethyl-1,2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2-ethyl-2,3- Dimethylbutoxy, 1,2-dimethylcyclohexyloxy, 1,3-dimethylcyclohexyloxy, 1,4-dimethylcyclohexyloxy, ethylcyclohexyloxy, n-nonyloxy, 3,5,5-trimethylhexyloxy Group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-pentadecanyloxy group, 2-decalinoxy group, 4- (t-butyl) cyclohexyloxy group,
Examples thereof include a linear alkoxy group having 1 to 20 carbon atoms, such as an icosanyloxy group, and a branched or cyclic alkoxy group having 1 to 10 carbon atoms.

Examples of the aralkyloxy group for R ₉ include:
Benzyloxy group, phenethyloxy group, 3-phenylpropoxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-naphthylethoxy 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 group, 2-chlorophenylmethoxy group, 3-chlorophenylmethoxy group, 4-chlorophenylmethoxy group, 2-bromophenylmethoxy group, 3-bromophenylmethoxy group, 4-bromophenylmethoxy group, 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-ethoxyphenylmethoxy 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-
A methoxyphenylethoxy group, a 2-ethoxyphenylethoxy group, a 3-ethoxyphenylethoxy group, a 4-ethoxyphenylethoxy group, a 2-n-propoxyphenylethoxy group, a 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
And aralkyloxy groups such as -ethylfluoren-9-yloxy group, 9-propylfluoren-9-yloxy group, and 9-butyl-fluoren-9-yloxy group.

Examples of the aryloxy group for R ₉ include a phenyloxy group, a naphthyloxy group, an anthranyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, 3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-
Dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,6
-Dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group,
2,4,5-trimethylphenyloxy group, 2,4,6
-Trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group, butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, octylphenyloxy group, 2 -Methyl-1-naphthyloxy group, 3-methyl-1-naphthyloxy group,
4-methyl-1-naphthyloxy group, 5-methyl-1-
Naphthyloxy group, 6-methyl-1-naphthyloxy group, 7-methyl-1-naphthyloxy group, 8-methyl-
1-naphthyloxy group, 1-methyl-2-naphthyloxy group, 3-methyl-2-naphthyloxy group, 4-methyl-2-naphthyloxy group, 5-methyl-2-naphthyloxy group, 6-methyl- A linear, branched or cyclic C1-C10 group such as a 2-naphthyloxy group, a 7-methyl-2-naphthyloxy group, an 8-methyl-2-naphthyloxy group, or a 2-ethyl-1-naphthyloxy group. An aryloxy group substituted with an alkyl group, a 3-methoxyphenyloxy group,
4-methoxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 2,6-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy Group, 3,5-dimethoxyphenyloxy group,
3,6-dimethoxyphenyloxy group, 2,3,4-trimethoxyphenyloxy group, 2,3,5-trimethoxyphenyloxy group, 2,3,6-trimethoxyphenyloxy group, 2,4,5 -Trimethoxyphenyloxy group, 2,4,6-trimethoxyphenyloxy group, 3,
4,5-trimethoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, butoxyphenyloxy group, hexyloxyphenyloxy group, cyclohexyloxyphenyloxy group, octyloxyphenyloxy group, 2-methoxy-1 -Naphthyloxy group, 3-methoxy-1-naphthyloxy group, 4-
Methoxy-1-naphthyloxy group, 5-methoxy-1-
Naphthyloxy group, 6-methoxy-1-naphthyloxy group, 7-methoxy-1-naphthyloxy group, 8-methoxy-1-naphthyloxy group, 1-methoxy-2-naphthyloxy group, 3-methoxy-2- Naphthyloxy group, 4
-Methoxy-2-naphthyloxy group, 5-methoxy-2
1 to 1 carbon atoms such as a naphthyloxy group, a 6-methoxy-2-naphthyloxy group, a 7-methoxy-2-naphthyloxy group, an 8-methoxy-2-naphthyloxy group, and a 2-ethoxy-1-naphthyloxy group. Aryloxy group, chlorophenyloxy group, dichlorophenyloxy group, trichlorophenyloxy group, bromophenyloxy group, dibromophenyloxy group, iodophenyloxy group, fluorophenyloxy group substituted with 10 linear, branched or cyclic alkoxy groups An aryloxy group substituted with a halogen atom such as a difluorophenyloxy group, a trifluorophenyloxy group, a tetrafluorophenyloxy group, a pentafluorophenyloxy group, or an aryl substituted with a halogenated alkyl group such as a trifluoromethylphenyloxy group Oxy , N- methylamino phenyl group, N, N- dimethylaminophenyl group, N, N
-Diethylaminophenyloxy group, N-phenyl-N
-Methylaminophenyloxy group, N-tolyl-N-ethylaminophenyloxy group, N-chlorophenyl-N
N-mono-substituted aminoaryloxy groups such as -cyclohexylaminophenyloxy group, N, N-ditolylaminophenyloxy group, N, N-disubstituted aminoaryloxy group, methylthiophenyloxy group, ethylthiophenyloxy group, Substituted or unsubstituted aryloxy groups such as an alkylthioaryloxy group such as a methylthionaphthyloxy group and a phenylthiophenyloxy group, and an arylthioaryloxy group.

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

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

The dipyrromethene boron complex compound represented by the general formula (1) of the present invention is typically represented by the general formula (2) R _{4 in} the presence of an acid such as hydrobromic acid or trifluoroacetic acid. —CHO (2) (wherein R ₄ is as defined above) and a compound represented by the general formula (3) and / or the general formula (4)

[0036]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R ₇ are the same as described above).
Alternatively, the compound is oxidized with an oxidizing agent such as chloranil or the like, and subsequently reacted with boron trihalide to obtain a compound represented by the general formula (5):

[0037]

Embedded image (Wherein, R _{1 to} R ₇ are the same as described above, and X represents a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom). The dipyrromethene boron complex compound represented by the general formula (1) can be easily produced by substituting one or both halogen atoms.

The dipyrromethene boron complex compound represented by the general formula (1) according to the present invention, wherein R ₄ is a hydrogen atom, may be prepared, for example, in the presence of an acid such as hydrobromic acid by the above-mentioned general formula (3). And the general formula (6)

[0039]

Embedded image (Wherein R ₁ , R ₂ , and R ₃ are the same as described above), and subsequently reacted with boron trihalide to obtain a compound represented by the general formula (7):

[0040]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R ₇ are the same as above, and X represents a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.) After obtaining the compound, the compound can be easily prepared by substituting a halogen atom in the same manner as described above.

The halogen substitution is carried out by, for example, using a solvent such as an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon or an amide in the general formula (8) M-OR ₈ (8) R ₈ is the same as described above, and M represents an alkali metal atom such as a sodium atom, a potassium atom, and a lithium atom.) And / or a general formula (9) M′-Z (9) , Z is an alkoxy group, an aryloxy group, or an aralkyloxy group, and M ′ is a compound represented by an alkali metal atom such as a sodium atom, a potassium atom, and a lithium atom. be able to.

The photosensitizer contains at least one photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1), and is used in combination with other known photosensitizers. Is also 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. No.

In this case, the content of the photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) in the photosensitizer is not particularly limited, but a desired effect can be obtained in the present invention. For this purpose, the content of the photosensitizer of the dipyrromethene boron complex 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 more preferably 30% by weight or more, and a photosensitizer containing 50% by weight or more is particularly preferable.

The amount of the dipyrromethene boron complex compound used as the photosensitizer depends on the type and amount of the dipyrromethene boron complex compound represented by the general formula (1) contained in the photosensitizer. The amount of the photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) is usually 0.1 to 10 parts by weight, per 100 parts by weight of the resin component, depending on the type of the resin component to act. Preferably, the amount is in the range of 0.3 to 5 parts by weight. If the amount of the photosensitizer of the dipyrromethene boron complex compound is too less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease, and if it exceeds 10 parts by weight, from the viewpoint of solubility, It tends to be difficult to keep the composition homogeneous.

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, a coating material) which decomposes upon exposure and shows solubility in a developing solution. , An ink, an adhesive, a printing plate material, a resist material for a printed wiring board) containing a photosensitizer of a dipyrromethene boron complex compound represented by the general formula (1) as an essential component. is there.

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

Examples of the positive visible light-sensitive resin in the composition include a resin containing a photoacid generator, a resin containing a component other than the photoacid generator component (for example, 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 containing, as a main component, a resin in which quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group through a sulfonic ester bond. -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, functional groups (hydroxyl group, carboxyl group, etc.) which control solubility in a developer in a resin are blocked (acid-labile groups) to make them insoluble, and the blocks are blocked 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.

Further, as the components thereof, a two-component system comprising a resin having an acid labile group and a photoacid generator, and a three-component system comprising 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.

When 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 other polymerizable unsaturated monomers (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) 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 film 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 alkaline aqueous solution, then irradiate with active energy rays, and then further 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 alkaline aqueous 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. 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 above is
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, the 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.

Further, 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, a coloring agent such as a fluidity regulator, a plasticizer, a dye and a pigment may be added to the composition of the present invention, if necessary.

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, and plate materials (plate materials for plate and letterpress, offset materials). It can be used for a wide range of applications, such as printing PS plates, information recording materials, and relief image forming materials.

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 (eg, chloroform, trichloroethylene, dichloromethane), alcohols (eg, ethyl alcohol, benzyl alcohol), others (eg, dimethylformamide, dimethyl sulfoxide), and water. .

As the support, 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, 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-solubilization of the positive-type visible light-sensitive resin composition is performed 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). Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine, and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as sodium hydroxide and sodium hydroxide; ammonia; Further, examples of the acid neutralizing agent include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent used is the amount of the ionic group 1 contained in the photosensitive resin composition.
0.2 to 1.0 equivalent, particularly 0.3 to 1.0 equivalent per equivalent
A range of 0.8 equivalents is desirable.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n- Butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used is generally 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, for example, a petroleum solvent such as toluene or xylene; methyl ethyl ketone, methyl isobutyl, 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 visible light-sensitive resin composition as an electrodeposition paint can be carried out by a conventionally known method. For example, a resin or a resin mixture that has been made water-soluble by the neutralization, a photosensitizer of a dipyrromethene boron complex compound, and further, if necessary, a solvent and other components are thoroughly mixed,
It can be prepared by adding water.

The composition thus prepared is further diluted with water in a usual manner, for example, in a pH range of 4 to 9 and a bath concentration (solid content concentration) of 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 resulting 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 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 decomposed. An image can be formed by removing the exposed portion by a developing process.

As the light source for exposure, light sources such as ultra-high pressure, high pressure, medium pressure and low pressure mercury 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 where 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, or 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.

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 off 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.

After the protective film is peeled off from the dry film resist, the resist film can be bonded to the support by thermocompression bonding so that the resist film comes into contact with the dry film resist 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.

[0090]

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 product, and NAI-
105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name)
10 parts and compound 1.5 of Table 1-1 as a photosensitizer
A part 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 solution was applied on 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.

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

Examples 2 to 40 Photosensitive liquids were prepared in the same manner as in Example 1 except that 1-2 to 1-40 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 photosensitive sensitivity.

Example 41 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: 1,000), 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 no reduction or swelling of the film in the unexposed portion was observed. Xenon lamp (light beam whose ultraviolet wavelength range is cut) and second harmonic of YAG laser (532 nm)
Irradiation gave similar results.

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 42 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.

[0102] Using this photosensitive solution, similarly to form a photosensitive layer as in Example 1, argon laser 5 mJ / cm ² intensity through the positive pattern mask onto a substrate which is obtained by heating for 8 minutes at 120 ° C. 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 no reduction or swelling of the film in the unexposed portion was observed. Xenon lamp (light beam whose ultraviolet wavelength range is cut) and second harmonic of YAG laser (532 nm)
Irradiation gave similar results.

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

Example 43 100 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 resulting water-dispersed resin solution was used as an electrodeposition coating bath, anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, washed with water, and 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 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.

Further, after the photosensitive layer was allowed to stand at room temperature for 6 months, the same evaluation was carried out.

Example 44 200 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 to a dry film thickness of 5 μm, followed by washing with water and drying at 120 ° C. for 8 hours.
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 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 carried out. As a result, no change was found in the above-mentioned photosensitive sensitivity.

Example 45 To 1,000 parts of tetrahydrofuran, 50 parts of poly (t-butoxycarbonyloxystyrene) (molecular weight: 1000),
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 and refluxing 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, the solvent was evaporated, and 5 mJ / cm ² of argon was applied to the substrate via a positive pattern mask. A laser is applied to the photosensitive layer to emit 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 no reduction or swelling of the film in the unexposed portion was observed. Xenon lamp (light beam whose ultraviolet wavelength range is cut) and second harmonic of YAG laser (532 nm)
Irradiation gave similar results.

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 46 100 parts of poly (tetrahydropyranyl ether styrene) (molecular weight: 1000) was added to 1000 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 liquid, 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 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 carried out. As a result, no change was found in the 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.
A 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.

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

[0119]

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 Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C09K 3/00 H01L 21/30 502R (72) Inventor Hideo Kogure 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. (72) Inventor Akira Ogiso, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd. (72) Inventor Denmi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd. 72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Chemicals Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama Mitsui Chemicals, Inc. F-term (reference) 2H025 AA01 AA11 AB03 AB20 AC01 AC08 AD03 BE00 BE10 BG00 CA28 CA39 CB17 CB41 CC03 FA12 FA15 FA17 4H048 AA03 AB76 AB92 VA11 VA12 VA13 VA20 VA22 VA30 VA32 VA40 VA75 VB20 4J011 QA08 QA09 QA19 QA48 QB29 QC07 RA11 RA12 SA78 SA86 TA07 UA02 WA05 WA01 WA01

Claims (4)

[Claims] 1. A positive visible light-sensitive resin composition comprising a positive visible light-sensitive resin and a photosensitizer,
A positive-type visible light-sensitive resin composition comprising a dipyrromethene boron complex compound represented by the general formula (1) as a photosensitizer. Embedded image [Wherein, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group. , Alkyl group, halogenoalkyl group, alkoxyalkyl group, acyl group, alkoxycarbonyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, arylcarbonylamino group, arylaminocarbonyl group, aryloxy Carbonyl group, aralkyl group, aryl group, heteroaryl group, alkylthio group, arylthio group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, Rokishiarukiru) aminocarbonyl group,
Represents a di (hydroxyalkyl) aminocarbonyl group, a mono (alkoxyalkyl) aminocarbonyl group, a di (alkoxyalkyl) aminocarbonyl group or an alkenyl group, and R ₄ represents a hydrogen atom, a cyano group, an alkyl group, an aralkyl group, an aryl group, Represents a heteroaryl group or an alkenyl group, R ₈ represents an alkyl group, an aryl group or an aralkyl group, and R ₉ represents a halogen atom, an alkoxy group, an aryloxy group or an aralkyloxy group. ] 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.