JP2002169275A - Photoacid producing agent and visible ray photosensitive resin composition by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a visible ray photosensitive resin composition having sufficient sensitivity in the visible ray region, especially for the second harmonic waves of a He-Cd laser, Ar laser and YAG laser and having superior storage stability. SOLUTION: In the visible ray photosensitive resin composition containing a visible ray photosensitive resin and a photoacid producing agent, the composition contains a dipyrromethene compound expressed by general formula (1) as the photoacid producing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a visible light-sensitive resin composition containing a dipyrromethene compound having a specific structure as a photoacid generator and exhibiting high sensitivity to light in the visible light region, and its use. .

[0002]

2. Description of the Related Art In recent years, the development of high-power laser technology and the development of photosensitive materials corresponding thereto have been progressing, and at this time, improvement in cost performance related to laser maintenance is required. For this reason, there is a high demand for high sensitivity as well as high resolution corresponding to miniaturization of processing dimensions, and as a highly sensitive photoresist, a chemically amplified resist using a photoacid generator, which is a photosensitive agent, is good. Are known. The chemically amplified resist is characterized in that an acid is generated from a photoacid generator as a contained component by light irradiation, and an acid-catalyzed reaction occurs on a base resin or the like of the resist in a heat treatment after exposure. In this way, a remarkably high sensitivity is achieved as compared with a conventional resist having a photoreaction efficiency (the number of reactions per photon) of less than 1.

[0003] In plate making in the field of circuit formation and printing of electronic devices, positive photosensitive resin compositions are used. The photosensitive resin composition used for these applications contains, as essential components, a resin in which a functional group in a polymer that is solubilized in an alkaline solution is protected with an acid-decomposable group, and a compound that generates an acid by light irradiation. The composition is a composition in which exposed portions are dissolved in an alkaline solution, while unexposed portions are not dissolved but remain as a resin, and a pattern is formed on a substrate or a lithographic plate.

Conventionally, a recording method in which an image is formed by ultraviolet exposure using a film original or the like has been used, and a resin composition used for the purpose includes, for example, a known compound such as a phenol resin and o-quinonediazide. And the like. At present, due to the development of electronic devices, manuscripts edited electronically by computers,
A method of directly drawing and recording with a high-power laser without using a film 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.

[0005] Many commonly used high-output and stable laser light sources have an output wavelength in the visible region. Specifically, the wavelengths of 488 nm and 514.5 n
An argon laser having a stable oscillation line at m, a YAG laser having a bright line at 532 nm as a second harmonic, a He-Cd laser having an oscillation line at 430 nm, and the like are widely used. Although a blue-violet laser having a line has been developed, a sufficient sensitivity cannot be obtained with respect to these visible light lasers because the sensitivity wavelength region of the conventional resin composition is an ultraviolet region.

As a positive resin composition having sensitivity to an argon laser light source, for example, JP-A-2-1614
45, JP-A-3-75633 discloses a resin composition containing a poly (p-hydroxystyrene) derivative and an iron arene complex as an acid generator. Japanese Patent Application Laid-Open No. 3-2002 describes a composition using a photosensitive resin composition containing a compound capable of generating an acid upon irradiation with an actinic ray and a compound having photosensitivity in the visible region.
57, JP-A-4-153655, JP-A-5-4034
2, JP-A-8-240908 and JP-A-9-24423
3, JP-A-11-202483 and the like.

[0007] In JP-A-2-161445, the absorption wavelength range of the iron arene complex is limited to 300 nm to 560 nm, and cannot be used for other visible light sources. In JP-A-3-75633, the absorption wavelength range is 300 nm to 500 nm. It is limited and cannot be used with the second harmonic of the YAG laser. In the above-mentioned JP-A-3-200257, JP-A-4-153655 and JP-A-5-40342, even when irradiated with visible light, since they are ultraviolet-absorbing acid generators, they do not generate an acid, Sensitizers need to be added.

Further, in the above-mentioned JP-A-8-240908, JP-A-9-244233 and JP-A-11-202483,
In order to obtain an image pattern, it is necessary to perform two-step exposure of sequentially irradiating a visible light laser light source and another light source, which is problematic. In addition, ionic photoacid generators generally have poor solubility in non-polar solvents, leaving room for improvement.

[0009]

SUMMARY OF THE INVENTION The present invention relates to an oscillation line having a wavelength of 488 nm or 514.5 nm of an argon laser, a laser beam having a long wavelength in a visible light region such as 532 nm which is a second harmonic of a YAG laser, or He. -Cd
A photoacid generator which is highly sensitive and excellent in storage stability to various kinds of high power laser light in the visible light region, such as a laser wavelength of 430 nm oscillation line and a blue-violet laser wavelength of 405 nm oscillation line; An object of the present invention is to provide a visible light-sensitive resin composition containing an acid generator.

[0010]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a photoacid generator using a dipyrromethene compound having a specific structure, and a photoacid generator using the dipyrromethene compound. The inventors have found that a visible light-sensitive resin composition containing an acid generator solves the conventional problems, and has completed the present invention.

That is, the present invention relates to a compound represented by the following general formula (1):

[0012]

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[Wherein at least one of R ^{1 to} R ⁷ is a halogen atom, and the others are each independently a hydrogen atom, a nitro group, a cyano group, a carbamoyl group, a substituted or unsubstituted alkyl group, an aralkyl Group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, acyl group, acyloxy group, heteroaryl group, acylamino group L ¹ and L ² each independently represent a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
Aralkyloxy group, an aryloxy group, R ¹ ~
Adjacent groups in R ³ and / or R ^{5 to} R ⁷ may be bonded to each other to form a substituted or unsubstituted ring. ]
A photoacid generator comprising at least one dipyrromethene compound represented by the formula: General formula (2)

[0014]

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[Wherein at least one of R ^{8 to} R ¹⁶ is a halogen atom, and the others are each independently a hydrogen atom,
Nitro group, cyano group, carbamoyl group, substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group , alkenylthio group, an acyl group, an acyloxy group, a heteroaryl group, an acylamino group, L ^1, L ² represents L ^1, L ² the same group in the formula (1), adjacent in R ⁷ to R ⁹ May combine with each other to form a substituted or unsubstituted ring. ]
A photoacid generator comprising at least one dipyrromethene compound represented by the formula: The visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and contains the photoacid generator according to claim 1 or 2 as a photoacid generator. Visible light-sensitive resin composition. A visible light-sensitive resin composition used under an environment of safety light having a large relative luminous efficiency having a maximum wavelength selected from the range of 500 to 620 nm and having an absorbance of an unphotosensitive film formed from the composition. The visible light-sensitive resin composition according to claim 3, wherein the wavelength is 0.5 or less in a range of ± 30 nm of a maximum wavelength selected from the maximum wavelength range of the safety light. The visible light-sensitive resin composition according to claim 4, wherein the safety light is generated by a discharge lamp containing sodium as a main component (mainly a D line having a light wavelength of 589 nm). A composition for a visible light-sensitive material, comprising the visible light-sensitive resin composition according to any one of claims 3 to 5 and a solvent. A visible light-sensitive resist material comprising the visible light-sensitive resin composition according to claim 3 on a substrate. A dipyrromethene boron complex compound represented by the following formula (3):

[0016]

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[In the formula, A represents a residue which forms a saturated ring by bonding to an adjacent carbon atom, and R ^{17 to} R ²² each independently represent a hydrogen atom, a nitro group, a cyano group, a carbamoyl group. A substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, acyl group, X represents a halogen atom, T represents an aryl group or a heteroaryl group, L represents an acyloxy group, a heteroaryl group, or an acylamino group;
¹ and L ² represent the same groups as L ¹ and L ² in the formula (1). ]

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photoacid generator of the dipyrromethene compound represented by the general formula (1) (Chem. 7) can be used as a Lewis acid or a Bronsted acid by irradiating light in the visible light region of 400 to 700 nm, in particular, light of 400 to 600 nm. Is a compound that generates

[0019]

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[Wherein at least one of R ^{1 to} R ⁷ is a halogen atom, and the others are each independently a hydrogen atom, a nitro group, a cyano group, a carbamoyl group, a substituted or unsubstituted alkyl group, an aralkyl Group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group, arylthio group, alkenylthio group, acyl group, acyloxy group, heteroaryl group, acylamino group L ¹ and L ² each independently represent a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
Aralkyloxy group, an aryloxy group, R ¹ ~
Adjacent groups in R ³ and / or R ^{5 to} R ⁷ may be bonded to each other to form a substituted or unsubstituted ring. ] Is represented.

In the compounds represented by the general formula (1) according to the present invention, R ^{1 to} R ⁷ in the formula include, for example, halogen atoms such as fluorine, chlorine, bromine and iodine. Other specific substituents include a hydrogen atom; a nitro group; a cyano group; a carbamoyl group; a methyl group, an ethyl group, an n-propyl group, and an iso-
Propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 1-methylbutyl, neo-pentyl, 1,
2-dimethylpropyl group, 1,1-dimethylpropyl group, cycl
o-pentyl group, n-hexyl group, 4-methylpentyl group, 3-
Methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,
2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,
2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-
Ethyl-2-methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group,
4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,
5-dimethylhexyl group, 2,5,5-trimethylpentyl group,
2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4, 5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl -4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,
5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-
Dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyc
a substituted or unsubstituted alkyl group such as lo-hexyl-2,2-dimethylpropyl group, preferably a substituted or unsubstituted alkyl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl,
Dimethylbenzyl group, trimethylbenzyl group, dichlorobenzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, A substituted or unsubstituted aralkyl group such as a trifluoromethylnaphthylmethyl group, preferably a substituted or unsubstituted aralkyl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl,
Dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, Di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di ( (iso-butyl) phenyl, tri (iso-butyl) phenyl, sec-butylphenyl, di (sec-butyl) phenyl, tri (sec-butyl) phenyl, t-butylphenyl, di (t-butyl) (Butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group,
Iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, Chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group,
A substituted or unsubstituted aryl group such as a trifluoromethylnaphthyl group and an N, N-dimethylaminonaphthyl group, preferably a substituted or unsubstituted aryl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

A vinyl group, a propenyl group, a 1-butenyl group,
iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-
Methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-
Methylcarboxyl vinyl group, 2-cyano-2-methylsulfone vinyl group, substituted or unsubstituted alkenyl group such as 2-phenyl-1-butenyl group, preferably having 20 or less carbon atoms,
More preferably a substituted or unsubstituted alkenyl group having 15 or less carbon atoms;

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy,
Substituted or unsubstituted alkoxy groups such as iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group, preferably substituted or unsubstituted having 20 or less carbon atoms, more preferably 15 or less carbon atoms An alkoxy group of

Benzyloxy, nitrobenzyloxy, cyanobenzyloxy, hydroxybenzyloxy, methylbenzyloxy, trimethylbenzyloxy, dichlorobenzyloxy, methoxybenzyloxy, ethoxybenzyloxy, trifluoromethyl A substituted or unsubstituted aralkyloxy group such as a benzyloxy group, a naphthylmethyloxy group, a nitronaphthylmethyloxy group, a cyanonaphthylmethyloxy group, a hydroxynaphthylmethyloxy group, a methylnaphthylmethoxy group, and a trifluoromethylnaphthylmethoxy group, preferably Is a substituted or unsubstituted aralkyloxy group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Phenoxy group, 2-methylphenoxy group, 4-
A substituted or unsubstituted aryloxy group such as a methylphenoxy group, a 4-t-butylphenoxy group, a 2-methoxyphenoxy group, a 4-iso-propylphenoxy group, preferably having 20 or less carbon atoms, and more preferably having 15 or less carbon atoms A substituted or unsubstituted aryloxy group;

Vinyloxy group, propenyloxy group, 1-
Butenyloxy group, iso-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxy group, 2-methyl-2-butenyloxy group, 2,2 -Dicyanovinyloxy group, 2-cyano-2-methylcarboxylvinyloxy group, 2
-Cyano-2-methylsulfone vinyloxy group, 2-phenyl
A substituted or unsubstituted alkenyl group such as a 1-butenyloxy group, preferably a substituted or unsubstituted alkenyl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, iso-butylthio, sec-butylthio, t-butylthio, n-pentylthio, iso-pentylthio, 2 -Methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,
A substituted or unsubstituted alkylthio group such as a 2-dimethylpropylthio group or a 1,1-dimethylpropylthio group, preferably a substituted or unsubstituted alkylthio group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

A benzylthio group, a nitrobenzylthio group,
Cyanobenzylthio, hydroxybenzylthio, methylbenzylthio, trimethylbenzylthio, dichlorobenzylthio, methoxybenzylthio, ethoxybenzylthio, trifluoromethylbenzylthio, naphthylmethylthio, nitronaphthylmethylthio A substituted or unsubstituted aralkylthio group such as a cyanonaphthylmethylthio group, a hydroxynaphthylmethylthio group, a methylnaphthylmethylthio group, a trifluoromethylnaphthylmethylthio group, preferably a substituent having 20 or less carbon atoms, more preferably a substituent having 15 or less carbon atoms or Unsubstituted aralkylthio group;

A substituted or unsubstituted arylthio group such as a phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group, etc., preferably having 20 or less carbon atoms, more preferably A substituted or unsubstituted arylthio group having 15 or less carbon atoms;

Vinylthio, propenylthio, 1-butenylthio, iso-butenylthio, 1-pentenylthio, 2-pentenylthio, 2-methyl-1-butenylthio, 3-methyl-1-butenylthio, 2-methyl-2-butenylthio group, 2,2-dicyanovinylthio group, 2-cyano-2-methylcarboxylvinylthio group, 2-cyano-2-methylsulfonevinylthio group, 2-phenyl-1-butenylthio group Or a substituted or unsubstituted alkenylthio group, preferably a substituted or unsubstituted alkenylthio group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Formyl, acetyl, ethylcarbonyl, n-propylcarbonyl, iso-propylcarbonyl, n-butylcarbonyl, iso-butylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl,
n-pentylcarbonyl group, iso-pentylcarbonyl group,
a substituted or unsubstituted acyl group such as a neo-pentylcarbonyl group, a 2-methylbutylcarbonyl group, a nitrobenzylcarbonyl group or the like, preferably a substituted or unsubstituted acyl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms; A substituted or unsubstituted acyloxy group such as a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a 2,4-dimethylbutyloxycarbonyl group, preferably a substituted or unsubstituted acyl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms. A substituted acyloxy group;

Substitution of a pyrrolyl group, a thienyl group, a furanyl group, an oxazoyl group, an isoxazoyl group, an oxadiazoyl group, an imidazoyl group, a benzooxazoyl group, a benzothiazoyl group, a benzimidazoyl group, a benzofuranyl group, an indoyl group, an isoindoyl group, etc. Or an unsubstituted heteroaryl group, preferably having 20 or less carbon atoms,
More preferably, a substituted or unsubstituted heteroaryl group having 15 or less carbon atoms; a substituted or unsubstituted acylamino group such as an acetylamino group, an ethylcarbonylamino group, a butylcarbonylamino group, and the like, preferably 20 or less carbon atoms, more preferably A substituted or unsubstituted acylamino group having 15 or less carbon atoms;

In the formula, specific examples of L ¹ and L ² include fluorine,
Halogen atoms such as chlorine, bromine and iodine; methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-
Butyl group, sec-butyl group, t-butyl group, n-pentyl group,
iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group,
4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,
2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group,
1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-
Trimethylbutyl group, 1-ethyl-2-methylpropyl group, c
yclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl Group, 2,5-dimethylhexyl group, 2,
5,5-trimethylpentyl group, 2,4-dimethylhexyl group,
2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group,
4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n
-Dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-
Dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,
Substituted or unsubstituted alkyl groups such as 5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group, preferably having 20 or less carbon atoms More preferably a substituted or unsubstituted alkyl group having 15 or less carbon atoms;

Phenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, methylphenyl,
Dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, di (n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, Di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n-butyl) phenyl group, tri (n-butyl) phenyl group, iso-butylphenyl group, di ( (iso-butyl) phenyl, tri (iso-butyl) phenyl, sec-butylphenyl, di (sec-butyl) phenyl, tri (sec-butyl) phenyl, t-butylphenyl, di (t-butyl) (Butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group,
Iodophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, Chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, methoxynaphthyl group,
A substituted or unsubstituted aryl group such as a trifluoromethylnaphthyl group and an N, N-dimethylaminonaphthyl group, preferably a substituted or unsubstituted aryl group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl,
Trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group, fluorene-9-
A substituted or unsubstituted aralkyl group such as an ylethyl group,
Preferably it has 20 or less carbon atoms, more preferably 15 carbon atoms.
The following substituted or unsubstituted aralkyl groups:

Methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy,
Substituted or unsubstituted alkoxy groups such as iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group, preferably substituted or unsubstituted having 20 or less carbon atoms, more preferably 15 or less carbon atoms An alkoxy group of

Benzyloxy, nitrobenzyloxy, cyanobenzyloxy, hydroxybenzyloxy, methylbenzyloxy, trimethylbenzyloxy, dichlorobenzyloxy, methoxybenzyloxy, ethoxybenzyloxy, trifluoromethyl A substituted or unsubstituted aralkyloxy group such as a benzyloxy group, a naphthylmethyloxy group, a nitronaphthylmethyloxy group, a cyanonaphthylmethyloxy group, a hydroxynaphthylmethyloxy group, a methylnaphthylmethoxy group, and a trifluoromethylnaphthylmethoxy group, preferably Is a substituted or unsubstituted aralkyloxy group having 20 or less carbon atoms, more preferably 15 or less carbon atoms;

Phenoxy group, 2-methylphenoxy group, 4-
A substituted or unsubstituted aryloxy group such as a methylphenoxy group, a 4-t-butylphenoxy group, a 2-methoxyphenoxy group, a 4-iso-propylphenoxy group, preferably having 20 or less carbon atoms, and more preferably having 15 or less carbon atoms A substituted or unsubstituted aryloxy group; and the like.

In R ^{1 to} R ³ and / or R ^{5 to} R ⁷ in the formula, examples of the substituted or unsubstituted ring formed by bonding adjacent groups include the following general formula (4) ( A saturated aliphatic ring represented by the following chemical formula (8), (5) (chemical formula 9), (6) (chemical formula 1)
And aliphatic ring compounds such as unsaturated aliphatic rings represented by 0).

[0042]

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[0043]

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[0044]

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[In the formulas (4) to (6), r ^{1 to} r ²⁰ represent hydrogen, an alkyl group, an alkoxy group, or an aryl group, and n represents 0 or 1. ]

Of these aliphatic rings, preferably -C
_{H 2 CH 2 CH 2 CH 2} -, - CH = CHCH 2 CH 2 -, -
_{CH 2 CH = CHCH 2 -,} - CH 2 CH 2 CH 2 -, - C
_{H 2 C (CH 3) 2} CH 2 CH 2 -, - CH 2 C (CH 3) 2 C
H _2- and the like. In addition, the following general formula (7) (Formula 1)
The aromatic ring represented by 1) is also included.

[0047]

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[In the formula (7), r ^{21 to} r ²⁴ represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or an aryl group, and n represents 0 or 1. ]

Of these aromatic rings, preferably -C
H = CH-CH = CH - , - CH = CH-C (CH 3)
= CH -, - CH = CH -C (CH 2 CH 3) = CH-,
-CH = CH-C (CH [CH _{3] 2)} = CH -, - CH
ＣＨCH—C (OCH ₃ ) ＝ CH— and the like.

In addition, -CH ₂ OCH _2- , -CH
Heterocyclic compounds such as ₂ SCH ₂ — also have R ^{1 to} R ³ and / or R ^5.
Examples of the substituted or unsubstituted ring formed by bonding adjacent groups in R 1 to R ⁷ are given.

The dipyrromethene boron complex compound of the present invention represented by the general formula (1) can be typically produced by the following method.

First, a compound represented by the general formula (8) (Chemical formula 12) and a compound represented by the general formula (9) (Chemical formula 13) are reacted in the presence of an acid catalyst such as hydrobromic acid or hydrochloric acid. By reacting in an appropriate solvent, a dipyrromethene compound represented by the general formula (10) (Formula 14) is obtained. Then, the compound is reacted with boron trihalide to form Q represented by the general formula (11) (formula 15).
Is a halogen atom, a compound of the formula (1)
By substituting one or both of the halogen atoms represented by L, an alkyl group, an aryl group, an aralkyl group,
A dipyrromethene boron complex compound represented by the general formula (1) having an alkoxy group, an aralkyloxy group, and an aryloxy group can be easily produced.

[0053]

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[0054]

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[0055]

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[0056]

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(In the formulas (8) to (11), R ^{1 to} R ⁷
Represents the same group as R ^{1 to} R ⁷ in the formula (1), and Q represents a halogen atom such as fluorine, chlorine, bromine and iodine. )

The halogen substitution can be carried out, for example, in a solvent such as an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon or an amide, by the general formula (12)

[0059]

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(Wherein L ¹ is the same as above, and M represents an alkali metal atom such as a sodium atom, a potassium atom, and a lithium atom), and can be easily substituted. .

Specific examples of the pyrromethene boron complex compound represented by the general formula (1) are not limited thereto, but include the compounds shown in Table 1 (Tables 1 and 2).

[0062]

[Table 1]

[0063]

[Table 2]

In the compound represented by the general formula (2) according to the present invention, specific examples of R ^{8 to} R ^{16 in} the formula include the substituents described above as specific examples of R ^{1 to} R ⁷ in the general formula (1). A substituent group similar to the group hydrogen atom; nitro group; cyano group; carbamoyl group; substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyl group, Examples thereof include an alkylthio group, an aralkylthio group, an arylthio group, an alkenylthio group, an acyl group, an acyloxy group, a heteroaryl group, and an acylamino group. A group having 20 or less carbon atoms is preferable, and a group having 15 or less carbon atoms is preferable. .

[0065] Specific examples in L ^1, L ² expression, general formula (1) in L ^1, L of the same substituents described above as specific examples of the ² substituent group, and the like.

In R ^{8 to} R ¹⁰ , examples of the substituted or unsubstituted ring formed by bonding adjacent groups to each other include R ^{1 to} R ³ and / or R ⁵ to R ⁵ in the general formula (1). R ⁷
Aforementioned general formula Specific examples of (4) to the same alicyclic compound (6), the aromatic ring compound (7), and -CH ₂ OC
Heterocyclic compounds represented by H ₂ —, —CH ₂ SCH ₂ — and the like are mentioned, and preferable rings are also the same as those described above for R ^{1 to} R ³ and / or R ^{5 to} R ⁷ in the general formula (1). The same ring as the ring is exemplified.

Specific examples of the pyrromethene boron complex compound represented by the general formula (2) include, but are not limited to, compounds shown in Table 2 (Tables 3 and 4).

[0068]

[Table 3]

[0069]

[Table 4]

In the compound represented by the general formula (3) according to the present invention, specific examples of A in the formula include -CH ₂ -CH _{2
-, - CH 2 -, -} O -, - S -, - C (CH 3) 2 -C
H ₂ —, —C (CH ₃ ) ₂ —, and the like.

In the formula, specific examples of R ^{17 to} R ²² include R ¹ to R ^22.
Substituent groups similar to the substituent groups described above as specific examples of R ⁷ Hydrogen atom; Nitro group; Cyano group; Carbamoyl group; Substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, alkoxy group An aralkyloxy group, an aryloxy group, an alkenyl group, an alkylthio group, an aralkylthio group, an arylthio group, an alkenylthio group, an acyl group, an acyloxy group, a heteroaryl group,
An acylamino group and the like are mentioned, and a group having 20 or less carbon atoms is preferable, and a group having 15 or less carbon atoms is more preferable.

Specific examples of L ¹ and L ^{2 in} the formula include the same substituent groups as those described above as specific examples of L ¹ and L ^{2 in} the general formula (1).

In the formula, specific examples of X include fluorine, chlorine,
Examples thereof include halogen atoms such as bromine and iodine.

Specific examples of T in the formula include a phenyl group, a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, and a triethylphenyl group. , N-propylphenyl group, di
(n-propyl) phenyl group, tri (n-propyl) phenyl group, iso-propylphenyl group, di (iso-propyl) phenyl group, tri (iso-propyl) phenyl group, n-butylphenyl group, di (n -Butyl) phenyl, tri (n-butyl) phenyl, iso-butylphenyl, di (iso-butyl) phenyl, tri (iso-butyl) phenyl, sec-butylphenyl, di (sec-butyl) phenyl ) Phenyl group, tri (sec-butyl)
Phenyl group, t-butylphenyl group, di (t-butyl) phenyl group, tri (t-butyl) phenyl group, dimethyl-t-butylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, Methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group,
A substituted or unsubstituted aryl group such as a chloronaphthyl group, a bromonaphthyl group, an iodonaphthyl group, a methoxynaphthyl group, a trifluoromethylnaphthyl group, an N, N-dimethylaminonaphthyl group, preferably having 20 or less carbon atoms, more preferably A substituted or unsubstituted aryl group having 15 or less carbon atoms;

Substitution of pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group, isoindyl group, etc. Or an unsubstituted heteroaryl group, preferably having 20 or less carbon atoms,
More preferably, a substituted or unsubstituted heteroaryl group having 15 or less carbon atoms;

Specific examples of the pyrromethene boron complex compound represented by the general formula (3) include, but are not limited to, compounds shown in Table 3 (Tables 5 to 6).

[0077]

[Table 5]

[0078]

[Table 6]

The photoacid generator of the present invention contains at least one photoacid generator of a dipyrromethene boron complex compound represented by the general formula (1), and is used in combination with other known photoacid generators. It may be.

The known photoacid generator is not particularly limited as long as it is a commonly used photoacid generator. For example, SISchlesinger, Photogr. Sci. Eng., 18, 387 (197
4), TSBal et al., Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056
No. Re 27,992, ammonium salts described in JP-A-3-140140, etc., DCNecker et al., Macromolecules, 17, 2468
(1984), CSWenetal, Teh, Proc.Conf.Rad.Curing ASIA,
p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,
069,056, etc., phosphonium salts, JVCrivello et
al, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. New
s, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514 and the like, iodonium salts described in JP-A-2-296,514, etc.
ello etal, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al., J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14,279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivelloe
tal, J. PolymerSci., Polymer Chem. Ed., 17, 2877 (1979),
European Patent Nos. 370,693, 161,811, 410,201,
339,049, 233,567, 297,443, 297,442,
U.S. Pat.Nos. 3,902,114, 4,933,377 and 4,760,013
No. 4,734,444, No. 2,833,827, German Patent No. 2,904,
626, 3,604,580, 3,604,581, JP-A-7-2
Sulfonium salts described in Nos. 8237 and 8-27102, JVCrivello et al., Macromorecules, 10 (6), 1307.
(1977), JVCrivello etal, J. PolymerSci., Polymer Ch
em.Ed., 17,1047 (1979) and the like,
S.Wen etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 Toky
o, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605,
No. 48-36281, JP-A-55-32070, JP-A-60-239736,
JP-A-61-169835, JP-A-61-169837, JP-A-62-582
No. 41, JP-A-62-212401, JP-A-63-70243, JP-A-6
Organohalogen compounds described in 3-298339, K. Meier et.
al, J. Rad. Curing, 13 (4), 26 (1986), TPGill et al, I
norg.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.Res., 1
9 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-146445, S. Hayase et al., J. Polymer Sc
i., 25,753 (1987), E.Reichmanisetal, J.Pholymer Sci., P
olymer Chem.Ed., 23,1 (1985), QQZhu et al, J.Photoche
m., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron Let
t., (24) 2205 (1973), DHR Barton et al., J. Chem Soc., 35
71 (1965), PM Collins et al., J. Chem. SoC., Perkin I, 16
95 (1975), M. Rudinstein et al., Tetrahedron Lett., (17),
1445 (1975), JWWalker etal J. Am. Chem. Soc., 110, 7170
(1988), SCBusman et al., J. Imaging Technol., 11 (4), 19
1 (1985), HM Houlihan et al, Macormolecules, 21, 2001 (1
988), PMCollins et al., J. Chem. Soc., Chem. Commun., 53
2 (1972), S. Hayase etal, Macromolecules, 18, 1799 (198
5), E. Reichman et al., J. Electrochem. Soc., Solid State
Sci.Technol., 130 (6), FMHoulihan et al, Macromolcule
s, 21, 2001 (1988), European Patent Nos. 0290,750 and 046,083
No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538
, A photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA et al., Polyme
r Preprints Japan, 35 (8), G. Berner et al., J. Rad. Curin
g, 13 (4), WJMijs etal, Coating Technol., 55 (697), 45
(1983), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 044,115
No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A 2-2457
No. 56, iminosulfone described in JP-A-3-140109 and the like
Compounds that generate sulfonic acid upon photolysis, such as those disclosed in JP-A-61-166544, JP-A-2-71270, JP-A-3-103854,
Examples thereof include diazoketosulfones and diazodisulfone compounds described in JP-A-3-103856 and JP-A-210960.

In this case, the content of the dipyrromethene boron complex compound represented by the general formula (1) in the photoacid generator is not particularly limited, but the desired effects of the present invention can be obtained. In order to obtain, the content of the dipyrromethene boron complex compound represented by the general formula (1) in the photoacid generator is 10% by weight.
Or more, more preferably 20% by weight.
Or more, more preferably 30% by weight or more,
Photoacid generators containing 50% by weight or more are particularly preferred.

The amount of the photoacid generator of the dipyrromethene boron complex compound used depends on the kind and amount of the photoacid generator of the dipyrromethene boron complex compound represented by the general formula (1) contained in the photoacid generator, The amount of the photoacid generator of the dipyrromethene boron complex compound represented by the general formula (1) is usually 0.1 to 10 per 100 parts by weight of the resin component, although it varies depending on the type of the resin component to be acted on. Parts by weight, preferably 0.1 parts by weight.
A range of 3 to 5 parts by weight is suitable. When the use amount of the photoacid generator of the dipyrromethene complex compound is too less than 0.1 part by weight, there is a tendency that sufficient pattern forming ability cannot be obtained,
If the amount is more than 10 parts by weight, it tends to be difficult to keep the composition in a uniform state from the viewpoint of solubility.

The visible light-sensitive resin composition of the present invention can obtain the desired sensitivity by using only the photoacid generator, but a sensitizer may be added if necessary. The known sensitizer is not particularly limited as long as it is a commonly used photosensitizer. Ketocoumarin, coumarin-6, and JP-A-4-14-1 can be used.
Coumarin compound described in JP-A-888 / 88
And dipyrromethene boron complex compounds described in JP-A-322744 and the like.

The visible light-sensitive resin composition of the present invention changes the solubility in a developing solution due to decomposition or cross-linking of the compound upon exposure, and forms a pattern in the developing step. A photosensitive resin composition (for example, a paint, an ink, an adhesive, a printing plate material, a resist material for a printed wiring board) or a negative visible light-sensitive resin composition (for example, a hologram material,
Used in printing plates, etc.) to the general formula (1)
The photoacid generator of the dipyrromethene boron complex compound represented by the following formula is contained as an essential component.

A resin composition containing a resin which is insoluble in a developer but is solubilized in a developer by a decomposition reaction due to an acid group generated from a photoacid generator and the acid generator of the present invention is a positive-type visible light-sensitive resin. It can be used as a conductive resin composition. In addition, if the photoacid generator of the present invention is contained in a resin which has high solubility in a developer but becomes insoluble in the developer when an acid group causes a curing reaction, a negative visible light-sensitive resin It can also be used as a composition.

The visible light-sensitive resin of the present invention is not limited to either a positive type or a negative type. In particular, a positive type visible light-sensitive resin composition which is a useful application of the present invention will be described below. Will be described.

Examples of the composition include a resin containing a photoacid generator, a resin containing components other than the photoacid generator component (eg, a photosensitizer, etc.), and a resin composition which decomposes itself by light. And the like. 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 composition may contain a component such as a photoacid generator or 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. These resins may further contain other resins for adjusting the solubility of the developer, if necessary.

The resin composition containing the above-described photoacid generator component is a resin in which the photoacid generator is incorporated in a resin skeleton (for example, the resin generates an acid group upon exposure to light, thereby enabling alkali development. ) Or a mixture of a photoacid generator and a resin (acids generated by the photoacid generator cause the resin to be cut to have a low molecular weight,
A soluble substance (for example, a mixture which changes into a (poly) P-hydroxystyrene) and thereby becomes dispersible or soluble in an organic solvent or an aqueous developer]. Compositions mainly composed of a resin in which quinonediazidesulfonic acids are bonded to a base resin such as an acrylic resin having a forming group via a sulfonic acid ester bond (JP-A-61-206293, JP-A-7-133449) Etc.), 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;
Chemical amplification-based photosensitization utilizing the change in solubility between irradiated and unirradiated parts by causing a elimination reaction to occur in the base resin (polymer) in a chain using a photoacid generator that generates an acid group by irradiation light as a catalyst. Materials (Japanese Patent Laid-Open No. 4-226461, U.S. Pat.
No. 628, JP-A-59-45439, JP-A-63-250642, Po
lymers in Electronics ”edited by Davidson T. ACS Symposi
um Series 242, American Chemical Society, Washington
DC, 1984, 11 ", N. Hayashi, T. Ueno, M. Toriumi, et.
c, ACS Polym.materials Sci. Eng., 61,417 (1989), H.It
o, CGWilson, ACS Symp. Ser., 242, 11 (1984), etc.);
A crosslinked film insoluble in a solvent or an alkaline aqueous solution is formed by heating, and the crosslinked structure is further cut by a photoacid generator that generates an acid group by irradiation with light, and the irradiated portion becomes soluble in the solvent or the aqueous alkaline solution. Positive photosensitive composition utilizing a mechanism (JP-A-6-295064,
6-308733, JP-A-6-313134, JP-A-6-3131
No. 35, JP-A-6-313136, JP-A-77-146552, etc.).

Of the above resin compositions, the functional groups (hydroxyl groups, carboxyl groups, etc.) that affect the solubility in a developing solution in the resin are converted into insoluble acid-decomposable groups in the developing solution. Is a resin composition that protects (protecting group), generates an acid from a photoacid generator at the time of light irradiation, releases the protecting group, and restores the solubility of the polymer.

As a functional group which affects solubility, a protecting group (R of --OR) for protecting a typical hydroxyl group (--OH group)
Group) includes a t-butoxycarbonyl group (t-BOC)
Group), t-butoxy group, t-butoxycarbonylmethyl group, tetrahydropyranyl group, trimethylsilyl group, i
The resin having a hydroxyl group is not particularly limited as long as it exhibits the above-mentioned effects, and examples thereof include a resin having a phenolic hydroxyl group.

As the protecting group, particularly, a t-BOC group, t-
-Butoxy groups are preferred, and resins having this protecting group, poly (t-butoxycarbonyloxystyrene), poly (t-butoxycarbonyloxy-α-styrene), poly (t-butoxystyrene) and these monomers and other A copolymer with a polymerizable monomer (eg, an alkyl or cycloalkyl methyl (meth) acrylate, maleimide, sulfone, or the like) is preferable as the base resin. Taking the composition of poly (t-butoxycarbonyloxystyrene) containing a t-BOC group as an example, t-BOC is generated by an acid generated by a photoacid generator.
The groups are decomposed to evaporate isobutene and carbon dioxide gas to form polystyrene, and the t-BOC group changes to a hydroxyl group to change (increase) the polarity of the resin, thereby improving the solubility in a developing solution (aqueous alkaline solution). I do. For this reason, the unexposed portion is insoluble in the developing solution, whereas the exposed portion is soluble in the developing solution.

Further, a protecting group (—COO group) for a carboxyl group (—COOH group) which affects the solubility in a developing solution.
Examples of the R ′ group of R ′) include a carboxylic acid ester derivative having a t-butyl group.

The resin composition can be used as a two-component system consisting of a resin having an acid-decomposable protecting group and a photoacid generator. Other resins may be added as a third component. For example, the physical properties of the resin composition can be appropriately adjusted, for example, by improving the coating workability of the composition or changing the solubility in a developer.

The resin composition described above comprises a resin (a) containing a carboxyl group and / or a hydroxyphenyl group, an olefinically unsaturated compound containing an ether bond (b), a photoacid generating an acid group upon irradiation with light. It is a liquid or solid resin composition containing a generator.

In the resin (a) containing a carboxyl group and / or a hydroxyphenyl group, examples of the resin containing a carboxyl group include acrylic resins and polyester resins.
It preferably has a number average molecular weight of about 0000, especially about 1500 to 30000, and a preferred carboxyl group content per kg of resin is about 0.5 to 10 mol, and about 0.7 to 5 mol is about 0.7 to 5 mol. Particularly preferred.

As the hydroxyphenyl group-containing resin,
Condensates of monofunctional or polyfunctional phenol compounds, alkylphenol compounds, or mixtures thereof with carbonyl compounds such as formaldehyde and acetone; hydroxyphenyl group-containing unsaturated monomers such as P-hydroxystyrene; Copolymers with other polymerizable unsaturated monomers and the like can be mentioned, but generally about 500 to about 10
It preferably has a number average molecular weight of about 0000, especially about 1500 to 30000, and a preferred hydroxyphenyl group content per kg of resin is about 1.0 mol or more, and about 2 to 8 mol is particularly preferred.

In addition, a resin containing a carboxyl group and a hydroxyphenyl group may be mixed and used, but the mixing ratio is 90/10 to 10/9.
It is preferred to mix at 0 weight ratio.

Alternatively, a resin having both a carboxyl group and a hydroxyphenyl group in the same molecule can be used. For example, a carboxyl group-containing polymerizable unsaturated monomer (such as (meth) acrylic acid) and a hydroxyphenyl group-containing polymerizable unsaturated monomer (such as hydroxystyrene), and if necessary, other polymerizable unsaturated monomers. (Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Copolymers with aromatic compounds, nitrogen-containing unsaturated monomers such as (meth) acrylonitrile, etc.); and hydroxybenzoic acids, gallic acid, resorcinic acid, etc., or phenol, naphthols, resorcinol, catechol, etc. Phenol resin etc. obtained by reacting the mixture with formaldehyde can be used. Generally from about 500 to about 100,000, especially about 1,500 to 30,000
It is preferable to have the number average molecular weight. The carboxyl group content per kg of the resin is preferably about 0.5 to 10 mol, particularly preferably about 0.7 to 5 mol, and the hydroxyphenyl group content is preferably about 1.0 mol or more, particularly preferably. Is about 2 to 8 mol.

The olefinically unsaturated compound (b) containing an ether bond includes, for example, about 1 to 4 unsaturated ether groups such as vinyl ether group, 1-propenyl ether group and 1-butenyl ether group at the molecular terminal. In one molecule, the formula -R "-O-α [where α
Represents a vinyl, 1-propenyl or 1-butenyl olefinically unsaturated group, and R ″ represents a linear or branched alkylene group having 1 to 6 carbon atoms such as ethylene, propylene and butylene. A low or high molecular weight compound containing at least one, preferably 2 to 4 unsaturated ether groups is preferred.

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 chloroethyl vinyl ether Condensates with halogenated alkyl unsaturated ethers such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. and hydroxyalkyl unsaturated ethers such as hydroxyethyl vinyl ether. No. In particular, the condensate of the above-mentioned polyphenol compound and an alkyl halide unsaturated ether and the reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl unsaturated ether are preferred in terms of etching resistance, precision of a formed pattern, and the like. It is suitable.

The unsaturated compound (b) is a resin (a) 100
It is mixed in an amount of usually about 5 to 150 parts by weight, preferably about 10 to 100 parts by weight with respect to parts by weight. Resin (a)
And a composition containing the unsaturated compound (b) component, when heated, is crosslinked by an addition reaction between a carboxyl group and / or a hydroxyphenyl group and an unsaturated ether group, and becomes insoluble in a solvent or an aqueous alkaline solution. . Here, irradiation with active energy rays, and further heating after irradiation, result in a positive photosensitive resin composition in which the crosslinked structure is cut by the catalytic action of the generated acid and the irradiated portion becomes soluble again in a solvent or an aqueous alkaline solution. .

In the positive photosensitive resin composition, an acid hydrolysis reaction occurs in an exposed portion due to an acid generated when a film to be formed is exposed. Is desirably present.
Therefore, in the composition of the present invention, polyethylene glycol, polypropylene glycol, methylcellulose, by including a hydrophilic resin such as ethylcellulose, so as to easily incorporate the water required for the above reaction in the formed coating film. By doing so, a suitable positive photosensitive resin composition can be obtained. The amount of the hydrophilic resin added is 20 parts by weight or less, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin component.

In order to adjust the solubility of the composition of the present invention in an organic solvent or an aqueous developer, a phenolic resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, silicone Resin, fluorine-based resin and a mixed resin or modified resin of two or more thereof, and also suitable flexibility for the composition of the present invention,
A plasticizer such as a phthalic acid ester, a polyester resin, an acrylic resin, or the like may be further blended as necessary to impart non-adhesiveness. In addition, a colorant such as a fluidity regulator, a plasticizer, a dye, and a pigment may be added to the composition of the present invention.

The positive-type visible light-sensitive resin composition of the present invention may be used as a known photosensitive material generally used, for example, paints, inks, adhesives, resist materials, and the like.
It can be used for a wide range of applications such as printing plate materials (plate making materials, plate making materials for letterpress, PS plates for offset printing, etc.), information recording materials, and relief image producing materials.

The use of the present invention as the positive visible light-sensitive resin will be described below. When used for a general positive photosensitive resist material, the positive visible light-sensitive resin composition of the present invention is dispersed or dissolved in a solvent (including water). Finely dispersed)
The photosensitive liquid can be used by preparing a photosensitive liquid, applying it on a support using a coating device (roller, roll coater, spin coater, etc.) and drying.

At this time, as a solvent used for dissolving or dispersing the resin composition, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, Methyl ether propionate), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenation Hydrocarbons (chloroform, trichloroethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, dimethylsulfoxide, etc.), water and the like. Metal sheets such as aluminum, magnesium, copper, zinc, chromium, nickel, and iron or alloys containing them, or printed circuit boards, plastic, glass or silicone wafers, carbon, etc., whose surfaces are treated with these metals No.

When the positive-type visible light-sensitive resin composition of the present invention is dispersed in water or made into an aqueous solution, it can be used as a positive resist material for electrodeposition coating. In the case where an anionic group such as a carboxyl group is introduced into the resin, if a cationic group such as an amino group neutralized with an alkali (neutralizing agent) is introduced into the resin, an acid (in the middle) is used. This is carried out by neutralization with a humectant. Monoethanolamine, diethanolamine,
Alkanolamines such as triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine; alkylalkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; , Alkali metal hydroxides such as sodium hydroxide; ammonia and the like;
Examples of the acid neutralizer 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 generally 0.2 to 1 equivalent of the ionic group contained in the photosensitive resin composition.
-1.0 equivalent is preferred, and 0.3-0.8 equivalent is particularly preferred.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, methanol, ethanol, isopropanol, n-butanol,
A hydrophilic solvent such as t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, and tetrahydrofuran can be added.
The amount used is preferably 300 parts by weight or less, more preferably 100 parts by weight or less, per 0 parts by weight.

Further, in order to increase the amount of coating on the object to be coated, petroleum solvents such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Esters;
Hydrophobic solvents such as alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added, but the amount is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, per 100 parts by weight of the resin solid component.

The preparation of a positive visible light photosensitive resin composition as a resist for electrodeposition coating can be performed by a known method, for example, a resin or a resin mixture which has been made water-soluble by the above-mentioned neutralization, a photosensitizer of an indolizine compound. If necessary, a solvent and other components can be mixed well, and water can be added.

The composition thus prepared may have, for example, a pH of 4 to 9 and a bath concentration (solids concentration) of 3 to 2
A resist for electrodeposition coating (or an electrodeposition bath) is prepared by an ordinary method such as dilution with water so as to be in the range of 5% by weight, preferably 5 to 15% by weight.

The resist for electrodeposition coating prepared as described above can be applied to the surface of a 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 controlled at 15 to 40 ° C, preferably 15 to 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 film thickness obtained is a dry film thickness, generally 0.5
５０50 μm, preferably 1-20 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then the water and the like contained in the electrodeposition coating film are dried and removed by hot air or the like (as a composition, the above-mentioned carboxyl group and / or hydroxyphenyl is used). When the group-containing resin (a) and the ether bond-containing olefinically unsaturated compound (b) are used, the coated substrate is treated with a carboxyl group- and / or hydroxyphenyl group-containing polymer and a vinyl ether group-containing compound. The coating is cross-linked and cured by heating at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes under the temperature and time conditions under which the cross-linking reaction substantially occurs.

As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material obtained by fixing these materials on the surface of plastic or glass by lamination, plating or the like can be used.
The visible light resist material thus formed on the conductor surface, and the visible light resist electrodeposition coating film obtained by electrodeposition coating are exposed to visible light according to the image, decomposed, and the exposed portion is developed. An image can be formed by removing by processing.

The light source for exposure is obtained from each of 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,
He-Cd laser, argon laser, second harmonic (532 nm) of YAG laser, or GaN laser (405 nm) is preferable.

The developing treatment is carried out by rinsing with an aqueous alkali solution when the non-exposed film is anionic, and with an aqueous acid solution having a pH of 5 or less when the 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 developing a photosensitive resin having no ionic group, the development is performed by dissolving an unexposed portion using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, or methylene chloride. The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. Also, if necessary,
After etching to remove the exposed conductor, the resist film is removed, and a printed circuit board can be manufactured.

When the resin (a) containing a carboxyl group and / or a hydroxyphenyl group and the olefinically unsaturated compound containing an ether bond (b) are used as the composition, the substrate irradiated with visible light is used. Under the temperature and time conditions under which the crosslinked structure of the cured coating film is cut in the presence of the acid generated by the irradiation, for example, about 60 to
The coating is heated at a temperature of about 150 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating on the irradiated portion. At that time, it is preferable that the substrate irradiated with visible light is brought into contact with water in advance.
This is because an acid is easily generated by contact with water, and the cutting reaction of the next crosslinked structure is facilitated.The contact with water is performed by immersing the substrate in room temperature water or warm water, or by spraying steam. It can be carried out.

The positive visible light-sensitive resin composition of the present invention may be used as a transparent resin film such as a polyester resin such as polyethylene terephthalate, an acrylic resin, polyethylene, or a polyvinyl chloride resin as a cover film layer. On top, the resin composition of the present invention was roll-coated.
And a resist film (dry film thickness of about 0.5 to 5) by applying and drying using a coater, blade coater, curtain flow coater or the like.
μm) can be used as a dry film resist in which a protective film is attached to the surface of the film. This dry film resist, after peeling off the protective film, can be bonded by a method such as thermocompression bonding to the support so that the resist film is in contact with the support, to form a resist film, similar to the above-mentioned electrodeposition coating film According to the method described above, an image can be formed by exposing to visible light and developing according to the image.

In general, the environment in which the photosensitive resin composition is used is required to be illuminated with a so-called safety light which does not cause a photoreaction with the photosensitive resin composition. In many cases, a fluorescent lamp colored red was used. However, the emission spectrum of a fluorescent lamp has a wide wavelength range from ultraviolet light to visible light (FIG. 4).
Therefore, even with a red fluorescent lamp, if the illumination intensity is high, even a visible light-sensitive resin coating portion that does not require a photoreaction partially reacts, and a clear resist pattern may not be formed. . For this reason, it is required to work with the intensity of the illumination light as small as possible, and there is a problem that the working environment is further darkened.

On the other hand, in the visible light-sensitive resin composition of the present invention, it is possible to use, as a safe light, irradiation light in a region having a high relative luminosity factor such as a sodium lamp having a sharp wavelength. Was found. For this reason, even in the case of the same illumination light intensity, it is possible to work in an environment of a safe light which is very bright for workers compared to the conventional safety light,
It solves the above problems and has excellent effects such as safe workability, work efficiency, and product quality stability.

The safe light used in the present invention is 500 to 62.
It is a visible light with a large relative luminous efficiency having a maximum wavelength in the range of 0 nm, preferably 510 to 600 nm. This safety light can be obtained, for example, by using a discharge lamp that emits light having a maximum wavelength in the above-mentioned range by discharging in a gas such as sodium. Among them, the sodium lamp emits light having a wavelength of 58 nm.
9 nm yellow D line is the main component, and since it is monochromatic light, the object can be seen sharply with little chromatic aberration, so that it is excellent in safety and work environment. FIG. 1 shows the wavelength of the spectral distribution of the low-pressure sodium lamp. In the spectral distribution diagram of the sodium lamp, as shown in the spectral distribution diagram 1, other than the D line having the maximum wavelength of the sodium lamp, a high-energy light (low wavelength) is used so as not to adversely affect the visible light curable resin composition. Region). Further, it is possible to use a sodium lamp in which a high energy ray other than the D ray is cut by applying a filter. FIG. 2 shows the spectral distribution of the sodium lamp from which high-energy rays have been cut.

A filter can be used for the safety light used in the present invention. As the filter,
For example, Fantuck FD-1081 Scarlet,
FANTAC FC-1431 Sunflower Yellow (trade name, manufactured by Kansai Paint Co., Ltd.), Lintec Lumicool Film NO. 1905 (trade name, manufactured by Lintec Corporation) and the like.

As the safe light used in the present invention, it is preferable to use a sharp single light color having a light ray of 589 nm like a sodium lamp. However, in addition to the maximum wavelength being within the above range, ultraviolet light and visible light are used. Alternatively, safety light having wavelengths distributed in the wavelength range of infrared light may be used. However, when using safety light having such a distribution, it is necessary that the distributed light beam region is a safe light region which does not adversely affect (photosensitize) the positive-type visible light photosensitive resin composition. It is.

Such a safe high-energy light region (low-wavelength region) is related to the energy intensity of the distributed light beam and the absorbance of the positive-type visible light-sensitive resin composition in that region, and the energy intensity of the light beam is large. In the case where the composition has a small absorbance, and in the case where the energy intensity of the light beam is small, the composition can be used in which the absorbance is relatively larger than that of the former, so that the composition is taken into consideration. Can have a high-energy ray region to such an extent that it does not adversely affect light. However, even if a normal fluorescent lamp having a maximum wavelength in the range of 500 to 620 nm is used as the safety light, the oscillation line has a large light energy intensity of less than 500 nm, especially 400 to 499 nm. It cannot be used as a safe light for a positive-type visible light photosensitive resin composition that is exposed to visible light laser.

The absorbance in the present invention is -log (I /
I0). Here, I is the intensity of the transmitted light of the coating obtained by applying the photosensitive resin composition to the surface of the transparent substrate and drying (removing the solvent), and I0 is the blank [for applying the sample (photosensitive resin composition)]. Of a transparent substrate (for example, a polyethylene terephthalate sheet)].

The brightness caused by the light entering the human eye can be represented by relative luminous efficiency. The relative luminous efficiency is JI
As defined in SZ8113, 2005, under certain observation conditions, when it is determined that the monochromatic radiation of a certain wavelength λ has the same brightness as the radiation used as a reference for comparison, the monochromatic radiation of a wavelength λ is determined. It is defined as the reciprocal of the relative value of the radiance, usually normalized such that the maximum value when λ is changed becomes 1. FIG. 3 shows a relative luminous efficiency curve of 380 to 780 nm, which is a wavelength region of visible light. In FIG. 3, the vertical axis represents the ratio, with the maximum value of the relative luminous efficiency set to 100. From this curve, it can be seen from the conventional safety light that the red wavelength 64
It can be seen that the relative luminous efficiency is low at 0 to 780 nm. In other words, it can be seen that the human eye perceives the brightness as being relatively low. For example, to make the human eye feel the same brightness as the wavelength of 589 nm, the radiation intensity must be further increased.
The maximum value of the visibility is about 555 nm (JIS-Z81).
132008).

The visible light-sensitive resin composition of the present invention is a visible light-sensitive resin composition containing a visible light-sensitive resin and a photoacid generator of a dipyrromethene compound having a specific structure. The absorbance of the unexposed film formed from the product is in the range of ± 30 nm (-30 nm to +30 nm), preferably ± 20 nm (−20 nm to +20 nm) of the maximum wavelength selected from the range of the maximum wavelength of the safe light; Furthermore, in the range of ± 10 nm (−10 nm to +10 nm), it is 0.5 or less, preferably 0.2 or less, and more preferably 0.1 or less.
These are:

[0128]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to embodiments. The present invention is not limited by the following embodiments. “Parts” in Examples and Comparative Examples indicates “parts by weight”.

Synthesis Example 1 Synthesis of dipyrromethene boron complex compound In 40 ml of ethanol, 0.62 g of 2-mesityl-4-methylisoindole and 0.49 g of 2-formylpyrrole
Was added and stirred at room temperature for 10 minutes to dissolve. After adding 0.47 g of a 47% aqueous solution of hydrobromic acid and stirring at room temperature for 8 hours, the solution discharged into 120 ml of water was extracted with chloroform to obtain 0.69 g of dipyrromethene. Next, 60 ml of DMF was added to 0.51 g of dipyrromethene obtained above,
After heating and dissolving at 50 ° C., the mixture was cooled to room temperature, 0.34 g of N-bromosuccinimide was added, and the mixture was stirred for 2 hours.
By discharging into 60 ml of water and washing with water, 0.46 g of brominated dipyrromethene was obtained. Further, 20 ml of toluene, 0.88 g of ethyldiisopropylamine, and 1.00 g of trifluoroboron ethyl ether complex were added to 0.43 g of the above brominated dipyrromethene, reacted at 70 ° C. for 2 hours, discharged into 100 ml of water, and extracted with toluene. Thus, 0.50 g of a dipyrromethene boron complex of the formula (1-1), which is a target compound, was obtained. Elemental analysis Found C: 67.29 H: 4.86 N: 4.92 Theoretical C: 67.05 H: 4.72 N: 5.05 MS: 554

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, a mixture of 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) and 10 parts of the compound of Synthesis Example 1 as an acid generator was dissolved in 100 parts of the mixture in diethylene glycol dimethyl ether. The solid content was adjusted to 20% to obtain a photosensitive solution. Next, this photosensitive liquid 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 an argon laser through a positive pattern mask onto the above 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 the reduction and swelling of the film in the unexposed portion were not observed at all. Xenon lamp (light beam whose ultraviolet wavelength region is cut) and the second harmonic (532n) of YAG laser
Similar good results were obtained by irradiation of m).

Examples 2 to 18 Photosensitive liquids were prepared in the same manner as in Example 1, except that 1-1 to 1-17 in Table 1 were used as photoacid generators. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and the resulting substrate was irradiated with an argon laser through a positive pattern mask to irradiate the photosensitive layer with light. After heating at 120 ° C for 10 minutes, 1%
Development was performed using an 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. 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 gave good results similar to those obtained with an argon laser.

Examples 19 to 42 Photosensitive liquids were prepared in the same manner as in Example 1, except that 2-1 to 2-24 in Table 2 were used as photoacid generators. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and the resulting substrate was irradiated with an argon laser through a positive pattern mask to irradiate the photosensitive layer with light. After heating at 120 ° C for 10 minutes, 1%
Development was performed using an 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. 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 gave good results similar to those obtained with an argon laser.

Examples 43 to 66 Photosensitive liquids were prepared in the same manner as in Example 1, except that 3-1 to 3-24 in Table 3 were used as photoacid generators. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and the resulting substrate was irradiated with an argon laser through a positive pattern mask to irradiate the photosensitive layer with light. After heating at 120 ° C for 10 minutes, 1%
Development was performed using an 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. 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 gave good results similar to those obtained with an argon laser.

Example 67 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 had been heated to 80 ° C. and stirred, over 2 hours, and then kept at that temperature for another 2 hours to obtain a solid content of about 62.5. %, 3 mol / kg of carboxyl group was obtained. 80 parts of the carboxyl group-containing polymer (solid content: 62.5%) obtained above, 20 parts of p-hydroxystyrene polymer (molecular weight: 1000), divinyl ether compound (1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) A mixture of 60 parts of a condensate with 2 parts of polyethylene glycol (average molecular weight: 400) and 10 parts of the photoacid generator 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 the substrate obtained by heating at 120 ° C. for 8 minutes was irradiated with an argon laser through a positive pattern mask, and the above photosensitive layer was irradiated with light. After heating at 120 ° C. for 10 minutes, development was performed 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. A xenon lamp (a light beam whose ultraviolet wavelength region has been cut) and a second harmonic (5
Irradiation of 32 nm) provided the same good results as in the case of the argon laser.

Example 68 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
00) A mixture of 2 parts and 10 parts of the photoacid generator used in Example 1 was dissolved in diethylene glycol dimethyl ether to obtain a 20% by weight photosensitive solution. 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 through a positive pattern mask, and the photosensitive layer was irradiated with light, and heated at 120 ° C. for 10 minutes. Then, 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. Xenon lamp (light beam with ultraviolet wavelength cut) and Y
Irradiation of the second harmonic (532 nm) of the AG laser gave good results similar to those of the argon laser.

Example 69 100 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 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, an anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, followed by washing with water.
The substrate was heated at 0 ° C. for 8 minutes, and the obtained substrate was irradiated with an argon laser through a positive pattern mask to irradiate the above photosensitive layer with light. After heating at 120 ° C. for 10 minutes, a 1% aqueous solution of sodium carbonate was used. Developed. 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 (light beam whose ultraviolet wavelength region is cut) and the second harmonic (532n) of YAG laser
The same good results as in the case of the argon laser were obtained by the irradiation of m).

Example 70 200 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 a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) was added to 100 parts of the photoacid generator 10 used in Example 1.
A part of the mixture was dissolved in diethylene glycol dimethyl ether to adjust the solid content to 60% to obtain a photosensitive solution. Aqueous dispersion resin solution (15% solid content) was obtained by mixing and stirring 0.8 equivalent of acetic acid with respect to amino group in 100 parts (solid content) of the photosensitive solution obtained above and dispersing in deionized water. . The obtained water-dispersed resin solution was used as an electrodeposition coating bath, cationic electrodeposition coating was performed so that the dry film thickness was 5 μm using the laminated copper plate as a cathode, and then washed with water and heated at 120 ° C. for 8 minutes. After heating the substrate at 120 ° C. for 8 minutes, the above-mentioned photosensitive layer was irradiated with an argon laser through a positive pattern mask and heated at 120 ° C. for 10 minutes. Development was performed using an aqueous solution of oxide. 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 decrease and swelling of the film in the unexposed portion were not observed at all. Xenon lamp (light beam whose ultraviolet wavelength region is cut) and YA
Irradiation of the second harmonic (532 nm) of the G laser also gave good results similar to those of the argon laser.

Example 71 50 parts of poly (t-butoxycarbonyloxystyrene) (molecular weight: 1000) was added to 1000 parts of tetrahydrofuran,
A photosensitive solution having a solid content of 9% was obtained by mixing 50 parts of the following novolak phenol resin and 10 parts of the photoacid generator used in Example 1. (Production of novolak phenolic resin) o-cresol 1
490 parts, 1145 parts of 30% formalin, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Next, 13.5 parts of 15% hydrochloric acid was added, and
After heating to reflux for one minute, 400 parts of deionized water at about 15 ° C. was added to keep the contents at about 75 ° C. to precipitate the resin. Then, a 35% sodium hydroxide solution was added to neutralize the solution, and after neutralization, the aqueous layer was removed. 400 parts of deionized water was added, the resin was washed at 75 ° C., the aqueous layer was removed, and the same washing operation was repeated twice. Thereafter, the resultant was dried 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, an argon laser was applied to the substrate through a positive pattern mask, and the photosensitive layer was irradiated with light. Irradiate, 120 ° C
And developed with a 1% aqueous sodium carbonate solution. As a result of examining the residual film after development with respect to the amount of visible light irradiation, a film with excellent contrast was formed,
No decrease or swelling of the film in the unexposed portion was not observed at all. 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 gave good results similar to those obtained with an argon laser.

Example 72 50 parts of poly (tetrahydropyranyl ether styrene) (molecular weight: 1000) were added to 1,000 parts of tetrahydrofuran,
50 parts of the novolak phenol resin of Example 25 and 10 parts of the photoacid generator used in Example 1 were blended to obtain a photosensitive solution having a solid content of 9%. Using this photosensitive liquid, a photosensitive layer was formed in the same manner as in Example 1, and after evaporating the solvent, the substrate was irradiated with an argon laser through a positive pattern mask to irradiate the photosensitive layer with light. After heating at ℃ for 10 minutes, 1%
Development was performed using an 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. 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 gave good results similar to those obtained with an argon laser.

Example 73 The photosensitive solution of Example 1 was applied to a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater to a dry film thickness of 5 μm, and dried at 120 ° C. for 8 minutes to form a resist film. Was prepared. Next, the surface of the substrate having the resist coating obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Then, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate as a developing solution at 30 ° C. for 1 minute. There was no adverse effect due to irradiation and the results were good. When the substrate having the resist film was irradiated with an argon laser, it was confirmed that the resin was quickly cured. Irradiation with a xenon lamp (cutting the ultraviolet wavelength region) and the second harmonic (532 nm) of the YAG laser gave the same good results as in the case of the argon laser. The above-mentioned photosensitive solution was applied to a transparent polyethylene terephthalate sheet with a bar coater so that the film thickness became 5 μm.
The absorbance of the film dried for 0 minutes was measured. as a result,
At 550 to 630 nm, which is a range of ± 30 nm or more of the maximum wavelength of the safe light in FIG. 1, the absorbance of the unexposed film is 0.5 or less, and the safe light has no adverse effect on the photosensitive solution. It can be confirmed from the relative luminosity curve of FIG. 3 that the safety light is bright.

Examples 74 to 90 Examples 1-1 to 1-1 in Table 1 were used as photoacid generators in Example 1.
A photosensitive solution having the same composition as in Example 1 was obtained except that -17 was used. This photosensitive solution was applied on a glass-fiber reinforced epoxy substrate plated with copper in a dark room with a bar coater so as to have a dry film thickness of 5 μm, and dried at 120 ° C. for 8 minutes to prepare a substrate having a resist coating. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 91 The photosensitive solution of Example 67 was applied to a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater to a dry film thickness of 5 μm, and dried at 120 ° C. for 8 minutes to form a resist film. Was prepared. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 92 The photosensitive solution of Example 68 was applied to a copper-plated glass fiber reinforced epoxy substrate in a dark room with a bar coater to a dry film thickness of 5 μm, and dried at 120 ° C. for 8 minutes to form a resist film. A substrate was prepared. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 93 100 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, an anion electrodeposition coating was performed using a laminated copper plate as an anode to a dry film thickness of 5 μm, followed by washing with water.
By heating at 0 ° C. for 8 minutes, a substrate having a resist film was prepared. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Then, the mixture was heated at 80 ° C. for 10 minutes in a dark room, and 30% aqueous solution of sodium carbonate was used as a developing solution.
As a result of immersion at 1 ° C. for 1 minute, the resist coating did not dissolve in the aqueous sodium carbonate solution, and was good without being adversely affected by irradiation with a sodium lamp.

Example 94 100 parts (solid content) of the photosensitive solution obtained in Example 69 was mixed with 0.8 equivalent of acetic acid with respect to the amino group and 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, a cation electrodeposition coating was performed so that the dried copper film was used as a cathode and the dry film thickness was 5 μm, then washed with water and heated at 120 ° C. for 8 minutes to form a resist. A substrate having a coating was prepared. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with a sodium lamp of FIG.
Irradiation was carried out for 24 hours so as to give looks. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 1 minute using a 1% aqueous solution of sodium carbonate as a developer. It was good without any adverse effects.

Example 95 Using the photosensitive solution obtained in Example 70, the dry film thickness was 5 μm.
m, and then heated at 120 ° C. for 8 minutes to prepare a substrate having a resist coating. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with a sodium lamp of FIG.
Irradiation was carried out for 24 hours so as to give looks. Next, this was heated in a dark room at 80 ° C. for 10 minutes, and then immersed in a 1% aqueous sodium carbonate solution as a developing solution at 30 ° C. for 1 minute. As a result, the resist film was not dissolved in the aqueous sodium carbonate solution but was irradiated with a sodium lamp. It was good without any adverse effects.

Example 96 Using the photosensitive solution of Example 71, a photosensitive layer was formed in the same manner as in Example 1, the solvent was evaporated, and the coating was performed so that the dry film thickness was 5 μm. After washing with water and heating at 120 ° C. for 8 minutes, a substrate having a resist film was prepared. Next, the surface of the substrate having the resist film (dry film thickness 5 μm) obtained above was irradiated with the sodium lamp of FIG. 1 for 24 hours so that the illuminance intensity became 40 lux. Then, after heating this at 80 ° C. for 10 minutes in a dark room,
As a result of immersing in a 1% aqueous solution of sodium carbonate as a developing solution at 30 ° C. for 1 minute, the resist film did not dissolve in the aqueous solution of sodium carbonate and was good without being adversely affected by irradiation with a sodium lamp.

Comparative Example 1 In Example 1, NAI-105 was used as the photoacid generator.
A photosensitive solution was prepared in the same manner as in Example 1 except that 10 parts (product name, iminosulfonate compound, manufactured by Midori Kagaku Co., Ltd.) was used. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and the resulting substrate was irradiated with an argon laser through a positive pattern mask to irradiate the photosensitive layer with light. After heating at 120 ° C. for 10 minutes, development was performed using a 1% aqueous sodium carbonate solution.
As a result of examining the residual amount of the film after the development with respect to the amount of visible light irradiation, the film did not dissolve and good results could not be obtained. 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 could not obtain a good result as in the case of an argon laser.

Comparative Example 2 A test was conducted in the same manner as in Example 1 except that a fluorescent lamp was used instead of the sodium lamp. As a result, the resist film was dissolved in the aqueous sodium carbonate solution, and good results could not be obtained.

FIG. 4 shows the spectral distribution of the fluorescent lamp used in the comparative example.

[0151]

The photoacid generator and visible light-sensitive resin composition containing the compound of the present invention are highly versatile photosensitive resin compositions having high compatibility with resins and high solubility in coating solutions. Yes, resist materials, especially 488 nm and 51
High sensitivity and high resolution characteristics for resist writing by direct writing and recording method using general-purpose visible laser such as argon laser with stable oscillation line at 4.5 nm and YAG laser with emission line at 532 nm as second harmonic. And the storage stability of the photosensitive layer over time is excellent. Furthermore, since work such as painting and printing is possible under the environment conditions of safety light irradiation, safety workability, work efficiency, product quality stability and the like are excellent.

[Brief description of the drawings]

FIG. 1 shows an example of a spectral distribution of a discharge lamp mainly containing sodium as a safety light that can be used in the present invention.

FIG. 2 Spectral distribution of filtered sodium discharge lamp

FIG. 3 Comparative luminous efficiency curve

FIG. 4 Spectral distribution of fluorescent lamp

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinobu Inoue 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Akira Ogiso 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co. 72) Inventor Megumi Misawa 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals Co., Ltd. BC011 BC021 BC051 BC121 EY016 FD206 GP03

Claims (8)

[Claims] 1. A compound represented by the general formula (1): [In the formula, at least one of R ^{1 to} R ⁷ is a halogen atom, and the others are each independently a hydrogen atom, a nitro group, a cyano group, a carbamoyl group, a substituted or unsubstituted alkyl group, an aralkyl group, an aryl group. Group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group,
Represents an arylthio group, an alkenylthio group, an acyl group, an acyloxy group, a heteroaryl group, an acylamino group,
L ¹ and L ² each independently represent a halogen atom, an alkyl group,
Represents an aryl group, an aralkyl group, an alkoxy group, an aralkyloxy group, or an aryloxy group, and adjacent groups in R ^{1 to} R ³ and / or R ^{5 to} R ⁷ are bonded to each other;
It may form a substituted or unsubstituted ring. ] A photoacid generator characterized by using at least one dipyrromethene compound represented by the formula: 2. A compound of the general formula (2) [In the formula, at least one of R ^{8 to} R ¹⁶ is a halogen atom, and the others are each independently a hydrogen atom, a nitro group, a cyano group, a carbamoyl group, a substituted or unsubstituted alkyl group, an aralkyl group, an aryl group. Group, alkenyl group, alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group, alkylthio group, aralkylthio group,
An arylthio group, an alkenylthio group, an acyl group, an acyloxy group, a heteroaryl group represents an acylamino group, or a, L ^1, L ² represents L ^1, L ² the same group in the formula (1), R ⁸ ~ Adjacent groups at R ¹⁰ may combine with each other to form a substituted or unsubstituted ring. ] A photoacid generator characterized by using at least one dipyrromethene compound represented by the formula: 3. The visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and contains the photoacid generator according to claim 1 as a photoacid generator. A visible light-sensitive resin composition. 4. A visible light-sensitive resin composition which is used in an environment in which a safety light having a maximum wavelength selected from the range of 500 to 620 nm and a high relative luminous efficiency is used, and which is formed from the composition. 4. The visible light-sensitive resin composition according to claim 3, wherein the absorbance of the photosensitive film is 0.5 or less in a range of ± 30 nm of the maximum wavelength selected from the maximum wavelength range of the safety light. 5. A discharge lamp mainly composed of sodium as a safety light (mainly a D line having a light wavelength of 589 nm).
The visible light-sensitive resin composition according to claim 4, wherein 6. A visible light-sensitive material composition comprising the visible light-sensitive resin composition according to claim 3 and a solvent. 7. A visible light-sensitive resist material comprising the visible light-sensitive resin composition according to claim 3 on a substrate. 8. A dipyro represented by the following formula (3):
Methene boron complex compound. Embedded imageWherein A is bonded to an adjacent carbon atom to form a saturated ring
Represents the residue that forms¹⁷~ R^{twenty two}Are each independently a hydrogen source
, Nitro, cyano, carbamoyl, substituted or
Unsubstituted alkyl group, aralkyl group, aryl group,
Kenyl group, alkoxy group, aralkyloxy group, aryl
Luoxy group, alkenyloxy group, alkylthio group,
Aralkylthio, arylthio, alkenylthio,
Acyl group, acyloxy group, heteroaryl group, acyl
X represents a halogen atom, T represents a substituted or unsubstituted amino group.
Or an unsubstituted aryl or heteroaryl group.
Then L ¹, L^TwoIs L in equation (1)¹, L^TwoWith the same group as
Represent. ]