JP2002236360A - Photosensitive resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type visible light sensitive resin composition having satisfactory sensitivity in the visible light region, particularly to second harmonics of an argon laser and a YAG(yttrium aluminum garnet) laser and excellent in shelf stability and to provide a positive type visible light sensitive resin composition excellent in safe working property, working efficiency and the quality stability of a product. SOLUTION: In each of the positive type visible light sensitive resin compositions containing a positive type visible light sensitive resin and a photosensitizer, a dipyromethene boron complex compound of formula (1) is contained as the photosensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive visible light-sensitive resin composition containing a dipyrromethene boron complex compound having a specific structure as a photosensitizer and exhibiting high sensitivity to light rays in the visible light region, and the same. For use.

[0002] The present invention also relates to a positive visible light-sensitive resin composition to be used under specific safety light irradiation.

[0003]

2. Description of the Related Art In recent years, in the field of information using a photopolymerization reaction or image recording, instead of a conventional recording method using ultraviolet light using a film original or the like, a manuscript electronically edited by a computer is directly output at a high output. A method of directly outputting and recording using a laser is being studied. This method has the advantage that the recording and image forming steps can be greatly simplified by direct writing with a laser.

At present, many of the generally used high-output and stable laser light sources have an output wavelength in the visible region. Specifically, the wavelength 488 nm and 51
Argon laser with stable oscillation line at 4.5 nm or YAG with emission line at 532 nm as second harmonic
Lasers and He-Cd lasers having an oscillation line at 430 nm are widely used, and recently, a wavelength of 405 nm is used.
A blue-violet laser having an oscillation line has been developed. Therefore, compounds that are highly sensitive to these wavelengths are desired, but in the case of a conventional photosensitive agent for ultraviolet light,
It could not be used due to low sensitivity in the visible region. Also,
With the addition of pyrylium salts or thiopyrylium salts,
Although the sensitivity in the visible region can be improved, the storage stability of the photosensitive layer is low and it has been difficult to use.

[0005] As compounds having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazoylcoumarin (common name: coumarin-6) or bis [3
-(7-diethylaminocoumaryl)] ketone (common name:
Ketocoumarin) is known, but since these have a maximum absorption wavelength of about 450 nm, they have a shorter wavelength than 488 nm of an argon laser and have insufficient sensitivity. Also, 4-substituted-3 described in JP-A-4-18088.
-The benzothiazoyl coumarin compound shows high photosensitivity at 488 nm of an argon laser, but is 514.5.
532 which is the second harmonic of nm or YAG laser
nm has almost no absorption, leaving room for improvement in sensitivity.

[0006] When handling the above visible light-sensitive resin composition which is cured by visible light, a dark red colorant is coated on the outer tube and a coating or dark red film is coated on the outer tube. Electric lights such as fluorescent lamps that are colored by being wound are used as safety lights (working lights).
However, under such a dark red safety light environment, it is not easy to inspect the state of the coating film after application, and it is not easy to inspect the coating device, irradiation device, transport device, etc. There is a problem that work efficiency, product quality stability and the like are inferior. When a non-colored fluorescent lamp is used as a safety light, the working environment is bright and there is no problem.

On the other hand, European Patent No. 0169520, US Pat. No. 5,498,641, JP-A-9-258444, JP-A-8-179504, JP-A-8-952
44, JP-A-8-76377, JP-A-8-76377
No. 6245, JP-A-7-225474, JP-A-7-219223, JP-A-7-5885, and JP-A-5-241338 discloses a photopolymerizable composition using a dipyrromethene-based boron compound, A so-called negative photosensitive resin composition is disclosed.

[0008]

However, when an image is formed using a photopolymerization system, the photopolymerizable composition is applied onto a support such as a wiring board and then the solvent is removed by drying to remove the solvent. Since a photosensitive material is prepared by providing a layer of the composition, when a support having holes is used, a step of closing the holes before coating is required. Also, if a hole defect occurs due to the attachment or detachment of dust or the like on the exposed portion, it remains as it is in the case of photo-curing. Have a disadvantageous process. On the other hand, a photosensitive material using a positive photosensitive resin can be formed into a film and set on a support as a photosensitive layer, and even if dust is attached to the exposed portion, the exposed portion is It has an advantage that it does not become a defect because it is washed and removed.

Hitherto, many positive photosensitive resin compositions using a photoacid generator sensitive to ultraviolet light have been known. However, since the ultraviolet-sensitive resin is not sensitive to visible laser light, a photosensitizer having a sensitizing effect on visible light is used with a small exposure energy to obtain a sufficient positive image. It is necessary. That is, a photosensitizer capable of being photosensitized even in a small amount with respect to the resin component to be used, or a high solubility in the composition. There has been an urgent need to develop photosensitizers that can be exposed to light.

[0010] The present invention relates to the use of an argon laser having a wavelength of 488 nm or 514.
5 nm oscillation line, 5 which is the second harmonic of YAG laser
Highly sensitive and preserves long-wavelength laser light such as 32 nm in the visible light range, or laser light in the visible light range such as a 430 nm oscillation line of a He-Cd laser or a 405 nm wavelength emission line of a blue-violet laser. An object of the present invention is to provide a positive visible light-sensitive resin composition containing a photosensitizer having excellent stability. Further, the present invention provides a visible light curable resin composition having excellent sensitivity and capable of being handled under specific bright safety light conditions.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a positive type visible light photosensitive composition containing a specific dipyrromethene boron complex compound as a photosensitizer. The present inventors have found that a conductive resin composition solves the conventional problems, and have completed the present invention.

That is, the present invention provides: In a positive visible light-sensitive resin composition containing a positive visible light-sensitive resin and a photosensitizer, a dipyrromethene boron complex compound represented by the general formula (1) or (3) is used as a photosensitizer. Positive visible light photosensitive resin composition, characterized by containing

[0013]

Embedded image

Wherein R1 to R6 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group, an aryl group, an alkenyl group, an alkylthio group, an aralkylthio group, an arylthio group; Group, heterocyclic group, heterocyclic thio group, or

[0015]

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[Wherein L 1 and L 2 are each independently a hydrogen atom, an alkyl group which may have a substituent,
Represents an aralkyl group or an aryl group. R1 to R3, R4 to R6, adjacent groups may be bonded to each other to form an alicyclic ring which may be substituted, and R7 has a hydrogen atom or a substituent. Represents an alkyl group, an aralkyl group, or an aryl group which may be
X1 and X2 represent a halogen atom, an alkyl group which may have a substituent, an aralkyl group, or an aryl group. ]

2. In the general formula (1), R1 to R6
And R7 each independently represents a hydrogen atom or an alkyl group which may have a substituent; The positive visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and these resins are exposed to visible light so that the exposed portions are dissolved in an organic solvent or an aqueous developing solution, and are not irradiated. Wherein the part is a resin that does not dissolve in an organic solvent or an aqueous developing solution, wherein the positive-type visible light-sensitive resin composition has a relative luminous efficiency having a maximum wavelength selected from the range of 4.500 to 620 nm. A positive visible light-sensitive resin composition used under a large safety light irradiation environment, wherein the absorbance of an unphotosensitive film formed from the composition has a maximum wavelength selected from the maximum wavelength range of the safety light. The positive visible light-sensitive resin composition according to the above, wherein the composition is 0.5 or less in a range of ± 30 nm. 5. The positive visible light-sensitive resin composition as described above, 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). 6. 6. a composition for a positive-type visible light-sensitive material, comprising the above-mentioned positive-type visible light-sensitive resin composition and a solvent; The present invention relates to a positive resist material comprising the above-mentioned positive visible light-sensitive resin composition on a substrate.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The positive visible light-sensitive resin composition of the present invention contains a photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1). It has been found that the photosensitive resin composition of the present invention using the dipyrromethene boron complex compound represented by the general formula (1) has excellent sensitivity to visible light. The photosensitive resin composition of the present invention has an extremely large absorption at the wavelength of blue-violet laser, He-Cd laser, argon laser light or YAG laser light, and has very high sensitivity to such light. ,
It is a very useful material as a positive photosensitive resin composition using a resin and a photoacid generator.

The safe light used in the present invention is a safe light that does not cause a photoreaction with the visible light-sensitive resin composition of the present invention, and the safe light used has a high relative luminous efficiency to humans. Since it is an area, it feels very bright at the same illumination light intensity as compared with the conventional one, and exhibits excellent effects such as safe workability, work efficiency, and product quality stability.

The conventional safety light is a fluorescent light obtained by coloring a fluorescent lamp in red. However, since the emission spectrum of the fluorescent lamp has a wavelength range (FIG. 4) covering a wide range from ultraviolet light to visible light. There is a possibility that a clear resist pattern may not be formed due to the development process, even the visible light-sensitive resin coating portion which should not be reacted. Therefore, there is a problem that the working environment is further darkened in order to cope with the situation by reducing the intensity of the illumination light. On the other hand, the photosensitive resin composition of the present invention is a safe light having a specific sharp wavelength,
For example, since the photoreaction does not occur for the sodium lamp, the above-mentioned problem is solved.

The safety 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.

Further, 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. In addition, the safety light used in the present invention has a light beam of 5 like a sodium lamp.
It is preferable to use a sharp single light color of 89 nm, but in addition to using the safety light having a wavelength distributed in the wavelength range of ultraviolet light, visible light, and infrared light, in addition to the maximum wavelength being within the above range. No problem. 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 ray region (low wavelength region) is related to the energy intensity of the distributed light beam and the absorbance of the positive-type visible light photosensitive 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 an ordinary fluorescent lamp having a maximum wavelength in the range of 500 to 620 nm is used as the safety light, the fluorescent lamp is still 50 mils.
Since it has a large light energy intensity of less than 0 nm, particularly 400 to 499 nm, it cannot be used as a safety light for a positive type visible light photosensitive resin composition which is exposed to a visible light laser having an oscillation line at 488 nm or 532 nm.

The absorbance used 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 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, the conventional red wavelength of 640 to 780 nm
It can be seen that the relative luminous efficiency is low and the brightness perceived by human eyes is low. For example, in order to make 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-Z
8113 2008).

The positive visible light-sensitive resin composition of the present invention comprises a positive visible light-sensitive resin containing a positive visible light-sensitive resin and a photosensitizer of a dipyrromethene boron complex compound having a specific structure. A composition, wherein the absorbance of the unexposed film formed from the composition is within ± 30 nm of the maximum wavelength selected from the maximum wavelength range of the safe light (−30 nm).
nm to +30 nm), preferably in the range of ± 20 nm (−
20 nm to +20 nm), and a 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.

The term "composition for positive-type visible light-sensitive material" used in the present invention includes, for example, paints, inks, adhesives,
It means a printing plate material, a resist material, and a non-photosensitive film formed from these materials. Hereinafter, the present invention will be described in more detail.

The photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) is excited by absorbing light in the visible light region of 400 to 700 nm, in particular, light of 400 to 600 nm, and becomes a resin. And compounds that interact with the photoacid generator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited photosensitizer to the resin or photoacid generator. For this reason, the photosensitizer used here is an extremely useful compound as a photosensitizer.

In the compound represented by formula (1) according to the present invention, specific examples of R1 to R6 include a hydrogen atom; and a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. .

Other specific examples include the following substituents. Examples of the alkyl group which may have a substituent represented by R1 to R6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an iso group.
-Butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group,
1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl 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, Cyclohexyl 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, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclopentyl-2,2 -Dimethylpropyl group, 1-cyclohexyl-2,2-dimethylpropyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl 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-
A linear, branched, or cyclic alkyl having 1 to 20 carbon atoms such as a 4-butyloctyl group, an n-tetradecyl group, an n-pentadecyl group, a decalyl group, an adamantyl group, an icosanyl group, and a 4-t-butylcyclohexyldecyl group; Group;

Chloromethyl, chloroethyl, bromoethyl, iodoethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2,2
Carbon substituted by a halogen atom such as 2-trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group, perfluorodecyl group, perfluoroicosanyl group, etc. Alkyl groups of formulas 1 to 20;

Hydroxymethyl, 2-hydroxyethyl, 4-hydroxybutyl, 2-hydroxy-3-
Methoxypropyl group, 2-hydroxy-3-chloropropyl group, 2-hydroxy-3-ethoxypropyl group, 3
-Butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, carbon number 1-substituted by a hydroxyl group such as 4-hydroxydecalyl group. 10 alkyl groups;

Hydroxymethoxymethyl group, hydroxyethoxyethyl group, 2- (2'-hydroxy-1'-methylethoxy) -1-methylethyl group, 2- (3'-fluoro-2'-hydroxypropoxy) ethyl group , 2-
(3'-chloro-2'-hydroxypropoxy) an alkyl group having 2 to 10 carbon atoms substituted with a hydroxyalkoxy group such as an ethyl group or a hydroxybutoxycyclohexyl group;

Hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [2 '-(2'-
(Hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2′-fluoro-1′-hydroxyethoxy) -1′-methylethoxy] ethoxyethyl group, [2′- (2'-chloro-1 '
-Hydroxyethoxy) -1′-methylethoxy] an alkyl group having 3 to 10 carbon atoms substituted with a hydroxyalkoxyalkoxy group such as an ethoxyethyl group;

Cyanomethyl group, 2-cyanoethyl group, 4
-Cyanophthyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-
C2-C10 substituted with a cyano group such as a 3-ethoxypropyl group, a 3-butoxy-2-cyanopropyl group, a 2-cyano-3-cyclohexylpropyl group, a 2-cyanopropyl group, or a 2-cyanobutyl group; An alkyl group;

Methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, n-hexyloxyethyl, (4-methyl Pentoxy) ethyl group, (1,3-
(Dimethylbutoxy) ethyl group, (2-ethylhexyloxy) ethyl group, n-octyloxyethyl group, (3,
5,5-trimethylhexyloxy) ethyl group, (2-
A methyl-1-iso-propylpropoxy) ethyl group,
(3-methyl-1-iso-propylbutyloxy) ethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group, (3,3,3-trifluoropropoxy) ethyl group, (3,3 , 3-trichloropropoxy)
An alkyl group having 2 to 15 carbon atoms, which is substituted with an alkoxy group such as an ethyl group and adamantyloxyethyl;

Methoxymethoxymethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, cyclohexyloxyethoxyethyl group, decalyloxypropoxyethoxy group, (1,2-dimethylpropoxy) ethoxy Ethyl group, (3-methyl-1-iso-butylbutoxy) ethoxyethyl group, (2-methoxy-1-methylethoxy) ethyl group, (2-butoxy-1-methylethoxy) ethyl group, 2- (2 ′ -Ethoxy-1′-methylethoxy) -1-methylethyl group, (3,3,3-trifluoropropoxy) ethoxyethyl group, (3,3
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxyalkoxy group such as 3-trichloropropoxy) ethoxyethyl group;

Methoxymethoxymethoxymethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, cyclohexyloxy, propoxypropoxypropoxy group, (2,2,2-trifluoroethoxy) ethoxyethoxyethyl group , (2,2,2-trichloroethoxy)
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxyalkoxy group such as an ethoxyethoxyethyl group;

Phenoxymethyl, phenoxyethyl, (4-t-butylphenoxy) ethyl, naphthyloxymethyl, biphenyloxyethyl, (3-methylphenyl) oxyethyl, 4- (1-pyrenyloxy) butyl An alkyl group having 7 to 15 carbon atoms substituted with an aryloxy group;

C8-20 carbon atoms such as benzyloxymethyl, benzyloxyethyl, phenethyloxymethyl, phenethyloxyethyl, (4-cyclohexyloxybenzyloxy) methyl and 9-fluorenylmethoxyhexyl; An alkyl group having 8 to 20 carbon atoms substituted with an aralkyloxy group;

A formylmethyl group, a 2-oxobutyl group,
3-oxobutyl group, 4-oxobutyl group, 2,6-dioxocyclohexane-1-yl group, 2-oxo-5-
an alkyl group having 2 to 10 carbon atoms substituted with an acyl group such as a t-butylcyclohexane-1-yl group;

Formyloxymethyl, acetoxyethyl, propionyloxyethyl, butanoyloxyethyl, valeryloxyethyl, (2-ethylhexanoyloxy) ethyl, (3,5,5-trimethylhexanoyl) Carbon substituted with an acyloxy group such as an (oxy) ethyl group, a (3,5,5-trimethylhexanoyloxy) hexyl group, a (3-fluorobutyryloxy) ethyl group, a (3-chlorobutyryloxy) ethyl group An alkyl group of the formulas 2 to 15;

Formyloxymethoxymethyl group, acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethyl group, (3,5
5-trimethylhexanoyloxy) butoxyethyl group, (3,5,5-trimethylhexanoyloxyethoxy) ethyl group, (2-fluoropropionyloxy)
Ethoxyethyl group, (2-chloropropionyloxy)
An alkyl group having 3 to 15 carbon atoms and substituted with an acyloxyalkoxy group such as an ethoxyethyl group;

Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy)
Ethoxyethoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethoxyethyl group, (2
An alkyl group having 5 to 15 carbon atoms, which is substituted with an acyloxyalkoxyalkoxy group such as -fluoropropionyloxy) ethoxyethoxyethyl group or (2-chloropropionyloxy) ethoxyethoxyethyl group;

A methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a butoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylethyl group, a butoxycarbonylethyl group, a (p-ethylcyclohexyloxycarbonyl) cyclohexyl group,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyl group such as a 2,3,3-tetrafluoropropoxycarbonyl) methyl group or a (2,2,3,3-tetrachloropropoxycarbonyl) methyl group;

C8-C15 substituted with an aryloxycarbonyl group such as a phenoxycarbonylmethyl group, a phenoxycarbonylethyl group, a (4-t-butylphenoxycarbonyl) ethyl group, a naphthyloxycarbonylmethyl group or a biphenyloxycarbonylethyl group. An alkyl group of

The number of carbon atoms substituted by an aralkyloxycarbonyl group having 9 to 15 carbon atoms such as a benzyloxycarbonylmethyl group, a benzyloxycarbonylethyl group, a phenethyloxycarbonylmethyl group and a (4-cyclohexyloxybenzyloxycarbonyl) methyl group 9-1
5 alkyl groups;

An alkyl group having 4 to 10 carbon atoms substituted by an alkenyloxycarbonyl group such as a vinyloxycarbonylmethyl group, a vinyloxycarbonylethyl group, an allyloxycarbonylmethyl group and an octenoxycarbonylmethyl group;

Methoxycarbonyloxymethyl, methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, butoxycarbonyloxyethyl,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyloxy group such as a (2,2,2-trifluoroethoxy) carbonyloxyethyl group or a (2,2,2-trichloroethoxy) carbonyloxyethyl group;

Methoxymethoxycarbonyloxymethyl, methoxyethoxycarbonyloxyethyl, ethoxyethoxycarbonyloxyethyl, butoxyethoxycarbonyloxyethyl, (2,2,2-trifluoroethoxy) ethoxycarbonyloxyethyl,
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxycarbonyloxy group such as a (2,2,2-trichloroethoxy) ethoxycarbonyloxyethyl group;

Dimethylaminomethyl, diethylaminomethyl, di-n-butylaminomethyl, di-n-hexylaminomethyl, di-n-octylaminomethyl, di-n-decylaminomethyl, N- Isoamyl-
N-methylaminomethyl group, piperidinomethyl group, di (methoxymethyl) aminomethyl group, di (methoxyethyl) aminomethyl group, di (ethoxymethyl) aminomethyl group, di (ethoxyethyl) aminomethyl group, di (propoxyethyl) ) Aminomethyl group, di (butoxyethyl)
Aminomethyl group, bis (2-cyclohexyloxyethyl) aminomethyl group, dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group, di-n-hexylaminoethyl group, di-n-octylaminoethyl Group, di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group, piperidinoethyl group, di (methoxymethyl) aminoethyl group, di (methoxyethyl) aminoethyl group, di (ethoxymethyl) aminoethyl Group, di (ethoxyethyl) aminoethyl group, di (propoxyethyl) aminoethyl group, di (butoxyethyl) aminoethyl group, bis (2-cyclohexyloxyethyl) aminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, Di-n-butylaminopropyl group, di-n Hexyl aminopropyl group, di -
n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxymethyl) aminopropyl group, di (methoxyethyl) aminopropyl group Di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis (2-cyclohexyloxyethyl) aminopropyl group, dimethyl Aminobutyl group, diethylaminobutyl group, di-n-butylaminobutyl group, di-n
-Hexylaminobutyl group, di-n-octylaminobutyl group, di-n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group, piperidinobutyl group,
Di (methoxymethyl) aminobutyl group, di (methoxyethyl) aminobutyl group, di (ethoxymethyl) aminobutyl group, di (ethoxyethyl) aminobutyl group, di (propoxyethyl) aminobutyl group, di (butoxyethyl) An alkyl group having 3 to 20 carbon atoms substituted with a dialkylamino group such as an aminobutyl group or a bis (2-cyclohexyloxyethyl) aminobutyl group;

Substitution with an acylamino group such as an acetylaminomethyl group, an acetylaminoethyl group, a propionylaminoethyl group, a butanoylaminoethyl group, a cyclohexanecarbonylaminoethyl group, a p-methylcyclohexanecarbonylaminoethyl group, and a succiniminoethyl group. An alkyl group having 3 to 10 carbon atoms;

An alkyl group having 2 to 10 carbon atoms substituted by an alkylsulfonamino group such as a methylsulfonaminomethyl group, a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, and an octylsulfonaminoethyl group. ;

Methylsulfonylmethyl, ethylsulfonylmethyl, butylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylethyl, butylsulfonylethyl, 2-ethylhexylsulfonylethyl, (2,2,3,3-tetra An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonyl group such as a (fluoropropyl) sulfonylmethyl group and a (2,2,3,3-tetrachloropropyl) sulfonylmethyl group;

Benzenesulfonylmethyl, benzenesulfonylethyl, benzenesulfonylpropyl, benzenesulfonylbutyl, toluenesulfonylmethyl, toluenesulfonylethyl, toluenesulfonylpropyl, toluenesulfonylbutyl, xylenesulfonylmethyl, xylenesulfonyl C7-C7 substituted with an arylsulfonyl group such as an ethyl group, a xylenesulfonylpropyl group and a xylenesulfonylbutyl group
12 alkyl groups;

Thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethyl group, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolyl group, triazolinomethyl group, morpholinomethyl group, indolinomethyl group,
Examples thereof include an alkyl group having 2 to 13 carbon atoms substituted with a heterocyclic group such as a benzimidazolinomethyl group and a carbazolinomethyl group.

Examples of the aralkyl group which may have a substituent of R1 to R6 include the aralkyl group having the same substituent as the above-mentioned alkyl group, preferably a benzyl group or a nitrobenzyl group. , Cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group, Examples thereof include an aralkyl group having 7 to 15 carbon atoms such as a fluoren-9-ylethyl group.

Examples of the aryl group which may have a substituent of R1 to R6 include the aryl group having the same substituent as the above-mentioned alkyl group.
Phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group, Examples thereof include aryl groups having 6 to 15 carbon atoms such as a methoxycarbonylphenyl group, a 4- (5'-methylbenzoxazol-2'-yl) phenyl group, and a dibutylaminocarbonylphenyl group.

Examples of the alkenyl group which may have a substituent represented by R1 to R6 are the alkenyl groups having the same substituents as the above-mentioned alkyl groups, preferably a vinyl group, a propenyl group, 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-methylcarboxylvinyl group, 2-cyano- A 2-methylsulfone vinyl group, a styryl group, a 2-phenyl-2-butenyl group or the like having 2 to 2 carbon atoms
And 10 alkenyl groups.

Examples of the alkylthio group which may have a substituent of R1 to R6 include the alkylthio groups having the same substituents as the above-mentioned alkyl groups, preferably a methylthio group, an ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, i
so-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neopentylthio group, 2-methylbutylthio group, methylcarboxylethylthio group, 2-ethylhexylthio group, 3 , 5,5-trimethylhexylthio group, decalylthio group, and other alkylthio groups having 1 to 10 carbon atoms.

Examples of the aralkylthio group which may have a substituent of R1 to R6 include an aralkylthio group having the same substituent as the above-mentioned alkyl group.
Preferably, a benzylthio group, a nitrobenzylthio group,
Cyanobenzylthio, hydroxybenzylthio, methylbenzylthio, trifluoromethylbenzylthio, naphthylmethylthio, nitronaphthylmethylthio, cyanonaphthylmethylthio, hydroxynaphthylmethylthio, methylnaphthylmethylthio, trifluoromethylnaphthyl Examples thereof include an aralkylthio group having 7 to 12 carbon atoms such as a methylthio group and a fluoren-9-ylethylthio group.

Examples of the arylthio group which may have a substituent for R1 to R6 include the arylthio groups having the same substituents as the above-mentioned alkyl groups, and are preferably a phenylthio group and a 4-methylphenyl group. Thio group, 2
And arylthio groups having 6 to 10 carbon atoms, such as -methoxyphenylthio group, 4-t-butylphenylthio group, and naphthylthio group.

Examples of the heterocyclic group which may have a substituent represented by R1 to R6 include the same heterocyclic group as the above-mentioned alkyl group, preferably a furanyl group, a pyrrolyl group. Group, 3-pyrrolino group, pyrazolyl group,
Imidazolyl group, oxazolyl group, thiazolyl group, 1,
2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl Group, benzofuranyl group, indoleyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group,
Benzotriazol-2-yl, benzotriazol-1-yl, purinyl, quinolinyl, isoquinolinyl, coumarinyl, cinnolinyl, quinoxalinyl, dibenzofuranyl, carbazolyl, phenanthronylyl, pheno Unsubstituted heteroaryl groups such as thiazinyl group, flavonyl group, phthalimido group, naphthylimido group; 1,3-oxolanyl group, 2-pyrazolinyl group, pyrazolidinyl group, 4H-pyranyl group, piperidinyl group, dioxanyl group, morpholinyl group, piperazinyl An alicyclic heterocyclic group such as a group;

Alternatively, the following substituents: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, etc. An alkoxy group; an aralkyloxy group such as a benzyloxy group or a phenethyloxy group; an aryloxy group such as a phenoxy group, a tolyloxy group, a naphthoxy group, a xylyloxy group, a mesityloxy group, a chlorophenoxy group, or a methoxyphenoxy group; B Alkenyl groups such as benzyl group, butadienyl group, pentenyl group and octenyl group; alkenyloxy groups such as vinyloxy group, allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group and octenyloxy group; methylthio group and ethylthio group ,
Alkylthio groups such as propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; benzylthio group, phenethylthio group Aralkylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group, etc .; dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, etc. An acyl group such as an acetyl group, a propionyl group or a butanoyl group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a benzyloxycarbonyl group; Aralkyloxycarbonyl groups such as tyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group and methoxyphenoxycarbonyl group Group;
Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group, Propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group,
3,5,5-trimethylhexylaminocarbonyl group,
2 to 2 carbon atoms such as a 2-ethylhexylaminocarbonyl group
10, monoalkylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, Carbon number 3 such as piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4-ethylpiperazinocarbonyl group, etc.
Alkylaminocarbonyl groups such as dialkylaminocarbonyl groups of no. To 20; furanyl, pyrrolyl, 3-pyrrolino, pyrrolidino, 1,3-oxolanyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, imidazolyl, oxazolyl Group, thiazolyl group, 1,
2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group , Pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indoleyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group A heterocyclic group substituted by a substituent such as a dibenzofuranyl group, a carbazolyl group, a phenanthronylyl group, a phenothiazinyl group, or a flavonyl group;

Examples of the optionally substituted heterocyclic thio group represented by R1 to R6 are the same heterocyclic thio groups having the same substituents as the above-mentioned alkyl groups, preferably a furanylthio group. , A pyrrolylthio group, a 3-pyrrolinothio group, a pyrazolylthio group, an imidazolylthio group, an oxazolylthio group, a thiazolylthio group, a 1,2,3-oxadiazolylthio group, a 1,2,3-triazolylthio group,
1,2,4-triazolylthio group, 1,3,4-thiadiazolylthio group, pyridinylthio group, pyridazinylthio group, pyrimidinylthio group, pyrazinylthio group, piperazinylthio group, triazinylthio group, benzofuranylthio group, indolylthio group, Thionaphthenylthio group, benzimidazolylthio group, benzothiazolylthio group, benzotriazol-2-ylthio group, benzotriazol-1-ylthio group, prenylthio group, quinolinylthio group, isoquinolinylthio group, coumarinylthio group, cinnolinylthio group , Quinoxalinylthio, dibenzofuranylthio, carbazolylthio, phenanthronylylthio, phenothiazinylthio, flavonylthio, phthalimidothio, naphthylimidothio, unsubstituted heteroarylthio Groups; 1,3 Okisoraniruchio group, 2-Pirazoriniruchio group, pyrazolidinylimidazolinyl thione group,
An alicyclic heterocyclic thio group such as a 4H-pyranylthio group, a piperidinylthio group, a dioxanylthio group, a morpholinylthio group, a piperazinylthio group;

Alternatively, the following substituents: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, etc. An alkoxy group; an aralkyloxy group such as a benzyloxy group and a phenethyloxy group; an aryloxy group such as a phenoxy group, a tolyloxy group, a naphthoxy group, a xylyloxy group, a mesityloxy group, a chlorophenoxy group, and a methoxyphenoxy group; a vinyl group, an allyl group, B Alkenyl groups such as benzyl, butadienyl, pentenyl and octenyl; alkenyloxy such as vinyloxy, allyloxy, butenyloxy, butadienyloxy, pentenyloxy and octenyloxy; methylthio and ethylthio ,
Alkylthio groups such as propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; benzylthio group, phenethylthio group Aralkylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group, methoxyphenylthio group, etc .; dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, etc. An acyl group such as an acetyl group, a propionyl group or a butanoyl group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a benzyloxycarbonyl group; Aralkyloxycarbonyl groups such as tyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group and methoxyphenoxycarbonyl group Group;
Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, pentenyloxycarbonyl group, octenyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group, Propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group,
3,5,5-trimethylhexylaminocarbonyl group,
2 to 2 carbon atoms such as a 2-ethylhexylaminocarbonyl group
10, monoalkylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, Carbon number 3 such as piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, 4-ethylpiperazinocarbonyl group, etc.
Alkylaminocarbonyl groups such as dialkylaminocarbonyl groups of no. To 20; furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolyl Group, thiazolyl group, 1,
2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group , Pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indoleyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group A heterocyclic group substituted with a substituent such as a dibenzofuranyl group, a carbazolyl group, a phenanthronylyl group, a phenothiazinyl group, a flavonyl group;

Examples of the optionally substituted alkyl, aralkyl and aryl groups represented by the substituents L1 and L2 of the amino group represented by formula (2) according to the present invention include: , The aforementioned alkyl group; the aforementioned aralkyl group; the aforementioned aryl group; and the like.

Preferred examples of the formula (2) include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group and a 2-ethylhexylamino group. A monoalkylamino group having 1 to 10 carbon atoms such as a cyclohexylamino group, a 3,5,5-trimethylhexylamino group, a nonylamino group, a decylamino group;

Benzylamino group, phenethylamino group,
3-phenylpropylamino group, 4-ethylbenzylamino group, 4-isopropylbenzylamino group, N-methylbenzylamino group, N-ethylbenzylamino group, N
-Allylbenzylamino group, N- (2-cyanoethyl)
A monoaralkylamino group having 7 to 10 carbon atoms, such as a benzylamino group or an N- (2-acetoxyethyl) benzylamino group;

Anilino, naphthylamino, toluidino, xylidino, ethylanilino, isopropylanilino, methoxyanilino, ethoxyanilino, chloroanilino, acetylanilino, methoxycarbonylanilino, ethoxycarbonyl A monoarylamino group having 6 to 10 carbon atoms, such as an anilino group, a propoxycarbonylanilino group, an N-methylanilino group, an N-ethylanilino group, an N-methyltoluidino group;

Formylamino, methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, iso-propylcarbonylamino,
n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t
-Butylcarbonylamino group, n-pentylcarbonylamino group, iso-pentylcarbonylamino group, neopentylcarbonylamino group, 2-methylbutylcarbonylamino group, benzoylamino group, methylbenzoylamino group, ethylbenzoylamino group, tolylcarbonyl An amino group, a propylbenzoylamino group, a 4-t-butylbenzoylamino group, a nitrobenzylcarbonylamino group, a 3-butoxy-2-naphthoylamino group, a cinnamoylamino group, and a C1-C15 acylamino group; Mono-substituted amino group;

Dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino, di-n-hexylamino, dicyclohexylamino, dioctylamino, bis (methoxyethyl) amino, bis (methoxyethyl) amino, Ethoxyethyl) amino group, bis (propoxyethyl) amino group, bis (butoxyethyl) amino group, di (acetyloxyethyl) amino group,
Di (hydroxyethyl) amino group, N-ethyl-N-
A dialkylamino group having 2 to 16 carbon atoms such as a (2-cyanoethyl) amino group and a di (propionyloxyethyl) amino group;

Dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, bis (4-
14 to 2 carbon atoms such as isopropylbenzyl) amino group
0 diaralkylamino group; C12-14 diarylamino group such as diphenylamino group, ditolylamino group, N-phenyl-N-tolylamino group;

Diformylamino, di (methylcarbonyl) amino, di (ethylcarbonyl) amino, di (n-propylcarbonyl) amino, di (iso-propylcarbonyl) amino, di (n-butylcarbonyl) ) Amino group, di (iso-butylcarbonyl) amino group, di (sec-butylcarbonyl) amino group, di (t
-Butylcarbonyl) amino group, di (n-pentylcarbonyl) amino group, di (iso-pentylcarbonyl)
Amino group, di (neopentylcarbonyl) amino group, di (2-methylbutylcarbonyl) amino group, di (benzoyl) amino group, di (methylbenzoyl) amino group, di (ethylbenzoyl) amino group, di (tolylcarbonyl) ) Amino group, di (propylbenzoyl) amino group, di (4-t-butylbenzoyl) amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-
Naphthoyl) amino group, di (cinnamoyl) amino group,
A diacylamino group having 2 to 30 carbon atoms such as an imino succinate group; having a substituent such as an N- (2-acetyloxyethyl) -N-ethylamino group or an N-tolyl-N-methylamino group; And a disubstituted amino group having 3 to 10 carbon atoms selected from an alkyl group, an aralkyl group and an aryl group.

Examples of the optionally substituted alicyclic ring formed by bonding adjacent groups in R1 to R3 and R4 to R6 include those represented by the formula (3) or (4). ) Or formula (5)

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

(Wherein, r1 to r20 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkyl group similar to the alkyl groups represented by R1 to R8, a methoxy group, Ethoxy, propoxy, butoxy, pentoxy, hexyloxy,
Heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group,
Represents an alkoxy group such as a 3,5,5-trimethylhexyloxy group, and n1 to n3 represent 0 or 1. And alicyclic rings which may be substituted. Preferably, -CH2-CH2-CH2-CH2- and the like are mentioned.

Examples of the optionally substituted alkyl group, aralkyl group and aryl group represented by R7 in the formula (1) include the above-mentioned alkyl group; the above-mentioned aralkyl group;
The aforementioned aryl group; and the like. X1 in equation (1)
Examples of the halogen atom, an optionally substituted alkyl group, an aralkyl group and an aryl group represented by X2 and X2 include the aforementioned halogen atom; the aforementioned alkyl group; the aforementioned aralkyl group; And the like.

In the specific examples illustrated above, R
1 to R6 and R7 are each independently a hydrogen atom or an optionally substituted alkyl group;
And dipyrromethene boron complex compounds in which X2 is a halogen atom or an alkyl group which may have a substituent. Further, a compound in which R1 to R6 are an alkyl group which may have a substituent and R7 is a hydrogen atom is more preferable, and a compound in which X1 and X2 are halogen atoms is particularly preferable.

The method for producing the dipyrromethene boron complex compound represented by the general formula (1) according to the present invention is described in, for example, Liebigs Ann. Chem. 718 , pp. 208-233 (1969),
-196865, U.S. Pat.
No., Heteroatom Chemistry, Vol. 1, Number 5, pp 389-399 (1
990), and can be produced by the following method according to the method described in JP-A-10-279614. That is, typically, for example, in the presence of an acid such as hydrobromic acid or trifluoroacetic acid, a compound represented by the general formula (6) R ⁷ —CHO (6) (where R ⁷ is the same as R 7 in the formula (1)) And a compound represented by the general formula (7) and / or the general formula (8)

[0083]

Embedded image

[0084]

Embedded image

(Wherein, R 1 to R 6 represent R 1 in the formula (1))
Represents the same meaning as R6. ) And then oxidized with an oxidizing agent such as air oxidation or chloranil to obtain a compound represented by the general formula (9).

[0086]

Embedded image

(Wherein R 1 to R 7 are the same as R 1 in the formula (1))
Represents the same meaning as R7. The dipyrromethene compound represented by the formula (1) is then reacted with boron trihalide to obtain a compound of the general formula (10) wherein X1 and X2 in the formula (1) are halogen atoms.

[0088]

[Formula 11]

(Wherein R 1 to R 7 are the same as R 1 in the formula (1))
X represents the same meaning as R7, and X represents a halogen atom. ) Can be obtained. further,
One or both of the halogen atoms represented by X in the general formula (10) is an alkyl metal compound, an aryl metal compound,
By using an aralkyl metal compound, or an organometallic reagent such as a heterocyclic metal compound, by performing a substitution reaction in a solvent,
The compound of the general formula (1) can be easily produced.
Alternatively, instead of the general formula (6), for example, the general formula (1)
1) (Chemical formula 12)

[0090]

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(Wherein R 7 has the same meaning as R 7 in formula (1)) and a compound of formula (7) and / or (8) By doing so, a compound of the general formula (9) or a hydrogen halide salt thereof can be obtained. The dipyrromethene boron complex compound of the general formula (1) according to the present invention, wherein R7 is a hydrogen atom, may be prepared, for example, in the presence of an acid such as hydrobromic acid by the general formula (7) (12) (Chemical 1
3) or the general formula (8) and the general formula (13)
(Formula 14)

[0092]

Embedded image

[0093]

Embedded image

(Wherein R1 to R7 are the same as R1 of the formula (1))
Represents the same meaning as R7. ) Is reacted with a compound represented by the general formula (14), wherein -R7 in the general formula (9) is a hydrogen atom.

[0095]

Embedded image

(Wherein R 1 to R 6 represent R 1 in the formula (1)
Represents the same meaning as R6. ) Can be obtained.

With respect to specific examples of the compound represented by the general formula (1), the following compounds having substituents (1-
1) to (1-15) (Tables 1 and 2).

[0098]

[Table 1]

[0099]

[Table 2]

The photosensitizer contains at least one photosensitizer of a dipyrromethene boron complex compound represented by the general formula (1).

In this case, the content of the photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) in the photosensitizer is not particularly limited, but a desired effect can be obtained in the present invention. For this purpose, the content of the photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) in the photosensitizer is preferably 10% by weight or more, more preferably 20% by weight or more. And more preferably 30% by weight or more, and particularly preferably substantially 100% by weight.

The amount of the dipyrromethene boron complex compound used as the photosensitizer depends on the type and amount of the dipyrromethene boron complex compound represented by the general formula (1) contained in the photosensitizer. The amount of the photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) per 100 parts by weight of the resin component is usually 0, although it depends on the type and amount of the resin component to be acted and the photoacid generator. An appropriate amount is in the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When the use amount of the photosensitizer of the dipyrromethene boron complex compound is too small, the photosensitivity of the formed film tends to decrease when it is less than 0.05 part by weight, and when it exceeds 10 parts by weight, from the viewpoint of solubility, It tends to be difficult to keep the composition homogeneous. Further, the photosensitizer of the general formula (1) is used in a weight ratio of less than 0.1 weight ratio to 1 weight ratio of the photoacid generator used in the positive visible light-sensitive resin composition of the present invention. It is possible.

The positive-type visible light-sensitive resin composition of the present invention comprises a conventionally known positive-type visible light-sensitive resin composition (for example, a coating material) which decomposes upon exposure and shows solubility in a developing solution. , An ink, an adhesive, a printing plate material, a resist material for a printed wiring board) containing a photosensitizer of the dipyrromethene boron complex compound represented by the general formula (1) as an essential component. is there.

Representative examples of the above-mentioned conventionally known positive-type visible light-sensitive resin compositions will be described below. Examples of the composition include a resin containing a photoacid generator, a resin containing components other than the photoacid generator component (for example, a photobase generator, etc.), and a resin that itself decomposes by light. When these resins are decomposed by light, their properties, such as polarity and molecular weight, change, whereby the resins become soluble in substances such as a developer (aqueous solution, organic solvent, etc.). The resin may include 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 containing the photoacid generator component will be described. The resin includes a resin in which a photoacid generator is incorporated in a resin skeleton (for example, a resin in which a resin generates an acid group upon exposure to light, thereby enabling alkali development) or a mixture of a photoacid generator and a resin [ The acid generated by the photoacid generator causes the resin to be cut to have a low molecular weight, an acid group to be added to the resin, or a change into a soluble substance (for example, (poly) P-hydroxystyrene). Or exhibiting dispersibility or solubility in an organic solvent or an aqueous developer].

Examples of such a composition include a composition mainly composed of a resin in which quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group through a sulfonic ester bond (Japanese Patent Application Laid-Open No. Sho 61 (1986)). -206293
JP-A-7-334449), that is, a naphthoquinonediazide photosensitive composition utilizing a reaction in which a quinonediazide group is photolyzed by irradiation light to form indenecarboxylic acid via ketene; A chemically amplified photosensitive material utilizing a change in solubility between irradiated and unirradiated parts by causing a elimination reaction in a base resin (polymer) in a chain using a photoacid generator that generates an acid group as a catalyst (particularly, Kaihei 4-2264
No. 61, U.S. Pat.No. 4,491,628, JP-A-59-45439
No., JP-A-63-250642, Polymers in Electronic
s ”DavidsonT. Edited. ACS Symposium Series 242, America
n Chemical Society, Washington DC, 1984, p. 11 ",
N.Hayashi, T.Ueno, M.Toriumi, etc, ACS Polym.materials
Sci. Eng., 61, 417 (1989), H. Ito, CGWilson, ACS Symp.
Ser., 242, 11 (1984), etc.); a crosslinked film insoluble in a solvent or an aqueous alkali solution is formed by heating, and the crosslinked structure is cut by a photoacid generator which generates an acid group by irradiation with light. Positive photosensitive compositions utilizing a mechanism in which the irradiated part becomes soluble in a solvent or an aqueous alkali solution (JP-A-6-295064, JP-A-6-308733, JP-A-6-313134, JP-A-6-313134) No. 6-313135, JP-A-6-31
No. 3136, JP-A-77-146552) and the like.

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

[0108] The components of the resin include a two-component system of a resin having an acid labile group and a photoacid generator, and a three-component system of a resin having an acid labile group, a photoacid generator, and other resins. Can be used as The other resin is
By using this, for example, the coating workability of the composition can be improved or the solubility of the composition in a developer can be changed.

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

In the case where the resin (a) has both a carboxyl group and a hydroxyphenyl group, even if these groups are contained in the same molecule, a mixture of resins containing these groups differently is used. Either resin or both may be used.

Examples of the carboxyl group-containing resin (a-1) include acrylic resins and polyester resins. The above resin (a-1) is generally about 500
It preferably has a number average molecular weight of about 10000 to about 100000, especially about 1500 to 30000, and the carboxyl group is preferably about 0.5 to 10 mol, particularly preferably about 0.7 to 5 mol per kg of resin. .

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

The above resin (a-2) is generally used in an amount of about 500
It preferably has a number average molecular weight of about 100,000, especially about 1500 to 30000, and the hydroxyphenyl group is preferably about 1.0 mol or more, and more preferably about 2 to 8 mol per kg of resin.

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

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

The above resin (a-3) is generally used in an amount of about 500
It preferably has a number average molecular weight of about 10000 to about 100000, especially about 1500 to 30000, and the carboxyl group is preferably about 0.5 to 10 mol, particularly preferably about 0.7 to 5 mol per kg of resin. . The hydroxyphenyl group is present in an amount of about 1.0 mol or more, preferably about 2 to 8
Molar is preferred.

Examples of the olefinically unsaturated compound (b) containing an ether bond include about 1 to 4 unsaturated ether groups such as a vinyl ether group, 1-propenyl ether group, and 1-butenyl ether group at the molecular terminal. To do. The compound (b) has the formula -R "
-O-α [where α represents a vinyl group, a 1-propenyl group or an olefinically unsaturated group of 1-butenyl, and R ″ represents a linear or branched C1-C6 group such as ethylene, propylene or butylene. A low molecular weight or high molecular weight compound containing at least one, preferably 2 to 4 unsaturated ether groups represented by the following formulas: bisphenol A, bisphenol F, bisphenol S , Polyphenol compounds such as phenolic resins, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane,
Condensates of polyols such as pentaerythritol with alkyl halide unsaturated ethers such as chloroethyl vinyl ether; polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and hydroxy such as hydroxyethyl vinyl ether Reaction products with alkyl unsaturated ethers and the like can be mentioned. 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 compound (b)
Is usually about 5 to 15 parts per 100 parts by weight of the resin (a).
0 parts by weight, preferably in the range of about 10-100 parts by weight.

In the composition containing the components (a) and (b), the coating film formed therefrom is crosslinked by heating, by addition reaction between a carboxyl group and / or a hydroxyphenyl group and an unsaturated ether group, and When it becomes insoluble in water or alkaline aqueous solution, then is irradiated with active energy rays, and then heated, the crosslinked structure is cut by the catalytic action of the generated acid, and the irradiated part becomes soluble again in solvent or aqueous alkaline solution. It is a type photosensitive resin composition.

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

Further, the photoacid generator described above is
It is a compound that generates an acid upon exposure to light and decomposes the resin using the generated acid as a catalyst. Conventionally known compounds can be used. Examples thereof include sulfonium salts, ammonium salts, phosphonium salts, onium salts such as iodonium salts, selenium salts, iron-allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfones Acid esters, sulfonic acid imide esters, halogen compounds and the like can be used.
In addition to the above, JP-A-77-146552, Japanese Patent Application No.
The photoacid generator described in No. 289218 can also be used.
This photoacid generator component may be a mixture with the above-mentioned resin or a compound bonded to the resin. The mixing ratio of the photoacid generator is about 0.1 to 100 parts by weight of the resin.
It is preferred that the content be 40 parts by weight, particularly about 0.2 to 20 parts by weight.

In the composition of the present invention, in addition to the above-mentioned resins, solubility in an organic solvent or an aqueous developer can be improved,
In addition, the above-mentioned other resins which are insoluble or dissolved (or dispersed) in water or an organic solvent, which can make the composition worse, can be blended as required.
Specifically, for example, a phenolic resin, a polyester resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, an epoxy resin, a silicon resin, a fluorine resin, and a mixture or modified product of two or more of these resins Is mentioned. Further, in order to impart appropriate flexibility, non-adhesiveness, and the like to a film formed using the composition of the present invention, the composition of the present invention includes a plasticizer such as a phthalate ester, a polyester resin, An acrylic resin or the like can be added. Further, a coloring agent such as a fluidity regulator, a plasticizer, a dye, and a pigment may be added to the composition of the present invention, if necessary.

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

Next, typical resist materials of the positive visible light-sensitive resin composition of the present invention (for example, a general positive photosensitive resist material and a positive resist material for electrodeposition coating)
Will be described.

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

Solvents used for dissolving or dispersing the positive-type visible light photosensitive resin composition include, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and esters (ethyl acetate, butyl acetate, benzoic acid) Methyl ether, methyl propionate, etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) , Halogenated hydrocarbons (chloroform, trichloroethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, dimethylsulfoxide, etc.), water and the like. .

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

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

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

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n- Butanol, t-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used is generally 30 parts by weight per 100 parts by weight of the resin solid component.
It can be up to 0 parts by weight, preferably up to 100 parts by weight.

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

The preparation of a positive visible light-sensitive resin composition as an electrodeposition coating composition can be carried out by a conventionally known method. For example, a resin or a resin mixture that has been made water-soluble by the above-described neutralization, a photosensitizer of a dipyrromethene boron complex compound, and if necessary, a solvent and other components are well mixed, and the mixture is prepared by adding water. it can.

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

The electrodeposition paint prepared as described above is
The coating can be performed on the surface of the conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is adjusted to 15 to 40 ° C, preferably 15 to 40 ° C.
Control at ~ 30 ° C. Next, in the electrodeposition coating bath controlled in this way, the conductor to be coated is immersed in a conductor to be coated as an anode when the electrodeposition coating is of an anionic type and as a cathode when the electrodeposition coating is of a cationic type. Apply DC current. An appropriate energization time is 10 seconds to 5 minutes.

The obtained film thickness is a dry film thickness, generally 0.5
５０50 μm, preferably 1-20 μm. After the electrodeposition coating, the object to be coated is pulled up from the electrodeposition bath and washed with water, and then the water and the like contained in the electrodeposition coating film are dried and removed with hot air or the like (the compositions (a) and (b) are used). In such a case, the coated substrate is subjected to a temperature and a time under which a crosslinking reaction between the carboxyl group and / or hydroxyphenyl group-containing polymer and the vinyl ether group-containing compound substantially occurs, for example, about 60 to 60 Heat at a temperature of about 150 ° C. for about 1 minute to about 30 minutes to crosslink and cure the coating).

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

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

As the light source for the exposure, light sources such as ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight and the like are used. Among the light sources used, there can be used light rays in the visible region in which ultraviolet rays are cut by an ultraviolet cut filter, various lasers having oscillation lines in the visible region, and the like. As a high power and stable laser light source,
Second harmonic (532n) of GaN laser, He-Cd laser, argon laser, or YAG laser
m). In particular, the second harmonic (532 nm) of the YAG laser is preferable because it forms a film having excellent contrast.

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 non-exposed film is cationic. Alkaline aqueous solutions that can be neutralized with free carboxylic acids in the coating film, such as sodium hydroxide, sodium carbonate, sodium hydroxide, aqueous ammonia, etc., to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used.

In the case of a photosensitive resin having no ionic group, the developing treatment is carried out by dissolving the unexposed portion using a solvent such as 1,1,1-trichloroethane, tricrene, methyl ethyl ketone, methylene chloride or the like. . 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 (a) and (b) are used as the composition, the cross-linked structure of the cured coating film is cut on the substrate irradiated with visible light in the presence of the acid generated by the irradiation. Under such temperature and time conditions, for example, heating is performed at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating film on the irradiated portion. In that case, preferably,
The substrate irradiated with visible light is brought into contact with water in advance. The contact with water facilitates the generation of an acid and facilitates the subsequent cleavage reaction of the crosslinked structure. The contact with water can be performed by immersing the substrate in normal temperature water or hot water, or by spraying water vapor.

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

After the protective film is peeled off from the dry film resist, the resist film can be adhered to the support by thermocompression bonding so that the resist film comes into contact with the dry film resist to form a resist film. The resist film can be exposed to visible light and developed according to the image in the same manner as the above-mentioned electrodeposition coating film to form an image.

[0143]

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

Example 1 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
1 part and 3 parts of azobisisobutyronitrile are mixed with 1 part
The reaction product obtained by reacting at 00 ° C. for 2 hours is 1500 c
The resulting mixture was poured into a toluene solvent (c) to precipitate and separate the reaction product. The precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / Kg. Next, 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) was added to 100 parts of this, and NAI-
105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name)
10 parts and 0.1 as a photosensitizing dye.
Five parts of the compound were dissolved in diethylene glycol dimethyl ether to adjust the solid content to 20% to obtain a photosensitive solution. Next, this photosensitive solution was applied on a copper-clad laminate using a spin coater so that the dry film thickness became 5 μm.
Heating was performed at 0 ° C. for 8 minutes to form a resist film. The substrate was irradiated with a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and a second harmonic (532 nm) of a YAG laser through the positive pattern mask, and the substrate was heated at 120 ° C. for 10 minutes. Thereafter, development was performed using a 1% aqueous solution of sodium carbonate. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Examples 2 to 15 Photosensitive liquids were prepared in the same manner as in Example 1, except that 1-2 to 1-15 in Table 1 were used as photosensitizers. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and YAG were applied to the obtained substrate through a positive pattern mask. The above-mentioned photosensitive layer is irradiated with the second harmonic (532 nm) of a laser at 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. Similar results were obtained by irradiation with an argon laser (488 nm). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 16 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 a P-hydroxystyrene polymer (molecular weight: 1000), divinyl ether compound (1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) 60 parts), 2 parts of polyethylene glycol (average molecular weight 400), NAI-105
(Photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) 10
Of a photosensitizer used in Example 1 was dissolved in diethylene glycol dimethyl ether to obtain a 20% by weight photosensitive solution. Example 1 using this photosensitive liquid
A photosensitive layer is formed in the same manner as described above, and the substrate obtained by heating at 120 ° C. for 8 minutes is irradiated with a xenon lamp (a light beam in which an ultraviolet wavelength region is cut) and a second harmonic (532 nm) of a YAG laser through a positive pattern mask. Was exposed to light, heated at 120 ° C. for 10 minutes, and developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 17 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) 2 parts, 10 parts of NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) and 0.5 part of the photosensitizer used in Example 1 were dissolved in diethylene glycol dimethyl ether. A photosensitive solution of 20% by weight was obtained. Using this photosensitive solution, a photosensitive layer was formed in the same manner as in Example 1, and 1
The substrate obtained by heating at 20 ° C. for 8 minutes was subjected to a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and a second harmonic (532n) of a YAG laser through a positive pattern mask.
m), the above photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm).
The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 18 100 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.
After heating at 0 ° C. for 8 minutes, a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and a second harmonic (532n) of a YAG laser were applied to the obtained substrate through a positive pattern mask.
m), the above photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm).
The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 19 200 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, 100 parts of the product, 60 parts of a divinyl ether compound (condensate of 1 mol of bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) and 10 parts of NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) A mixture of 0.5 part of the photosensitizer used in Example 1 was dissolved in diethylene glycol dimethyl ether to prepare a solid content of 60% to obtain a photosensitive solution. 100 parts of photosensitive solution obtained above (solid content)
After mixing and stirring 0.8 equivalents of acetic acid with respect to the amino group,
Disperse in deionized water to form a water-dispersed resin solution (solid content 15
%). The obtained water-dispersed resin solution was used as an electrodeposition coating bath, a cation electrodeposition coating was performed using a laminated copper plate as a cathode, and the dry film thickness was 5 μm.
After heating the obtained substrate at 120 ° C. for 8 minutes, the second harmonic (532 nm) of a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and a YAG laser was passed through a positive pattern mask. The photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 20 50 parts of poly (t-butoxycarbonyloxystyrene) (molecular weight: 1000) was added to 1,000 parts of tetrahydrofuran,
The following novolak phenolic resin 50 parts, NAI-105
10 parts of a photoacid generator (trade name, manufactured by Midori Kagaku Co., Ltd.) and 0.5 part of the photosensitizing dye used in Example 1 were blended to obtain a photosensitive solution having a solid content of 9%. (Production of novolak phenolic resin) 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 liquid obtained above, a photosensitive layer was formed in the same manner as in Example 1, and after the solvent was evaporated, a xenon lamp (a light beam in which the ultraviolet wavelength region was cut off) was applied to the substrate through a positive pattern mask. ) And the second harmonic (532 nm) of a YAG laser were applied to the above photosensitive layer and heated at 120 ° C. for 10 minutes.
% 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. Argon laser (488n
Similar results were obtained by irradiation in m). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months. As a result, no change was found in the above-mentioned sensitivity.

Example 21 50 parts of poly (tetrahydropyranyl ether styrene) (molecular weight: 1000) was added to 1,000 parts of tetrahydrofuran,
50 parts of the novolak phenolic resin of Example 45, NAI
10 parts of -105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name) and 0.5 parts of the photosensitizing dye 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 the solvent was evaporated, a xenon lamp (a light beam whose ultraviolet wavelength region was cut) and YA were applied to the substrate through a positive pattern mask.
The above-mentioned photosensitive layer was irradiated with the second harmonic (532 nm) of a G laser, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual film after the development with respect to the irradiation amount of visible light, a film having excellent contrast was formed, and the reduction and swelling of the film in the unexposed portion were not observed at all. Similar results were obtained by irradiation with an argon laser (488 nm). The same evaluation was performed after the photosensitive layer was left at room temperature for 6 months.
No change was observed in the photosensitive sensitivity.

Example 22 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.

Further, a xenon lamp (cutting an ultraviolet wavelength region) and a YAG
Irradiation with the second harmonic (532 nm) of the laser confirmed that the resin was quickly cured. Similar results were obtained by irradiation with an argon laser (488 nm). The photosensitive solution was applied to a transparent polyethylene terephthalate sheet with a bar coater so as to have a thickness of 5 μm, and dried at 60 ° C. for 10 minutes, and the absorbance of the film was measured. As a result, at 550 to 630 nm, which is the range of ± 30 nm or more of the maximum wavelength of the safe light in FIG. It can be confirmed that the safety light is bright light from the relative luminous efficiency curve of FIG.

Examples 23 to 36 In Examples 1, 1-2 to 1- of Table 1 were used as photosensitizers.
A photosensitive solution having the same composition as in Example 1 was obtained except that No. 15 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 37 The photosensitive solution of Example 16 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 38 The photosensitive solution of Example 17 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 39 100 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 and stirred, and then dispersed in deionized water to obtain an aqueous resin solution ( (Solid content 15%).

The resulting aqueous dispersion 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 and drying at 120 ° C. for 8 hours.
After heating for a minute, a substrate having a resist coating was prepared. Next, the resist film obtained above (dry film thickness 5 μm)
1 was irradiated for 24 hours with the sodium lamp of FIG. 1 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.

Example 40 In 100 parts (solid content) of the photosensitive solution obtained in Example 19, 0.8 equivalent of acetic acid was mixed and stirred with respect to amino group, 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 41 Using the photosensitive solution obtained in Example 20, 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 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 42 Using the photosensitive solution of Example 21, a photosensitive layer was formed in the same manner as in Example 1, the solvent was evaporated, and coating was performed so that the dry film thickness became 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, NKX-1595 was used as a photosensitizer.
A photosensitive solution was prepared in the same manner as in Example 1 except that 1.5 parts (trade name, coumarin-based compound, manufactured by Nippon Kosaku Dyeing 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 argon laser (48) was applied to the obtained substrate through a positive pattern mask.
8 nm), the photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the residual amount of the film after the development with respect to the amount of visible light irradiation, the film was not dissolved and was poor. 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 were also poor in the same result.

Comparative Example 2 A test was performed 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 poorly dissolved in the aqueous sodium carbonate solution. FIG. 4 shows the spectral distribution of the fluorescent lamp used in the comparative example.
Shown in

[0164]

According to the present invention, the positive-type visible light-sensitive resin composition containing a specific compound as a photosensitizer is a composition having extremely high practical utility. Extremely soluble and soluble in general-purpose coating solutions
A coated surface which is uniform on a support and excellent in storage stability over time can be obtained. In addition, the photosensitizer used in the present invention can be used for conventional visible lasers such as an argon laser having stable oscillation lines at 488 nm and 514.5 nm and a YAG laser having a bright line at 532 nm as a second harmonic. Very high sensitivity compared to technology. Therefore, the positive visible light-sensitive resin composition of the present invention can perform high-speed scanning exposure even when the amount of the photosensitizer used for the acid generator and the substrate resin is small, and an extremely fine high-resolution image is obtained. can get. Further, the positive-type visible light-sensitive resin composition of the present invention can be coated and printed under bright environmental conditions without thickening the composition under environmental conditions of safe light irradiation, so that safe work can be performed. It exerts a remarkable effect with excellent properties, work efficiency, product quality stability and the like.

[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 F term (reference) 2H025 AA00 AA01 AB03 AB20 AC01 AC08 AD03 BE00 BF00 BG00 CA50 CC03 FA03 FA12 FA17 2H096 AA06 AA30 BA09 BA10 BA11 BA20 EA02 EA04 FA01 GA08 LA16 4J011 QB02 SA86 UA01 UA01 VA01

Claims (7)

[Claims] 1. A photosensitive resin composition comprising a photosensitizer and a positive visible light-sensitive resin, wherein a dipyrromethene boron complex compound represented by the general formula (1) is contained as a photosensitizer. A photosensitive resin composition comprising: Embedded image [Wherein, R 1 to R 6 each independently represent a hydrogen atom,
A halogen atom, an alkyl group which may have a substituent,
Aralkyl groups, aryl groups, alkenyl groups, alkylthio groups, aralkylthio groups, arylthio groups, heterocyclic groups,
A heterocyclic thio group, or [Wherein L 1 and L 2 are each independently a hydrogen atom,
An alkyl group which may have a substituent, an aralkyl group,
Represents an aryl group. An amino group represented by the formula:
-R3, R4 -R6, adjacent groups may be bonded to each other to form an alicyclic ring which may be substituted, and R7 is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group, Represents an aryl group, X1 and X2
Represents a halogen atom, an alkyl group which may have a substituent, an aralkyl group, or an aryl group. ] 2. The photosensitive resin composition according to claim 1, wherein in the general formula (1), R1 to R6 and R7 are each independently a hydrogen atom or an alkyl group which may have a substituent. 3. The positive-type visible light-sensitive resin is a resin containing a photoacid generator component or a mixture thereof, and an exposed portion of these resins exposed to visible light is dissolved in an organic solvent or an aqueous developer. 3. The positive-type visible light-sensitive resin composition according to claim 1, wherein the unexposed portion is a resin that does not dissolve in an organic solvent or an aqueous developer. 4. A positive-type visible light-sensitive resin composition for use in an environment in which a safety light having a maximum wavelength selected from the range of 500 to 620 nm and a large relative luminous efficiency is used, and formed from the composition. 2. An absorbance of the unexposed film 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 positive visible light-sensitive resin composition according to any one of Items 1 to 3, wherein 5. A discharge lamp mainly composed of sodium as a safety light (mainly a D line having a light wavelength of 589 nm).
The positive visible light-sensitive resin composition according to claim 4, wherein 6. A composition for a positive-type visible light-sensitive material, comprising the positive-type visible light-sensitive resin composition according to claim 1 and a solvent. 7. A positive resist material comprising the positive visible light-sensitive resin composition according to claim 1 on a substrate.