JPH1045741A - Coumarin compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a photosensitizer, having high compatibility with photosensitive resins and giving a photosensitive resin enabling high-speed scanning light-exposure by the use of the compound as a photosensitizer. SOLUTION: The objective compound is expressed by the formula I [R1 and R2 are each H, an alkyl, an aryl, etc.; R3 is H, a halogen, an alkyl, an arylthio, etc.; Z is a group of the formula II (X is O, S, NH, etc.), etc.], e.g. the compound of the formula III. The compound of the formula I can be produced by the condensation reaction of a coumarin aldehyde compound of the formula IV with an amino compound of the formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, a coumarin compound, and a visible light-sensitive resin composition containing the compound as a photosensitizer and having high sensitivity to light in the visible light region.

[0002]

2. Description of the Related Art In recent years, in the field of information using a photopolymerization reaction or image recording, instead of a conventional recording method using ultraviolet light using a film original or the like, a manuscript electronically edited by a computer is directly output at a high output. A method of directly outputting and recording using a laser is being studied. This method has the advantage that the recording and image forming steps can be greatly simplified by direct writing with a laser.
At present, many high power and stable laser light sources generally used have an output wavelength in the visible region.
Specifically, an argon laser having stable oscillation lines at wavelengths of 488 nm and 514.5 nm, or a YA having a bright line at 532 nm as a second harmonic (abbreviated as SHG).
G lasers and the like are widely used. Conventionally used photosensitive compositions have almost no sensitivity in the visible region, so it is necessary to add a photosensitizer having sensitivity to visible light. Although the addition of a pyrylium salt or a thiopyrylium salt can improve the sensitivity in the visible region, the storage stability of the photosensitive layer is low and it has been difficult to use it.

As compounds having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazolyl coumarin (common name: coumarin-6) or bis [3-
(7-Diethylaminocoumalyl)] ketone (common name: ketocoumarin) is known, but since the maximum absorption wavelength is around 450 nm, it is difficult to use 4
The wavelength is shorter than 88 nm, and the sensitivity is insufficient.

In the field of information or image recording using a photopolymerization reaction, there is a demand for a visible light-sensitive resin composition having excellent practicality. A photosensitive resin generally has no sensitivity to visible light, and in order to perform direct writing with a visible light laser, various characteristics are required for a photosensitizer. Such photosensitizers have appropriate absorption wavelengths and extinction coefficients, are highly sensitive, have good solvent solubility and compatibility with other components, and have good storage stability as required characteristics. No. However, at present, it has not been sufficiently elucidated how the molecular structure of the photosensitizer or the interaction with other contained components causes the expression of each property. For this reason, it is a difficult task to select a photosensitizer that satisfies all of the required characteristics, and it is not easy to infer and select from known materials.

[0005]

SUMMARY OF THE INVENTION The present invention provides an argon laser or a YA which is a high power and stable laser light source.
An object of the present invention is to provide a photosensitizer highly sensitive to laser light in a visible light region such as a G laser (SHG) and a photosensitive resin composition.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an Ar laser and a Y laser have been developed.
The present inventors have found a compound having an absorption wavelength, high sensitivity, and sufficient solvent solubility sufficient for practical use with an AG laser (SHG), and have completed the present invention. That is, the present invention
A coumarin compound represented by the following general formula (1):
A photosensitizer containing the compound, a visible light-sensitive resin composition containing the photosensitizer, an ink for a visible light-sensitive material containing the visible light-sensitive resin composition and a solvent, And a visible light-sensitive material having the visible light-sensitive resin composition on a substrate.

[0007]

Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
Aryl group, alkenyl group, aralkyl group, alkoxyalkyl group, aryloxyalkyl group, alkenyloxyalkyl group, hydroxyalkyl group, or group represented by the following general formula (2)

[0008]

Embedded image (Wherein Q ₁ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group or a cycloalkyl group, and p and q each represent an integer of 1 to 5); ₁ and R ₂ may be bonded to each other or to a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ₃ may be a hydrogen atom,
A halogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkoxyalkoxy group, an alkylthio group, an arylthio group or a sulfonic acid group; ) Or a group represented by (4)

[0009]

Embedded image (Wherein X is an oxygen atom, a sulfur atom, a —NH— group or —
Represents an NR ₄ — group, wherein R ₄ represents an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkenyloxyalkyl group or the general formula (2); Y represents an oxygen atom or ＝ C (CN) ₂ group).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound of the present invention is a novel coumarin compound represented by the general formula (1) and useful as a photosensitizer. Since the compound of the present invention has excellent properties, it is most suitable for photocuring using a photocurable resin and a photopolymerization initiator, and is extremely useful. Furthermore, the sensitivity of the conventional photosensitive resin composition greatly fluctuated due to the difference in the coating method, but the photosensitive composition containing a photosensitizer of the present invention shows stable sensitivity in any method. It satisfies the needs of the market.

The coumarin compound of the present invention has the general formula (1)
It is represented by In the general formula (1), examples of R ₁ and R ₂ are each independently or identically a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be branched; a cycloalkyl group such as cyclopentyl and cyclohexyl; Aryl groups such as groups; alkenyl groups such as allyl, 2-butenyl and 2-pentenyl groups; aralkyl groups such as benzyl groups;
C2-C11 such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, etc.
Phenyloxymethyl, p-
Aryloxyalkyl groups such as methylphenyloxyethyl, m-methylphenyloxypropyl, o-methylphenyloxybutyl and 2,4-dimethylphenyloxypentyl; allyloxymethyl, 2-butenyloxyethyl, 2-pentenyloxy Alkenyloxyalkyl groups such as propyl group; hydroxymethyl, hydroxyethyl,
Hydroxyalkyl groups such as 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxybutyl groups; and groups represented by the general formula (2), for example, hydroxymethoxymethyl, hydroxyethoxyethyl, 2-hydroxypropoxy Hydroxyalkoxyalkyl groups such as methyl and 3-hydroxypropoxybutyl groups; hydroxypolyether groups such as hydroxyethoxyethoxybutyl, hydroxypropoxypropoxymethyl, hydroxymethoxyethoxypentyl, hydroxypropoxymethoxymethyl, hydroxyethoxyethoxyethoxyethyl groups; methoxymethoxy Methyl, methoxyethoxyethyl, ethoxymethoxypropyl, ethoxyethoxybutyl, ethoxypropoxypentyl, methoxyethoxyethoxyethyl, ethoxy And polyether groups such as ethoxyethoxyethoxyethyl. R ₁ and R ₂ may be bonded to each other to form a ring, or may form a ring with a benzene nucleus in the skeleton.
a) to (5e) (Formula 7) may be formed.

[0012]

Embedded image (Where R ₂ and R ₃ have the same meaning as in the general formula (1), and Q _{3 to} Q ₆ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

R ₁ and R ₂ are preferably an alkyl group, alkenyl group, alkoxyalkyl group, aryloxyalkyl group, alkenyloxyalkyl group, hydroxyalkyl group, formula (2) or formula (5a)
It is a substituent represented by (5e), more preferably an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, or a substituent represented by the general formula (2) or (5b).

In the general formula (1), examples of R ₃ include a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; a methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl group and the like. A hydroxyalkyl group such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 2-hydroxybutyl; chloromethyl, dichloromethyl, fluoromethyl and trifluoromethyl , Pentafluoroethyl,
A halogenoalkyl group having 1 to 10 carbon atoms such as nonafluorobutyl group; a hydroxyl group; an alkoxy group having 1 to 10 carbon atoms; phenyloxy, p-methylphenyloxy, m-methylphenyloxy, o-methylphenyloxy, 2,4- Aryloxy group such as dimethylphenyloxy group; having 2 to 1 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, n-propoxyethoxy, etc.
1 alkoxyalkoxy group; alkylthio group such as methylthio, ethylthio, n-butylthio group; arylthio group such as phenylthio, 2-methylphenylthio, 3-chlorophenylthio, 4-methoxyphenylthio group;
And a sulfonic acid group.

In the general formula (1), Z represents a group represented by the general formula (3) or (4). In formula (3), X is an oxygen atom, a sulfur atom, -NH- group or -NR ₄ - represents a group, R ₄ is an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an aryloxy group, an alkenyl Represents an oxyalkyl group, a hydroxyalkyl group or a substituent represented by the above formula (2). X is preferably an oxygen atom, a sulfur atom, -N
It is an R ₄ — group, more preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom. R ₄ is preferably an alkyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, a hydroxyalkyl group, a polyether group or a hydroxypolyether group, and more preferably an alkoxyalkyl group, a hydroxyalkyl group, or a polyether group. Or a hydroxypolyether group.

The ring A may be substituted. Examples of the optionally substituted group include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, n-propyl, i
so-propyl, n-butyl, iso-butyl, ter
an alkyl group having 2 to 11 carbon atoms such as an alkyl group such as t-butyl, methoxy, ethoxy, and propoxy group; a nitro group; an amino group; an alkylamino group having 2 to 12 carbon atoms such as dimethylamino, diethylamino and dibutylamino; Arylamino groups such as diphenylamino; and substituted amino groups substituted with alkyl groups, alkoxyalkyl groups, hydroxyalkyl groups, polyether groups or hydroxypolyether groups. In the general formula (4), Y represents an oxygen atom or a = C (CN) ₂ group, and is preferably a = C (CN) ₂ group. The coumarin compound of the present invention can be produced by a known method. A Schiff base compound in which Z in the general formula (1) is represented by the general formula (3):
For example, it can be produced according to the following reaction formula (Formula 8).

[0017]

Embedded image The compound represented by the general formula (8) is typically prepared by using a reaction accelerator in the presence of a coumarinaldehyde compound represented by the general formula (6) and an amino compound represented by the general formula (7). It is produced by a condensation reaction.

The coumarin aldehyde compound represented by the general formula (6) and the amino compound represented by the general formula (7) can be produced by a known production method. The coumarin aldehyde compound represented by the general formula (6) can be reacted by a known method, for example, a method described in DE 2413281, or by reacting according to a reaction formula (Chemical formula 9).
Obtainable. Note that the N-substituted salicylaldehyde compound in the reaction formula refers to the m-aminophenol compound as described in "New Experimental Chemistry Course 14 [II], 688-699.
(1977, edited by The Chemical Society of Japan) "
It is obtained by performing formylation by an er reaction.

[0019]

Embedded image Further, the amino compound represented by the general formula (7) is “Comp
rehensive HeterocyclicChemistry vol.6 (1984
Pergamon Press) ”or“ New Experimental Chemistry Course 14 [iv], 2212, 2228, 2231 (1
978, edited by The Chemical Society of Japan).

The compound represented by the general formula (8) is described, for example, in "Organic Synthesis vol. 61, 14-17 (1983)".
In addition, for example, a coumarin aldehyde compound represented by the general formula (6) and an amino compound represented by the general formula (7) are converted into methanol, ethanol, N, N-dimethylformamide (hereinafter abbreviated as DMF). In a polar solvent such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), if necessary.
A catalytic amount of a base (eg, amines such as piperidine, pyrrolidine, pyridine, aniline, caustic soda,
0-100 ° C.
For 1 to 12 hours. The olefin compound in which Z in the general formula (1) is represented by the general formula (4) can be produced, for example, according to the following reaction formula (Formula 10).

[0021]

Embedded image The compound represented by the general formula (10) is typically prepared by using a coumarin aldehyde compound represented by the general formula (6) and a pyran compound represented by the general formula (9) in the presence of a reaction accelerator. It is produced by a condensation reaction.

The pyran compound represented by the general formula (9) is
It can be manufactured by a known manufacturing method. For example, "Comprehens
ive Heterocyclic Chemistry vol.3 (1984 Perga
monPress) ”, or when Y is an oxygen atom,“ New Experimental Chemistry Course 14 [iv], 2021 (1
978, edited by The Chemical Society of Japan), and when Y is = C (CN) ₂ ,
0-83035. The compound represented by the general formula (10) is described, for example, in JP-A-60-8
No. 3035, the method described in JP-A-6-329654, for example, the coumarin aldehyde compound represented by the general formula (6) and the pyran compound represented by the general formula (9)
In a polar solvent such as methanol, ethanol, N, N-dimethylformamide (hereinafter abbreviated as DMF), dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI), if necessary. For example, a weak base (for example, amines such as piperidine, pyrrolidine, pyridine, and aniline) having a catalytic amount of about 1/10 is added, and 0 to 10
It is obtained by reacting at 100 ° C. for 1 to 12 hours.

The coumarin compound of the present invention represented by the general formula (1) is excited by absorbing light in the visible light region of 400 to 700 nm, particularly light of 400 to 600 nm, to form a photocurable resin, It is a compound that interacts with the polymerization initiator. The term "interaction" as used herein includes energy transfer and electron transfer from the excited compound of the present invention to the photocurable resin or the polymerization initiator. Therefore, the compound of the present invention is a very useful compound as a photosensitizer.

The photosensitizer of the present invention contains at least one coumarin compound represented by the general formula (1), and may contain other known photosensitizers. The known photosensitizer is not particularly limited as long as it is a commonly used photosensitizer, and examples thereof include ketocoumarin, coumarin-6, and coumarin compounds described in JP-A-4-18088. In this case, the content of the coumarin compound represented by the general formula (1) in the photosensitizer is not particularly limited, but in order to obtain a desired effect in the present invention, the content in the photosensitizer is not limited. The content of the coumarin compound represented by the general formula (1) is preferably at least 10% by weight, more preferably at least 20% by weight, further preferably at least 30% by weight, and at least 50% by weight. The contained photosensitizer is particularly preferred.

The visible light-sensitive resin composition of the present invention contains a photocurable resin, a photopolymerization initiator and a photosensitizer, and, if necessary, contains a solvent and other photocurable resins. is there. Further, it may contain a substance called an activator or a starting aid. In the visible light-sensitive resin composition of the present invention, the amount of the photosensitizer used in the present invention depends on the type and amount of the coumarin compound represented by the general formula (1) contained in the photosensitizer, The amount of the coumarin compound of the present invention is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the photocurable resin component, although it varies depending on the type of the photocurable resin component to act. A range of parts by weight is suitable. If the amount of the present compound is less than 0.1 part by weight, the photosensitivity of the formed film tends to decrease,
If the amount is more than 0 parts by weight, it tends to be difficult to keep the composition in a uniform state from the viewpoint of solubility.

The photocurable resin used in the present invention is not particularly limited as long as it is a generally used photocurable resin having a photosensitive group which can be crosslinked or polymerized by light irradiation. JP-A-3-223759, page 2, right lower column, line 6 to page 6, lower left column, line 16, anionic photocurable resin containing (meth) acryloyl group as a photosensitive group, photosensitive group Examples thereof include a photocurable resin containing a cinnamoyl group and a photocurable resin containing an allyl group as a photosensitive group. Further, photopolymerizable or photocrosslinkable compounds having at least one ethylenically unsaturated double bond in the molecule, which are commonly used as photocurable resins, include monomers, prepolymers, dimers, and trimers. Oligomers, mixtures thereof, and copolymers thereof. Monofunctional and polyfunctional acrylates and methacrylates are generally used. Further, unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic alcohol compounds or aliphatic polyol compounds, and the like, are disclosed in JP-A-58-15503. The photocurable resin described on page 3 to page 4 of the publication can be used. The photocurable resin has different reactivity, viscosity and the like depending on the type thereof, and thus two or more types may be used in combination.

The visible light-sensitive resin composition of the present invention is not particularly limited as long as it is a commonly used photopolymerization initiator. For example, benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone, Aromatic carbonyl compounds such as anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α,
α'-dichloro-4-phenoxyacetophenone, 1-
Acetophenones such as hydroxy-1-cyclohexylacetophenone and acetophenone; benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyldioxide Organic peroxides such as peroxyisophthalate and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; carbon tetrachloride; Organic halides such as carbon tetrabromide, chloroform and iodoform, 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,
Heterocyclic and polycyclic compounds such as 3,5-triazinebenzanthrone and 9-phenylacridine; 2,2'-azo (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile , 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2
Azo compounds such as -methylbutyronitrile); iron-arene complexes (see European Patent No. 152377); titanocene compounds (JP-A-63-2211).
No. 10); a bisimidazole compound; an N-arylglycine compound; an acridine compound; a combination of an aromatic ketone and an aromatic amine.

Among the above polymerization initiators, di-t-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, iron-allene complex, titanocene The compound is a preferable compound because of its high activity for crosslinking or polymerization, and particularly preferably a titanocene compound. The amount of these photopolymerization initiators is not critical and can be varied in a wide range depending on the type and the like, but generally, the photocurable resin solid content per 100 parts by weight described above is
It can be in the range of 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight. When used in a large amount exceeding 25 parts by weight, the stability of the resulting composition tends to decrease.

Next, the use of the visible light-sensitive resin composition of the present invention will be described. The visible light-sensitive resin composition of the present invention can be handled in the same manner as a commonly used known photosensitive material. For example, the visible light-sensitive material ink (photosensitive liquid) of the present invention is obtained by dissolving a visible light-sensitive resin composition containing the compound of the present invention in a solvent (when a pigment is used as a coloring agent, the pigment is finely dispersed). To be obtained.
The visible light-sensitive material of the present invention has the photosensitive resin composition of the present invention on a substrate, and has various forms. For example, the photosensitive liquid is coated on a base material, for example, using a coating device such as a roller, a roll coater, a bar coater, a blade coater, a reverse coater, a die coater, a spin coater, or a spray coater, and dried. By doing so, it can be used as a visible light sensitive material.

Examples of the solvent to be used include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, methyl lactate, ethyl lactate, propyl lactate). Butyl lactate, etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), cellosolve acetates (methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol) Monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc.) Hydrogen (benzene, toluene,
Xylene, ethylbenzene, etc.), halogenated hydrocarbons (chloroform, trichloroethylene, dichloromethane, etc.), alcohols (methyl alcohol, ethyl alcohol, isopropyl alcohol, benzyl alcohol, etc.), and others (dimethylformamide, N-methylpyrrolidone, N, N-dimethyl) Imidazolidinone, dimethyl sulfoxide, etc.). As the base material, for example, a sheet of a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing them or a printed board, a surface of which is treated with these metals, plastic, glass or a silicon wafer ,
And carbon.

The visible light-sensitive composition of the present invention can also be used for PS plates for offset printing. As a procedure for manufacturing, first, the above-mentioned organic solvent, a photocurable resin,
The photosensitive resin composition containing a photopolymerization initiator, a photosensitizer and other additives is diluted to a solid concentration of 1 to 40% by weight, preferably 5 to 20% by weight. This photosensitive solution is applied to an aluminum substrate or polyethylene terephthalate (PE).
T) Drying on a film thickness of 0.2 to 10 g / m ^2, preferably coated to a 1 to 4 g / m ^2, dried to a photosensitive resin layer. It is preferable to provide an overcoat layer for blocking oxygen on the photosensitive resin layer. For the overcoat layer, polyvinyl alcohol (PVA)
And those having an average molecular weight of 300 to 1000 and a saponification ratio of 70 to 90% are preferred. For the preparation of the overcoat layer, a 5 to 20% by weight aqueous solution of PVA is used.
This overcoat layer is applied so as to have a dry film thickness of 0.5 to 5 μm, preferably 1 to 2 μm. By drying this, a PS plate is obtained.

The visible light-sensitive resin composition of the present invention can be handled in the same manner as ordinary photosensitive materials for electrodeposition coating, and can be used as a coating for electrodeposition coating.
In that case, first make the photocurable resin an aqueous dispersion,
Or a water-soluble product. Water-dispersion or water-solubilization of the photocurable resin is performed by neutralizing with an alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the photocurable resin, or by amino group or the like. When the cationic group is introduced, the reaction is carried out by neutralization with an acid (neutralizing agent). Examples of the alkali neutralizer used at that time include, for example, 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; As the acid neutralizer, for example, formic acid,
Monocarboxylic acids such as acetic acid, lactic acid, and butyric acid are exemplified. These neutralizing agents can be used alone or in combination. The amount of the neutralizing agent to be used is generally 0.2 to 1.0 equivalent, especially 0.3 to 0.1 equivalent, per equivalent of the ionic group contained in the photocurable resin.
A range of 8 equivalents is desirable.

In order to further improve the fluidity of the water-soluble or water-dispersed resin component, if necessary, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol, t-butanol may be added to the photocurable resin. ,
Methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether,
Dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent to be used can be generally up to 300 parts by weight, preferably up to 100 parts by weight, per 100 parts by weight of the resin solid component. Further, in order to increase the amount of coating on the object to be coated, for the photocurable resin,
Hydrophobic solvents, for example, petroleum solvents such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate;
Alcohols such as ethylhexyl alcohol and benzyl alcohol can also be added. The compounding amount of these hydrophobic solvents is usually 100 parts by weight of the resin solid component,
It can be up to 200 parts by weight, preferably 100 parts by weight or less.

The preparation of the visible light-sensitive composition as an electrodeposition paint can be carried out by a conventionally known method. For example,
The photocurable resin water-solubilized by the neutralization, the photosensitizer of the present invention, a polymerization initiator, and, if necessary, a nitrogen-containing compound, a solvent and other components are thoroughly mixed, and water is added. Can be prepared. The composition thus prepared is further diluted with water in a usual manner, for example, in a pH range of 4 to 9 and a bath concentration (solid content concentration) of 3 to 3.
Electrodeposition paint (or electrodeposition bath) can be in the range of 25% by weight, preferably 5 to 15% by weight.

The electrodeposition paint prepared as described above is
The coating can be performed on the surface of the conductor to be coated as follows. That is, first, the pH and bath concentration of the bath are adjusted to the above ranges, and the bath temperature is adjusted to 15 to 40 ° C., preferably 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. The energization time is suitably 30 seconds to 5 minutes, and the resulting film thickness is a dry film thickness, generally 0.5 to 50 μm, preferably
1 to 15 μm. After the electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then moisture and the like contained in the electrodeposition coating film are dried and removed with hot air or the like. As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material in which these are fixed to the surface of plastic or glass by lamination, plating or the like can be used.

The visible light-sensitive material formed on the base material or the conductor surface as described above, or the visible light-sensitive electrodeposited coating film obtained by electrodeposition coating, is exposed to visible light according to the image. An image can be formed by exposing, curing, and removing the unexposed portions by a developing treatment. Light sources for exposure include ultra-high, high, medium and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps,
Among the light sources obtained from each light source such as a metal halide lamp, a fluorescent lamp, a tungsten lamp, and sunlight, there can be used light rays in a visible region in which ultraviolet rays are cut by an ultraviolet cut filter, various lasers having oscillation lines in the visible region, and the like. As a high power and stable laser light source, an argon laser or a second harmonic of a YAG laser is preferable.

The developing treatment is carried out by rinsing with an aqueous alkali solution when the non-exposed portion film is anionic, and with an aqueous acid solution having a pH of 5 or less when the non-exposed film is cationic. Alkaline aqueous solutions are generally capable of imparting water solubility by neutralizing free carboxylic acids in the coating, such as caustic soda, sodium carbonate, caustic potash, and ammonia water, and acid aqueous solutions include acetic acid, formic acid, lactic acid, and the like. Can be used. In the case of a photocurable resin having no ionic group, development processing is performed by dissolving an unexposed portion using a solvent such as 1,1,1-trichloroethane, trichloroethylene, methyl ethyl ketone, or methylene chloride. The coated film after development is washed with water and dried with hot air or the like, so that a desired image is formed on the conductor. Also,
If necessary, the printed circuit board can be manufactured by performing etching and removing the exposed conductor portion, and then removing the resist film. The composition of the present invention includes a photoresist, a plate-making material for flat plates and letterpress, and a P for offset printing.
It can be applied to a wide range of applications such as S-plates, information recording materials, and relief image forming materials.

[0038]

EXAMPLES The present invention will be described below with reference to specific examples, but these are illustrative, and the present invention is not limited to these examples. Parts in Examples are parts by weight, and% means% by weight. Example 1 Under a nitrogen atmosphere, 2.5 parts of 3-formyl-7-diethylaminocoumarin, 1.8 parts of 2-amino-6-chlorobenzothiazole and 1.0 part of triethylamine were heated and refluxed in 25 parts of ethanol for 8 hours. And reacted. After cooling down,
After filtration, washing with ethanol and drying, the following formula (A)
2.1 parts of the compound of the formula (11) were obtained.

[0039]

Embedded image The analysis results of this compound were as follows. • Absorption spectrum; absorption maximum [λmax] 503 nm (in chloroform) • FD-MS spectrum; m / z = 411 (M ⁺ ) • Elemental analysis value (C ₂₁ H ₁₈ ClN ₃ O ₂ S) C (%) H ( %) N (%) Calculated S (%) 61.24 4.40 10.20 7.79 Found 61.17 4.46 10.40 7.72

Example 2 2,6-dimethyl-γ-pyrone 21.1 under a nitrogen atmosphere
And 12.3 parts of malononitrile were reacted in 63 parts of acetic anhydride by heating under reflux for 1 hour. After standing to cool, filtered,
After washing with methanol and drying, the following formula (B) (Formula 1)
20 parts of the compound of 2) were obtained. Under a nitrogen atmosphere, 3.6 parts of 3-formyl-7-dinorbutylaminocoumarin, the compound of the formula (B) and 1.2 parts of piperidine were reacted by heating and refluxing for 24 hours in 24 parts of ethanol. After cooling down,
The mixture was filtered, washed with ethanol, and dried. This was washed with chloroform, then washed with acetone, and dried to obtain 1.5 parts of a compound represented by the following formula (C).

[0041]

Embedded image The analysis results of the compound of the formula (C) were as follows. Absorption spectrum; absorption maximum [λmax] 487 nm (in chloroform) FD-MS spectrum; m / z = 455 (M ⁺ ) Elemental analysis value (C ₂₈ H ₂₉ N ₃ O ₃ ) C (%) H (% ) ) Calculated N (%) 73.83 6.41 9.23 Found 73.87 6.38 9.34

Example 3 Under a nitrogen atmosphere, 22.3 parts of a 3-aminophenol compound of the following formula (D) (Formula 13) were dissolved in 80 parts of dry DMF, and 30.6 parts of phosphorus oxychloride was added at room temperature. It was added dropwise and reacted at 70 ° C. for 7 hours. After the reaction, the reaction solution was discharged into 200 parts of ice water, neutralized with 28% aqueous ammonia, and extracted with ethyl acetate. After washing with water and concentration, the salicylaldehyde compound of the following formula (E)
8 parts were obtained. Under a nitrogen atmosphere, 4.5 parts of the compound of the formula (E) and 3.5 parts of diethyl malonate were dissolved in 40 parts of ethanol, 0.5 part of piperidine was added, and the mixture was refluxed for 7 hours. After cooling, the mixture was filtered to obtain 4.2 parts of a compound represented by the following formula (F). 4.0 parts of the compound of the following formula (F) was dispersed in 20 parts of water, 25 parts of 35% hydrochloric acid was added, and the mixture was refluxed for 5 hours. After cooling, the mixture was filtered, washed with water, and dried to obtain 2.8 parts of a compound of the following formula (G) (formula 13). Under a nitrogen atmosphere, 2.5 parts of the compound of the formula (G) was dissolved in 12 parts of dry DMF, 2.0 parts of phosphorus oxychloride was added dropwise at room temperature, and the mixture was reacted at 50 ° C. for 3 hours. After the reaction, the reaction solution was discharged into 20 parts of ice water, neutralized with 28% aqueous ammonia, and filtered. After washing with water and drying, the following formula (H)
2.5 parts of compound 3) were obtained. Under a nitrogen atmosphere, 1.0 part of a compound of the following formula (H), 0.9 part of 2-amino-5-methoxybenzoxazole and 0.9 part of triethylamine.
4 parts were refluxed for 3 hours in 30 parts of ethanol. After cooling, filtration, washing with ethanol, and drying, the following formula (I)
1.2 parts of the compound of formula (13) were obtained.

[0043]

Embedded image The analysis results of the compound of the formula (I) were as follows. - absorption spectrum; absorption maximum [λmax] 495 nm (in chloroform), FDMS spectrum; m / z = 463, elemental analysis _{(C 26 H 29 N 3 O} 5) C (%) H (%) N (%) calculated Value 67.38 6.30 9.07 found 67.32 6.21 9.08

Example 4 As a photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / benzyl methacrylate = 50/20/10
/ 20 of a mixture of / 20, a mixture of 55 parts of trimethylolpropane triacrylate, 20 parts of a titanocene compound of the following formula (J) (Formula 14) as a polymerization initiator, and a coumarin obtained in Example 1 as a photosensitizer. A photosensitive solution was prepared using 5 parts of the compound and 160 parts of methyl cellosolve as a solvent. This photosensitive solution was applied on a laminated copper plate using a spin coater so as to have a dry film thickness of 3.5 g / m ² . After drying, an aqueous solution of polyvinyl alcohol was applied and dried to form an overcoat layer. When the above-mentioned photosensitive layer was irradiated with the second harmonic (532 nm) of a YAG laser having an intensity of 5.0 mJ / cm ² , it was confirmed that the resin was quickly cured. After exposure, development was carried out with a 0.5% aqueous solution of sodium carbonate. The obtained pattern was a good pattern having no film loss by the developing solution and no resist residue in the unexposed portion. The photosensitive layer obtained in the same manner was further exposed to an argon laser having an intensity of 5.0 mJ / cm ² and then developed, whereby a good pattern was obtained.

[0045]

Embedded image

Example 5 A photosensitive layer was prepared in the same manner as in Example 4 except that the compound obtained in Example 2 was used instead of the compound obtained in Example 1 as the coumarin compound in Example 4. I got
This photosensitive layer was confirmed to be rapidly cured by the second harmonic (532 nm) of a YAG laser having an intensity of 5.0 mJ / cm ² . The photosensitive layer obtained in the same manner was further exposed to an argon laser having an intensity of 5.0 mJ / cm ² and then developed, whereby a good pattern was obtained.

Example 6 A photosensitive layer was prepared in the same manner as in Example 4 except that the compound obtained in Example 3 was used instead of the compound obtained in Example 1 as the coumarin compound in Example 4. I got
This photosensitive layer was confirmed to be rapidly cured by the second harmonic (532 nm) of a YAG laser having an intensity of 5.0 mJ / cm ² . The photosensitive layer obtained in the same manner was further exposed to an argon laser having an intensity of 5.0 mJ / cm ² and then developed, whereby a good pattern was obtained.

Examples 7 to 28 The coumarin compounds synthesized in the same manner as in Examples 1 to 3 are summarized in Table 1 (Tables 1 to 3). Using these compounds, evaluations were made in the same manner as in Examples 4 to 6, and the results were evaluated as the first
It is shown in the table. 5.0 mJ / c for the obtained photosensitive layer
The second harmonic of YAG laser m ² intensity (532 nm)
In addition, the photosensitive layer obtained in the same manner was further used for 5.0.
Scan exposure with an argon laser of mJ / cm ² intensity,
Developed. The state of the obtained pattern was evaluated as follows.

[0049]

[Table 1] Table 1

[0050]

[Table 2] Table 1 (continued)

[0051]

[Table 3] Table 1 (continued)

[0052]

The coumarin compound of the present invention is a compound having extremely high utility as a photosensitizer. That is,
The coumarin compound of the present invention has good compatibility with the photosensitive resin when preparing the visible light-sensitive resin composition, and is dissolved in a general-purpose coating solution, and is uniformly and smoothly coated on the substrate. Can be obtained. In addition, the coumarin compound of the present invention comprises 4
For general-purpose visible lasers such as an argon laser having stable oscillation lines at 88 nm and 514.5 nm, and a YAG laser having an emission line at 532 nm as a second harmonic,
Since it has very high sensitivity, the photosensitive material obtained using the photosensitizer of the present invention can be subjected to high-speed scanning exposure with these lasers. Further, the image obtained by the high-speed scanning exposure is an extremely high-resolution image.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07D 491/06 C07D 491/06 C08F 2/50 MDN C08F 2/50 MDN C08K 5/18 KAZ C08K 5 / 18 KAZ C08L 101/00 C08L 101/00 C09D 11/00 PTE C09D 11/00 PTE (72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] A coumarin compound represented by the general formula (1). Embedded image Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
An aryl group, an alkenyl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkenyloxyalkyl group, a hydroxyalkyl group, or a group represented by the following general formula (2) (Wherein Q ₁ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group or a cycloalkyl group, and p and q each represent an integer of 1 to 5); ₁ and R ₂ may be bonded to each other or to a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ₃ may be a hydrogen atom,
A halogen atom, an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkoxyalkoxy group, an alkylthio group, an arylthio group or a sulfonic acid group; ) Or (4) a group represented by (Chemical Formula 3) (Wherein X is an oxygen atom, a sulfur atom, a —NH— group or —
Represents an NR ₄ — group, wherein R ₄ represents an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkenyloxyalkyl group or the general formula (2); Y represents an oxygen atom or ＝ C (CN) ₂ group). 2. A photosensitizer containing the coumarin compound of claim 1. 3. A visible light-sensitive resin composition containing the photosensitizer according to claim 2. 4. An ink for a visible light-sensitive material, comprising the visible light-sensitive resin composition according to claim 3 and a solvent. 5. The visible light-sensitive resin composition according to claim 3,
A visible light-sensitive material provided on a substrate.