JP3512243B2 - Bis (3-coumaryl) thioketone compound and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel compound, a bis (3-coumaryl) thioketone compound, and a photosensitizer containing the bis (3-coumaryl) thioketone compound, which has high sensitivity to visible light rays. It relates to a resin composition.

[0002]

2. Description of the Related Art In recent years, in the field of information or image recording using a photopolymerization reaction, instead of the conventional recording method using ultraviolet rays such as film originals, electronically edited originals by a computer are directly output with high output. A method of directly outputting and recording with 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.
Currently, most of the commonly used high-power and stable laser light sources have their output wavelength in the visible region.
Specifically, an argon laser having stable oscillation lines at wavelengths of 488 nm and 514.5 nm, a YAG laser having a bright line at 532 nm as a second harmonic, and the like are widely used. Therefore, a compound having a high sensitivity to those wavelengths is desired, but a conventionally used photosensitizer for ultraviolet rays cannot be used because of its low sensitivity in the visible region. Further, although the sensitivity in the visible region can be improved by adding a pyrylium salt or a thiopyrylium salt, the storage stability of the photosensitive layer is low and it is difficult to use.

As a compound having photosensitivity in the visible region,
For example, 7-diethylamino-3-benzothiazoyl coumarin (common name: coumarin-6), or bis [3-
(7-Diethylaminocoumaryl)] ketone (common name: ketocoumarin) is known, but since these have a maximum absorption wavelength of around 450 nm, they have a wavelength shorter than 488 nm of an argon laser and thus have poor sensitivity. It is enough. Further, the 4-substituted-3-benzothiazoylcoumarin compound described in JP-A-4-18088 is an argon laser with a 4-substituted-3-benzothiazoylcoumarin compound.
Although it was sensitive to 88 nm, it had almost no absorption at 514.5 nm or 532 nm which is the second harmonic of the YAG laser, leaving room for improvement in sensitivity.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to 514.5 of an argon laser which is a high-power and stable laser light source.
to provide a photosensitizer having a high sensitivity to a laser beam having a long wavelength in the visible light region such as 532 nm which is the second harmonic of a YAG laser or the second harmonic of a YAG laser, and a photosensitive resin composition. Is.

[0005]

Means for Solving the Problems The inventors of the present invention have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention provides the following general formula (1)
A bis (3-coumaryl) thioketone compound represented by
The present invention relates to a photosensitizer comprising this compound and a visible light-sensitive resin composition containing the photosensitizer.

[0006]

[Chemical 3] [In the formula, R ₁ and R ₇ are each a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, or aryl. An oxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or the following substituent (Formula 4),

[0007]

[Chemical 4] (Here, Q _{1 to} Q ₄ are each a hydrogen atom, an alkyl group,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n, m, p and q each represent an integer of 1 to 5) R ₂ , R ₃ , R ₆ , R ₈ , R ₉ and R ₁₂ are each a hydrogen atom, a halogen atom, an alkyl group or an alkoxyalkyl group. , A hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group or a sulfonic acid group, and R ₄ , R ₅ , R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group, an alkoxyalkyl group or an alkenyl group. , A hydroxyalkyl group, an aralkyl group, an aryl group, an alkoxycarbonylalkyl group, and R ₄ and R
₅ , R ₁₀ and R ₁₁ may combine with each other to form a ring,
R ₃ and R ₄ , R ₅ and R ₆ , R ₉ and R ₁₀ , R ₁₁ and R
₁₂ may combine with each other to form a ring with a benzene nucleus substituted with an amino group in the skeleton]

The compound of the present invention is a novel bis (3-coumaryl) thioketone derivative useful as a photosensitizer. Conventionally, a coumarin-based compound has been known as a photosensitizer, but a compound having a thiocarbonyl group has not been known. The compound of the present invention is a compound into which a thiocarbonyl group has been newly introduced. That is, the compound of the present invention is
By introducing a thiocarbonyl group, a long absorption wavelength and high sensitivity were realized at the same time. A photocurable resin, for example, photopolymerization or photocrosslinking having at least one ethylenic unsaturated bond in the molecule. It is a compound that is extremely useful as a compound that can be applied to photocuring using a photopolymerization initiator. Furthermore, the sensitivity of conventional photosensitizers fluctuates greatly depending on the coating method, but the photosensitizer of the present invention shows stable sensitivity in any method and sufficiently satisfies the market demand. It is what makes me.

The present invention will be described in detail below. The compound of the present invention is a compound represented by the general formula (1). In the general formula (1), examples of R ₁ and R ₇ are a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, nona. A halogenoalkyl group such as a fluorobutyl group; a hydroxyl group; an alkoxy group having 1 to 10 carbon atoms; a cycloalkoxy group having 4 to 8 carbon atoms; a cyano group; a carboxyl group;
1 alkoxycarbonyl group; cycloalkoxycarbonyl group having 5 to 9 carbon atoms; phenoxycarbonyl, p-methylphenoxycarbonyl, m-methylphenoxycarbonyl, o-methylphenoxycarbonyl, 2,4-dimethylphenoxycarbonyl, 2,6- Aryloxycarbonyl groups such as dimethylphenoxycarbonyl, 2,4,6-trimethylphenoxycarbonyl and 4-phenylphenoxycarbonyl groups; alkenyloxycarbonyl groups such as propenoxycarbonyl and 2-butenoxycarbonyl groups; benzyloxycarbonyl, Aralkyloxycarbonyl groups such as methylbenzyloxycarbonyl and phenethyloxycarbonyl groups; methoxycarbonylmethoxycarbonyl, ethoxycarbonylmethoxycarbonyl, n-propoxycarbonylmethoxycarbonyl, is Alkoxycarbonylalkoxycarbonyl groups such as o-propoxycarbonylmethoxycarbonyl group; alkylcarbonylalkoxycarbonyl groups such as methylcarbonylmethoxycarbonyl and ethylcarbonylmethoxycarbonyl group;

Hydroxyalkoxycarbonyl groups such as hydroxymethoxycarbonyl, hydroxyethoxycarbonyl, 2-hydroxypropoxycarbonyl and 3-hydroxypropoxycarbonyl groups; hydroxypolyoxy groups such as hydroxyethoxyethoxycarbonyl, hydroxypropoxypropoxycarbonyl and hydroxyethoxyethoxyethoxycarbonyl groups. Ether carbonyl group; methoxymethoxycarbonyl, methoxyethoxycarbonyl,
Polyether carbonyl groups such as ethoxy methoxy carbonyl, ethoxy ethoxy carbonyl, γ-ethoxy propoxy carbonyl group, methoxy ethoxy ethoxy carbonyl, ethoxy ethoxy ethoxy ethoxy carbonyl;
Hydroxyalkylcarbonyl groups such as hydroxymethylcarbonyl, hydroxyethylcarbonyl and hydroxypropylcarbonyl; hydroxyalkoxyalkylcarbonyl groups such as hydroxymethoxymethylcarbonyl, hydroxyethoxypropylcarbonyl and hydroxybutoxypentylcarbonyl; hydroxymethoxyethoxyethylcarbonyl and hydroxyethoxypropoxypropyl Carbonyl, hydroxyethoxyethoxyethoxyethylcarbonyl and other hydroxypolyetheralkylcarbonyl groups; methoxyethylcarbonyl, ethoxymethylcarbonyl, propoxymethylcarbonyl and other alkoxyalkylcarbonyl groups; methoxyethoxymethylcarbonyl, propoxyethoxyethoxyethylcarbonyl, butoxy Butoxy polyether alkylcarbonyl groups such as ethoxyethoxy ethylcarbonyl;

Aminocarbonyl group; monoalkylaminocarbonyl group having 1 to 6 carbon atoms; dialkylaminocarbonyl group having 2 to 12 carbon atoms; hydroxyethylaminocarbonyl, 2-hydroxypropylaminocarbonyl, 3-hydroxypropylaminocarbonyl group, etc. Mono (hydroxyalkyl) aminocarbonyl group; di (hydroxyethyl) aminocarbonyl, di (2-hydroxypropyl)
Di (hydroxyalkyl) aminocarbonyl group such as aminocarbonyl and di (3-hydroxypropyl) aminocarbonyl group; mono (hydroxyalkoxyalkyl) such as hydroxyethoxyethylaminocarbonyl, hydroxypropoxyethylaminocarbonyl, hydroxypropoxypropylaminocarbonyl group Aminocarbonyl group; di (hydroxyethoxyethyl) aminocarbonyl, di (hydroxypropoxyethyl) aminocarbonyl, di (hydroxypropoxypropyl) aminocarbonyl group and other di (hydroxyalkoxyalkyl) aminocarbonyl groups; methoxymethylaminocarbonyl, methoxyethyl Aminocarbonyl, ethoxymethylaminocarbonyl, ethoxyethylaminocarbonyl, propoxyethylaminocarbo Mono (alkoxyalkyl) aminocarbonyl group such as a group; di (methoxymethyl) aminocarbonyl, di (methoxyethyl) aminocarbonyl, di (ethoxymethyl) aminocarbonyl, di (ethoxyethyl) aminocarbonyl, di (propoxyethyl) Di (alkoxyalkyl) such as aminocarbonyl group
Aminocarbonyl group; examples thereof include a cycloalkylaminocarbonyl group having 4 to 8 carbon atoms.

In the general formula (1), R ₂ ,
Examples of R ₃ , R ₆ , R ₈ , R ₉ and R ₁₂ are each independently a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, Alkoxyalkyl groups such as γ-ethoxypropyl group; hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
Hydroxyalkyl group such as 2-hydroxybutyl group; halogenoalkyl group such as chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl group; hydroxyl group; carbon number 1-10
Alkoxy groups such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, and n-propoxyethoxy; and sulfonic acid groups.

Similarly, in the general formula (1), R ₄ , R ₅ and R
Examples of ₁₀ and R ₁₁ are each independently a hydrogen atom;
An alkyl group having 1 to 6 carbon atoms; an alkoxyalkyl group such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, γ-ethoxypropyl group; an alkenyl group such as allyl, 2-butenyl, 2-pentenyl group; hydroxymethyl, Hydroxyethyl, 2-hydroxypropyl, 3-
Hydroxyalkyl groups such as hydroxypropyl and 2-hydroxybutyl groups; aralkyl groups such as benzyl and phenethyl groups; aryl such as phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl and 2,4-dimethylphenyl groups Group; examples thereof include alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl groups and the like. In addition, R ₄ and R ₅ , R ₁₀ and R ₁₁ are bonded to each other, and R ₃ and R ₄ , R ₅ and R ₆ , R ₉ and R ₁₀ , and R ₁₁ and R ₁₂ are bonded to each other. With the benzene nucleus substituted with the amino group in
You may form the ring like the following (Chemical formula 5).

[0014]

[Chemical 5] (Here, R ₂ , R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₁
And R ₁₂ have the same meaning as in the general formula (1), and Q _{5 to} Q
₈ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

The compound represented by the general formula (1) of the present invention can be produced, for example, by the following two reaction routes. In the general formula (1), a compound symmetrical about the thiocarbonyl group, that is, R ₁ = R ₇ ,
R ₂ = R ₈ , R ₃ = R ₉ , R ₄ = R ₁₀ , R ₅ = R ₁₁ , R
_The method for producing the compound represented by the general formula (2) (Chemical Formula 6) in which ₆ = R ₁₂ is as follows. That is, the general formula (3)
4-Substituted aminosalicylaldehydes represented by (Chemical Formula 6) and diethyl acetonedicarboxylate can be used, for example, in methanol, ethanol, N, N-dimethylformamide (hereinafter referred to as DMF).
Abbreviated), dimethyl sulfoxide, 1,3-dimethyl-2-
In a polar solvent such as imidazolidinone (hereinafter abbreviated as DMI) at a molar ratio of 2: 1, a weak base (for example, piperidine, pyrrolidine, pyridine, aniline) with a catalytic amount of about 1/10 is mixed. Amines such as
The mixture is reacted at 0 to 100 ° C., preferably 60 to 80 ° C. for 1 to 12 hours to produce a compound represented by the general formula (4) (formula 6). The obtained compound represented by the general formula (4) was treated with phosphorus pentasulfide or Lawesson's reagent in an organic solvent such as chloroform, benzene, toluene, xylene, and 4
When reacted at 0 to 140 ° C. for 1 to 8 hours, the general formula (2)
This gives a compound in which R ₁ is a hydrogen atom.

[0016]

[Chemical 6]

Further, the method for producing the general formula (1), which is a compound which is left-right asymmetrical about the thioketone, is as follows. That is, 4-substituted aminosalicylaldehydes represented by the general formula (5) (Chemical formula 7) and diethyl acetonedicarboxylate are mixed in a molar ratio of 1: 1 in the above polar solvent.
A weak base (the above) in a catalytic amount of about 1/10 is added to the mixture obtained in (1), and the mixture is reacted at 0 to 100 ° C., preferably 60 to 80 ° C. for 1 to 5 hours to give a compound of the general formula ( 6)
A compound represented by (Chemical Formula 7) is produced. Then, the obtained compound represented by the general formula (6) and the compound represented by the general formula (3) are mixed, for example, in the polar solvent at a molar ratio of 1: 1. A weak base (the above) in a catalytic amount of about 1/10 is added, and the mixture is allowed to react at 0 to 100 ° C., preferably 60 to 80 ° C. for 1 to 12 hours and represented by the general formula (7) To produce the compound. When the obtained compound represented by the general formula (7) is reacted with phosphorus pentasulfide or Lawesson's reagent in an organic solvent such as chloroform, benzene, toluene or xylene at 40 to 140 ° C. for 1 to 8 hours, A compound of the formula (1) in which R ₁ and R ₇ are hydrogen atoms is obtained.

[0018]

[Chemical 7]

In order to introduce the substituents represented by R ₁ and R ₇ in the general formula (1), for example, cyanation is carried out, and then different substituents are introduced. Cyanation was carried out by converting the compound (4) obtained by the above method into "Dyes and
Pigments Vol. 1, pp. 3-15 (1980) ", the coumarin compound is cyanated, and the reaction is performed with NaCN in DMF, followed by oxidation with bromine. By this method, a monocyano body (8) (chemical formula 8) or a dicyano body (9) (chemical formula 8) can be obtained.

[0020]

[Chemical 8]

The cyano groups in the cyano compounds (8) and (9) can be converted to carboxyl groups by hydrolysis with 50 to 98% by weight of sulfuric acid at 70 to 100 ° C. and hydrolysis.
Further, a compound containing a carboxyl group is reacted with alcohols, amines, halogenated alkyls, various tosylates, phenols or the like after once converted into an acid chloride with a chlorinating agent, or is reacted with an acid catalyst or dehydration. By the method of heating in the presence of an agent or without a catalyst, R ₁
It is possible to introduce an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, or the like. Further, concentrated sulfuric acid was added dropwise to a mixture of alcohols and the like containing approximately equimolar water with the cyano bodies (8) and (9),
Similar substituents can be introduced by a method of heating to -100 ° C. Cyanation can be similarly performed on the compound represented by the general formula (7), and can be induced to a different substituent. Further, in order to introduce a substituent other than the above into the substituents represented by R ₁ and R ₇ in the general formula (1), in the general formula (4) or (7), for example, brominated And the like, and then converted into an alkyl group, a hydroxyl group, an alkoxy group, a halogenoalkyl group, or the like.

Of the above-mentioned substituents, the substituent represented by R ₁ and R ₇ is preferably a hydrogen atom, a cyano group, a carbonyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkenyloxy group. A carbonyl group, an aralkyloxycarbonyl group, an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or the substituent of the above (formula 4), more preferably a hydrogen atom, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, or aryloxy. Carbonyl group, alkenyloxycarbonyl group, aralkyloxycarbonyl group, alkoxycarbonylalkoxycarbonyl group, alkylcarbonylalkoxycarbonyl group, or the above (formula 4)
Is a substituent of. The substituents represented by R ₂ , R ₃ , R ₆ , R ₈ , R ₉ and R ₁₂ are preferably hydrogen atoms.

The substituents represented by R ₄ , R ₅ , R ₁₀ and R ₁₁ are preferably hydrogen atoms, alkyl groups, alkoxyalkyl groups, hydroxyalkyl groups, aralkyl groups, aryl groups and alkoxy groups. A carbonylalkyl group, more preferably an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, an aralkyl group,
An aryl group and an alkoxycarbonylalkyl group,
Particularly preferably, an alkyl group, an alkoxyalkyl group,
It is a hydroxyalkyl group. Also, R ₄ , R ₅ , and R ₁₀
And as R _11, R ₃ and R _4, R ₅ and R _6, R ₉ and R _10, R ₁₁ and R ₁₂ are bonded to each other, the ring of the (Formula 5) is preferable. Further, among the compounds of the present invention, preferred is
The compound represented by the general formula (2) is a compound that is bilaterally symmetric with respect to the thiocarbonyl group.

The compound of the present invention is a compound that is excited by absorbing light in the visible light region of 400 to 700 nm, particularly light of 400 to 600 nm, and interacts with a photocurable resin or a polymerization initiator. is there. 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. From this, the compound of the present invention is a very useful compound as a photosensitizer.

The visible light-sensitive resin composition of the present invention is obtained by using the compound of the present invention as a photosensitizer and mixing a photocurable resin, a photopolymerization initiator and the like. In the visible light-sensitive resin composition of the present invention, the amount of the compound of the present invention used varies depending on the type and the type of the photocurable resin component to be interacted with, but is usually per 100 parts by weight of the photocurable resin component. ,
A range of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight is suitable. If the amount of the compound used is less than 0.1 parts by weight, the photosensitivity of the formed film tends to decrease, and if it is more than 10 parts by weight, the composition becomes uniform from the viewpoint of solubility. It tends to be difficult to keep. Further, in the invention, other known photosensitizers may be mixed and used. There is no particular limitation 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.

The photocurable resin used in the present invention is not particularly limited as long as it is a photocurable resin having a photosensitive group which can be cross-linked or polymerized by light irradiation which is generally used. Anionic photocurable resin and photosensitive group containing a (meth) acryloyl group as the photosensitive group described in page 6, right lower column, line 6 to page 6, left lower column, line 16 of Kaihei 3-223759. Examples thereof include a photocurable resin containing a cinnamoyl group and a photocurable resin containing an allyl group as a photosensitive group.

The photopolymerization initiator used in the present invention is not particularly limited as long as it is a commonly used photopolymerization initiator, and examples thereof include benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl,
Aromatic carbonyl compounds such as xanthone, thioxanthone and anthraquinone; acetophenones such as acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone and acetophenone Benzoyl peroxide,
t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di-t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra ( Organic peroxides such as t-butylperoxycarbonyl) benzophenone; diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; organic halides such as carbon tetrachloride, carbon tetrabromide, chloroform and iodoform, 3-phenyl -5-isoxazolone,
2,4,6-Tris (trichloromethyl) -1,3,5
-Heterocyclic and polycyclic compounds such as triazinebenzanthrone; 2,2'-azo (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1 '
-Azobis (cyclohexane-1-carbonitrile),
Azo compounds such as 2,2'-azobis (2-methylbutyronitrile); Iron-Arene Complex (see European Patent No. 152377); Titanocene compound (see Japanese Patent Laid-Open No. 63-221110) A bisimidazole compound, an N-arylglycine compound, an acridine compound, a combination of aromatic ketone / aromatic amine, and the like.

Among the above-mentioned polymerization initiators, di-t-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, iron-allene complex and titanocene compound. Is a preferable compound because it has high activity for crosslinking or polymerization. The amount of these polymerization initiators used is not critical and can be varied within a wide range depending on the type of the polymerization initiator. Generally, it is 0.1 per 100 parts by weight of the above-mentioned photocurable resin solid content. ~ 25 parts by weight, preferably 0.2 ~
It can be in the range of 10 parts by weight. If it is used in a large amount exceeding 25 parts by weight, the stability of the obtained composition tends to be lowered.

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 known photosensitive material that is generally used. That is, the visible light-sensitive resin composition containing the compound of the present invention is dissolved in a solvent (if the pigment is used as a colorant, the pigment is finely dispersed) to prepare a photosensitive solution, which is then placed on a support. For example, it can be used as a visible light-sensitive material by a method of coating using a coating device such as a roller, a coater, a spin coater, etc. and drying. As the solvent used, for example,
Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, 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 (dimethyl Formamide, dimethyl sulfone oxime, etc.) and the like. Further, as the support, for example, aluminum, magnesium, copper, zinc,
Examples thereof include a sheet of a metal such as chromium, nickel, iron or the like, or an alloy sheet containing them, or a printed circuit board whose surface is treated with these metals, plastic, glass or a silicon wafer, carbon and the like.

Further, the visible light-sensitive composition of the present invention can be handled in the same manner as an ordinary photosensitive material for electrodeposition coating, and can also be used as a coating material for electrodeposition coating. In that case, the photocurable resin is first made into an aqueous dispersion or a water-soluble product. Water-dispersed or water-solubilized photocurable resin is neutralized with an alkali (neutralizing agent) when an anionic group such as a carboxyl group in the photocurable resin is introduced, or an amino group or the like. When the cationic group of 1 is introduced, it is carried out by neutralizing with an acid (neutralizing agent). As the alkali neutralizing agent used at that time,
For example, monoethanolamine, diethanolamine,
Alkanolamines such as triethanolamine; triethylamine, diethylamine, monoethylamine,
Examples thereof include alkylamines such as diisopropylamine, trimethylamine, diisobutylamine; alkylalkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as caustic soda and caustica; ammonia. Further, as the acid neutralizing agent, for example, formic acid, acetic acid,
Examples include monocarboxylic acids such as lactic acid and butyric acid. These neutralizing agents can be used alone or in a mixture. The amount of the neutralizing agent used is 1 equivalent of the ionic group contained in the photocurable resin,
Generally, a range of 0.2 to 1.0 equivalent, particularly 0.3 to 0.8 equivalent 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 may be added to the photocurable resin, if necessary. ,
Methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether,
Dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used can be generally 300 parts by weight, preferably 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, the above photocurable resin,
Hydrophobic solvents such as 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; 2-
Alcohols such as ethylhexyl alcohol and benzyl alcohol can also be added. The blending 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 visible light-sensitive composition as an electrodeposition coating composition can be prepared by a conventionally known method. For example,
The photocurable resin 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 mixed well, and water is added. It can be prepared. The composition thus prepared is further diluted with water by a conventional method, for example, within a pH range of 4 to 9, and a bath concentration (solid content concentration) of 3 to
The electrodeposition coating (or electrodeposition bath) may be in the range of 25% by weight, preferably 5 to 15% by weight.

The electrodeposition paint prepared as described above is
The conductor surface, which is the object to be coated, can 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 15 to 40 ° C., preferably 15 to 30.
Control at ℃. Then, in a controlled electrodeposition coating bath, the conductor to be coated is immersed as an anode when the electrodeposition coating is an anion type and as a cathode when the electrodeposition coating is a cation type, and immersed at 5 to 200 V. Apply a direct current. A suitable energization time is 30 seconds to 5 minutes, and the obtained film thickness is a dry film thickness, generally 0.5 to 50 μm, and preferably 1 to 15 μm.
μm. After electrodeposition coating, the object to be coated is lifted from the electrodeposition bath and washed with water, and then the water content contained in the electrodeposition coating film is dried and removed with hot air or the like. As the conductor, metal, carbon,
It can be used by a conductive material such as tin oxide, or a person who fixes these to a plastic or glass surface by laminating, plating or the like.

The visible light-sensitive material formed on the conductor surface as described above and the visible light-sensitive electrodeposition coating film obtained by electrodeposition coating are exposed to visible light and cured according to the image. An image can be formed by removing the non-exposed portion by a developing process. As the light source for exposure, there are light sources such as ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and sunlight. Among them, light rays in the visible region obtained by cutting ultraviolet rays with an ultraviolet cut filter, various lasers having oscillation lines in the visible region, and the like can be used. Argon laser or YAG as a high power and stable laser light source
The second harmonic of the laser is preferred.

The development treatment is carried out by washing 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 it is cationic. Alkaline aqueous solutions are usually caustic soda, sodium carbonate, caustic potash, ammonia water, etc. that can neutralize the free carboxylic acid in the coating film to give water solubility, and the aqueous acid solutions include acetic acid, formic acid, lactic acid, etc. Can be used. In the case of a photocurable resin having no ionic group, the development treatment is carried out by dissolving the unexposed area with a solvent such as 1,1,1-trichloroethane, trichlene, methylethylketone or methylene chloride.
The coating film after development is washed with water and then dried with hot air or the like.
The desired image is formed on the conductor. If necessary, the exposed conductor portion may be removed by etching, and then the resist film may be removed to manufacture the printed circuit board. The composition of the present invention includes a photoresist, a plate-making material for flat plates and relief printing, a PS plate for offset printing,
It can be applied to a wide range of applications such as information recording materials and relief image forming materials.

[0036]

EXAMPLES The present invention will be described below with reference to specific examples, but these are merely examples, and the present invention is not limited to these. Parts in the examples are parts by weight, and% is% by weight. Example 1 To 57 parts of 4-diethylaminosalicylaldehyde and 25 parts of ethyl acetonedicarboxylate were added 2 parts of piperidine, and the mixture was reacted in an ethanol solvent at 80 ° C. for 4 hours. After cooling, the obtained crystals were filtered, washed with ethanol and then dried to obtain 55 parts of bis [3- (7-diethylaminocoumaryl)] ketone of the formula (A) (formula 9). 28 parts of the above compound and 13 parts of phosphorus pentasulfide were refluxed in 800 ml of chloroform for 3 hours. After cooling, the mixture was discharged into 1000 parts of water, extracted with chloroform, washed with water, and the solvent was distilled off under reduced pressure. The reaction mixture thus obtained was separated and purified by column chromatography to obtain 11 parts of bis [3- (7-diethylaminocoumaryl)] thioketone of the formula (B) (formula 9).

[0037]

[Chemical 9]

The results of analysis of this compound are as follows. Absorption spectrum; absorption maximum [λ max] 536 nm (in chloroform) ¹ H-NMR spectrum (δ / ppm): CDCl ₃
Medium 1.22-1.25 (t, 12H), 3.42-3.4
6 (q, 8H), 6.47 (d, 2H), 6.58-
6.60 (q, 2H), 7.40 to 7.42 (d, 2)
H), 8.31 (s, 2H) ¹³ C-NMR spectrum (δ / ppm): CDCl ₃
Medium 12.49, 45.12, 97.07, 10
9.59 109.70, 129.64, 131.49, 1
46.34 152.28, 157.97, 159.27, 2
22.25 FDMS spectrum; m / z = 476 (M ⁺ ), elemental analysis value (C ₂₇ H ₂₈ N ₂ O ₄ S) C (%) H (%) N (%) S (%) calculated value 68 0.055 5.92 5.88 6.73 Measured value 68.16 6.00 5.92 6.52 ・ Melting point: 230 ° C. As a photocurable resin (polymer binder), methyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate / Benzyl methacrylate = 50/20/10
/ 20 mixture 100 parts, trimethylolpropane triacrylate 55 parts, the following as a polymerization initiator (chemical formula 10)
A photosensitizing solution was prepared using 20 parts of the titanocene compound of Example 1, 5 parts of the compound of the formula (B) as a photosensitizer, and 160 parts of methyl cellosolve as a solvent. This photosensitive solution was applied on a laminated copper plate using a spinner so that the dry film pressure was 3.5 g / m ² . Next, 5 mJ / cm
^When the photosensitive layer was irradiated with a ^2- intensity argon laser, it was confirmed that the resin was cured rapidly.
Second harmonic of xenon lamp and YAG laser (5
The same result was obtained by irradiation with 32 nm).

[0039]

[Chemical 10]

Example 2 40 parts of bis [3- (7-diethylaminocoumaryl)] ketone obtained in the same manner as in Example 1 was suspended in 200 parts of DMF, to which 57 parts of 30% aqueous NaCN solution was added. Was added dropwise at room temperature and the reaction was continued for 1 hour, then 31 parts of bromine was added dropwise at 0 to 10 ° C. and stirred for 2 hours. After filtering the precipitate, wash it thoroughly with water,
After drying, 42 parts of bis [3- (4-cyano-7-diethylaminocoumaryl)] ketone was obtained. 9 parts of the above cyano body, 100 parts
98 parts of diethylene glycol monomethyl ether
After reacting with 21.6 parts of% sulfuric acid at 80 ° C for 3 hours and allowing to cool, 300
It was neutralized by discharging into some water. The precipitated crystals were filtered, washed well with water and dried to obtain 10 parts of the following compound (C) (Chemical Formula 11). Furthermore, the compound (C) was introduced with a thiocarbonyl group by the same method as in Example 1 to obtain the following compound (D) (Chemical Formula 11).

[0041]

[Chemical 11]

The absorption spectrum and elemental analysis results of this compound are as follows. - absorption spectrum; absorption maximum [λmax] 576 nm (in chloroform) Elemental analysis _{(C 39 H 48 N 2 O} 12 S) C (%) H (%) N (%) S (%) Calculated 60.93 6.29 3.64 4.17 Measured value 60.97 6.28 3.64 4.11 .Melting point: 216 ° C. A photosensitive solution having the same composition as in Example 1 was prepared using the ketocoumarin compound. Using this, a photosensitive layer was formed in the same manner as in Example 1, and when the photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Example 3 57 parts of 9-formyl-8-hydroxyeurolidine [compound (E) (Chemical formula 12)] and 25 parts of ethyl acetonedicarboxylate were mixed with 2 parts of piperidine, and the mixture was mixed in an ethanol solvent at 80 ° C. And reacted for 5 hours. After cooling, the obtained crystals were filtered, washed with ethanol, dried, and dried with bis (10-
Eurolysyl coumaryl) ketone [Compound (F)
2)] 57 parts were obtained. 44 parts of this compound was suspended in 200 parts of DMF, 57 parts of 30% NaCN aqueous solution was added dropwise thereto at room temperature, and the reaction was continued for 1 hour. Then, 31 parts of bromine was added at 0-10 ° C.
, Then stirred for 2 hours, filtered, washed well with water, dried,
45 parts of bis [10- (11-cyanoeurolidylcoumaryl)] ketone were obtained. Next, 10 parts of the cyano compound was reacted with 21.6 parts of 98% sulfuric acid in 100 parts of ethanol at 80 ° C. for 3 hours, allowed to cool, and then discharged into 300 parts of water for neutralization. The precipitated crystals were filtered, washed well with water, dried, and then compound (G)
(Chemical Formula 12) 11.5 parts were obtained. Further, the compound (G) was introduced with a thiocarbonyl group by the same method as in Example 1 to obtain the following compound (H) (Chemical Formula 12).

[0044]

[Chemical 12]

The absorption spectrum of this compound and the result of elemental analysis are as follows. Absorption spectrum; absorption maximum [λ max] 591 nm (in chloroform) Elemental analysis value (C ₃₇ H ₃₆ N ₂ O ₈ S) C (%) H (%) N (%) S (%) calculated value 66.45 5.42 4.19 4.80 Measured value 66.38 5.37 4.20 4.71. Melting point: 224 ° C. A photosensitive solution having the same composition as in Example 1 was prepared using the ketocoumarin compound. Using this, a photosensitive layer was formed in the same manner as in Example 1, and when the photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was rapidly cured. Similar results were obtained with the xenon lamp irradiation.

Examples 4 to 25 The bis [3- (4-substituted coumaryl)] thioketone compounds synthesized in the same manner as in Example 1 are shown in Table-1 (Table 1, Table 2, Table 3 and Table 3).
The results are summarized in Tables 4 and 5). All the compounds showed the same photosensitivity as the compound of Example 1.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

In the field of information recording using a photopolymerization reaction, a document which is electronically edited by a computer is directly output using a laser as it is for recording, and the sensitivity of the photosensitive layer and dissolution There was a problem such as poor storage stability and storage stability. However, the photosensitive layer obtained by coating the visible light-sensitive resin composition containing the compound of the present invention as a photosensitizer is excellent in sensitivity, solubility and storage stability. The present invention provides a photosensitizer and a visible light-sensitive resin composition which are extremely useful in practice.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07D 311/18 C09B 57/02 C09K 3/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A bis (3-coumaryl) thioketone compound represented by the following general formula (1) (formula 1). [Chemical 1] [In the formula, R ₁ and R ₇ are each a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, or aryl. An oxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxycarbonylalkoxycarbonyl group, an alkylcarbonylalkoxycarbonyl group, or the following substituent (Formula 2): (Here, Q _{1 to} Q ₄ are each a hydrogen atom, an alkyl group,
Shows a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, a cycloalkyl group,
n, m, p and q each represent an integer of 1 to 5) R ₂ , R ₃ , R ₆ , R ₈ , R ₉ and R ₁₂ are each a hydrogen atom, a halogen atom, an alkyl group or an alkoxyalkyl group. , A hydroxyalkyl group, a halogenoalkyl group, a hydroxyl group, an alkoxy group, an alkoxyalkoxy group or a sulfonic acid group, and R ₄ , R ₅ , R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group, an alkoxyalkyl group or an alkenyl group. , A hydroxyalkyl group, an aralkyl group, an aryl group, an alkoxycarbonylalkyl group, and R ₄ and R
₅ , R ₁₀ and R ₁₁ may combine with each other to form a ring,
R ₃ and R ₄ , R ₅ and R ₆ , R ₉ and R ₁₀ , R ₁₁ and R
₁₂ may combine with each other to form a ring with a benzene nucleus substituted with an amino group in the skeleton] 2. A photosensitizer comprising the bis (3-coumaryl) thioketone compound according to claim 1. 3. A visible light-sensitive resin composition containing the photosensitizer according to claim 2.