JPH0892234A - 4-Substituted carbonylcoumarin derivative and visible light-sensitive composition using the same - Google Patents

Abstract

PURPOSE: To obtain a new 4-substituted carbonyl coumarin derivative extremely useful as a photosensitive agent and capable of giving photosensitive materials enabling to form extremely fine high resolution picture image by a high speed scan exposure method. CONSTITUTION: The compound of formula I (R<1> , R<2> are independently H, alkyl, etc.; R<3> is H, halogen, etc.; X is H, alkyl, etc.; Y is H, alkylcarbonyl, etc.; Z<1> , Z<2> are independently O, S, wherein at least one is S), e.g. a compound of formula II. The compound is a coumarin derivative which is obtained by replacing the carbonyl oxygen of the coumarin skeleton with sulfur or replacing the carbonyl oxygen of the substituted carbonyl group at the 4-position of the coumarin skeleton with sulfur. The compound is highly sensitive to visible light laser, is good in compatibility with base resins, and can be dissolved in coating solvents for general uses. 0.1-10 pts.wt. of the compound is preferably generally dissolved in 100 pts.wt. of a photocurable resin component to produce the visible light-sensitive composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a novel compound.
-Substituted carbonyl coumarin derivative, and a visible light-sensitive composition containing the derivative as a photosensitizer.

[0002]

2. Description of the Related Art In recent years, in the field of information or image recording using a photopolymerization reaction, the conventional recording method by ultraviolet rays using a film original or the like has been changed, and an original electronically edited by a computer is directly used as a high power laser. A method of outputting and recording by using is being studied. This method
Since direct writing is performed by a laser, there is an advantage that the recording and image forming processes can be greatly simplified. However, most of the currently used high-power and stable laser light sources have their output wavelengths in the visible region, and thus the conventionally used UV photosensitizer has a sensitivity in the visible region. It was too low to use.

In recent years, especially as a visible laser, a wavelength of 4
Argon laser with stable oscillation lines at 88nm and 514.5nm, or 532n as the second harmonic
YAG lasers, etc., which have a bright line at m, are becoming popular. Therefore, it is desired to develop a compound having a high sensitivity to those oscillation wavelengths or a visible light-sensitive composition containing the high sensitivity compound. However, a photosensitive material capable of satisfying such a demand has not yet been put into practical use. One of the major reasons for this is that there are few photosensitive resins sensitive to light in the long wavelength region, but the second reason is that no photopolymerization initiator system well adapted to it has been found. .

Several proposals have hitherto been made for a photopolymerization initiator system effective for visible light. For example,
A system in which hexaarylbisimidazole is combined with p-dialkylaminobenzylidene ketone or dialkylaminochalcone (USP 3,652,275, JP-A-54-155292), and a system in which camphorquinone and a dye are combined (JP-A-48-081843). ), A system in which a diphenyliodonium salt and a Michler's ketone are combined (GB2,020,297A), and a system in which an S-triazine compound and a merocyanine dye are combined (Japanese Patent Laid-Open Publication No. 5 (1999) -58242).
4-151024), a system in which an S-triazine compound and a thiapyrylium salt are combined (JP-A-58-04030).
2) etc. are mentioned. However, although these photopolymerization initiators have the ability to initiate polymerization with respect to light in the visible region, their sensitivity cannot be said to be sufficient, and from the viewpoint of compatibility with the photopolymerization composition components. However, this is not always sufficient, and a more practical photopolymerization initiator system is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitizer which is excellent in compatibility with the components of the photopolymerization composition and can impart sufficient polymerization initiation ability to light in the visible region. It is to be.

[0006]

The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention is represented by the general formula (1)
The present invention relates to a 4-substituted carbonylcoumarin derivative represented by, a photosensitizer and a visible light-sensitive composition using the same.

[0007]

[Chemical 4] [In the formula, R ¹ and R ² each independently or independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other; It may combine with a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group or an alkoxyalkoxy. Group, an alkoxycarbonyl group, a sulfonic acid group, a halogenoalkyl group, X is a hydrogen atom, an alkyl group,
Cycloalkyl group, alkoxy group, cycloalkoxy group, hydroxyl group, aryl group, alkenyl group, aryloxy group, alkenyloxy group, aralkyl group, aralkyloxy group, alkoxycarbonylalkoxy group, alkylcarbonylalkoxy group, or the following substituents ( 5),

[0008]

[Chemical 5] (Here, R ^{4 to} R ⁸ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, or an alkylcarbonyl group, and m, n, r, and s are each 1 to 5 represents an integer of 5) Y represents a hydrogen atom, an alkylcarbonyl group, an alkoxycarbonyl group, an aryl group, an arylcarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylalkylcarbonyl group, an alkoxycarbonylalkoxycarbonyl group, or a heterocyclic group. Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom, and Z ¹ and Z ²
At least one of them is a sulfur atom)

The compound represented by the formula (1) of the present invention is a novel coumarin derivative useful as a photosensitizer. That is, the carbonyl oxygen of the coumarin skeleton is replaced with sulfur, or the carbonyl oxygen of the substituted carbonyl group at the 4-position of the coumarin skeleton is replaced with sulfur. As a result, the solubility in the resin is improved, the maximum absorption wavelength is increased, and the sensitivity is increased.A photocurable resin, for example, at least one ethylenic unsaturated bond in the molecule is used. It is an extremely useful compound that can be applied to photopolymerization or photocrosslinkable compounds that have and photocuring using a photopolymerization initiator. Further, the sensitivity of conventional sensitizers varies greatly depending on the coating method, but the sensitizers of the present invention exhibit stable sensitivity in any of the methods and sufficiently satisfy the demand.

The present invention will be described in detail below. In the compound of the present invention, the general formula (1), R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group and an alkoxycarbonylalkyl group, and are the same as each other. Or may be different. Specifically, a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl group; methoxymethyl, methoxyethyl. , Alkoxymethyl groups such as ethoxymethyl, ethoxyethyl, γ-methoxypropyl, γ-ethoxypropyl groups; allyl, 2-butenyl, 2-
Alkenyl groups such as pentenyl groups; hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl groups; aralkyl groups such as benzyl and phenethyl groups; phenyl, p-methylphenyl, Examples thereof include aryl groups such as m-methylphenyl, o-methylphenyl, and 2,4-dimethylphenyl groups; and alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, and ethoxycarbonylethyl groups. Further, R ¹ and R ² may be bonded to each other or to a benzene nucleus substituted by an amino group in the skeleton to form a ring represented by the following formula (Formula 6).

[0011]

[Chemical 6] (In the formula, R ² and R ³ have the same meanings as in the case of the general formula (1))

In the general formula (1), R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group,
An alkoxyalkoxy group, an alkoxycarbonyl group, a sulfonic acid group and a halogenoalkyl group are shown. In particular,
Hydrogen atom; halogen atom such as chlorine atom, fluorine atom and bromine atom; hydroxyl group; methyl, ethyl, n-propyl, is
Alkyl groups such as o-propyl and n-butyl groups; alkoxy groups such as methoxy, ethoxy, n-propoxy and n-butoxy groups; alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl groups; hydroxymethyl , Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and like hydroxyalkyl groups; methoxymethoxy, methoxyethoxy,
Alkoxyalkoxy groups such as ethoxymethoxy, ethoxyethoxy and n-propoxyethoxy groups; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl and iso-propoxycarbonyl groups; sulfonic acid groups; chloromethyl, 2-chloroethyl, Examples thereof include halogenoalkyl groups such as dichloromethyl and trifluoromethyl groups. Similarly, in the general formula (1), X is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a hydroxyl group, an aryl group, an alkenyl group, an aryloxy group, an alkenyloxy group, an aralkyl group or an aralkyloxy group. , An alkoxycarbonylalkoxy group, an alkylcarbonylalkoxy group, or the following substituent (Formula 7).

[0013]

[Chemical 7] (In the formula, R ^{4 to} R ⁸ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group and an alkylcarbonyl group, and n, m, r and s are each 1 to Indicates an integer of 5)

Specifically, hydrogen atom; methyl, ethyl, n
-Propyl, iso-propyl, n-butyl, sec-
Butyl, t-butyl, n-pentyl, n-hexyl, n
Alkyl groups such as heptyl and n-octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, Alkoxy groups such as n-pentyloxy, n-hexyloxy, n-heptyloxy and n-octyloxy groups; cycloalkoxy groups such as cyclopentyloxy and cyclohexyloxy groups; hydroxyl group; phenyl, p-methylphenyl, m-methylphenyl An aryl group such as o-methylphenyl group; an alkenyl group such as 2-butenyl and 2-pentenyl group; phenoxy, p-methylphenoxy, m-methylphenoxy, o-methylphenoxy, 2,4-dimethylphenoxy, 2, 6-dimethylphenoxy, 2,4 - trimethyl phenoxy, 4-
Aryloxy groups such as phenylphenoxy groups; alkenyloxy groups such as propenoxy and 2-butenoxy groups; aralkyl groups such as benzyl and phenethyl groups; aralkyloxy groups such as benzyloxy, methylbenzyloxy and phenethyloxy groups; methoxycarbonylmethoxy , Ethoxycarbonylmethoxy, n-propoxycarbonylmethoxy, iso-propoxycarbonylmethoxy and like alkoxycarbonylalkoxy groups; methylcarbonylmethoxy, ethylcarbonylmethoxy and like alkylcarbonylalkoxy groups;

Polyether groups such as hydroxyethyl, hydroxyethoxyethyl, hydroxyethoxyethoxyethyl, ethoxyethoxyethyl, hydroxyethoxy, hydroxyethoxyethoxy, hydroxypropoxypropoxy, hydroxyethoxyethoxyethoxy groups;
Amino group: methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-
Monoalkylamino groups such as hexylamino, n-heptylamino and n-octylamino groups; dialkylamino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino groups Hydroxyethylamino, 2-hydroxypropylamino,
Mono (hydroxyalkyl) amino group such as 3-hydroxypropylamino group; di (hydroxyethyl) amino,
Di (hydroxyalkyl) such as di (2-hydroxypropyl) amino, di (3-hydroxypropyl) amino group
Amino group: mono (hydroxyalkoxyalkyl) such as hydroxyethoxyethylamino, hydroxypropoxylamino, hydroxypropoxypropylamino group
Amino group; di (hydroxyalkoxyalkyl) amino group such as di (hydroxyethoxyethyl) amino, di (hydroxypropoxyethyl) amino, di (hydroxypropoxypropyl) amino group; methoxymethylamino,
Mono (alkoxyalkyl) amino groups such as methoxyethylamino, ethoxymethylamino, ethoxyethylamino, propoxyethylamino; di (methoxymethyl) amino, di (methoxyethyl) amino, di (ethoxymethyl) amino, di (ethoxyethyl) ) Amino, di (propoxyethyl) amino and other di (alkoxyalkyl) amino groups; cyclopentylamino, cyclohexylamino and other cycloalkylamino groups and the like.

In the general formula (1), Y is a hydrogen atom, an alkylcarbonyl group, an alkoxycarbonyl group,
An aryl group, an arylcarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylalkylcarbonyl group, an alkoxycarbonylalkoxycarbonyl group, or a heterocyclic group is shown. Specifically, a hydrogen atom; an alkylcarbonyl group such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl and n-butylcarbonyl;
Alkoxycarbonyl groups such as methoxycarbonyl, ethoxy cowbonyl, n-propoxycarbonyl, n-butoxycarbonyl groups; phenyl, p-methylphenyl, m
Aryl groups such as -methylphenyl and o-methylphenyl groups; arylcarbonyl groups such as benzoyl, p-methylbenzoyl, m-methylbenzoyl, o-methylbenzoyl groups; phenoxycarbonyl, p-methylphenoxycarbonyl, m-methylphenoxy Aryloxycarbonyl group such as carbonyl and o-methylphenoxycarbonyl group; alkoxycarbonylalkylcarbonyl group such as methoxycarbonylmethylcarbonyl and ethoxycarbonylmethylcarbonyl group; alkoxycarbonylalkoxycarbonyl group such as methoxycarbonylmethoxycarbonyl and ethoxycarbonylmethoxycarbonyl group ;
Alternatively, a heterocyclic group represented by the following formula (Formula 8) can be given. In the general formula (1), Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom, and Z ¹ and Z ²
At least one of them is a sulfur atom.

[0017]

Embedded image A particularly preferable compound as the photosensitizer is a 4-substituted carbonylcoumarin derivative represented by the following general formula (2) (formula 9).

[0018]

[Chemical 9] (In the formula, R ⁹ and R ¹⁰ each represent a lower alkyl group which may be the same or different, and R ¹¹ represents a hydrogen atom, a lower alkyl group, an alkoxyalkyl group, a hydroxyalkoxyalkyl group or an alkoxycarbonylalkyl group, Z ³ and Z ⁴ each independently represent an oxygen atom or a sulfur atom, and at least one of Z ³ and Z ⁴ is a sulfur atom)

In the general formula (2), R ⁹ and R ¹⁰ are methyl, ethyl, n-propyl, iso-propyl and n-.
A lower alkyl group having 1 to 4 carbon atoms such as butyl and iso-butyl group is shown. R ¹¹ is a hydrogen atom, or a lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl group; methoxymethyl, methoxyethyl, ethoxyethyl, Alkoxyalkyl groups such as propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl groups; hydroxyalkoxyalkyl groups such as hydroxymethoxyethyl, hydroxyethoxyethyl, hydroxypropoxyethyl, hydroxymethoxypropyl, hydroxyethoxypropyl, hydroxypropoxypropyl groups; methoxy Examples include alkoxycarbonylalkyl groups such as carbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylpropyl and butoxycarbonylbutyl groups. That. Also Z ³ , Z
⁴ independently represents an oxygen atom or a sulfur atom, and at least one of Z ³ and Z ⁴ is a sulfur atom.

The above general formula (1) or (2) of the present invention
The compound represented by, for example, JP-A-04-18088
Alternatively, after synthesizing a 4-substituted carbonylcoumarin compound by the method described in JP-A 03-223759,
It can be obtained by converting a carbonyl group into a thiocarbonyl group according to a conventional method using phosphorus pentasulfide, Lawesson's reagent and the like. The compound of the present invention is extremely useful as a photosensitizer. That is, by adding the compound of the present invention to a general-purpose photosensitive material containing a photopolymerization initiator,
The sensitivity to visible light is significantly improved, and writing with a visible laser and image formation can be performed easily and easily. That is, the present compound is a compound that is excited by absorbing light in the wavelength region of 400 to 700 nm (visible light), particularly light of 400 to 600 nm, and has an interaction with a photocurable resin or a photopolymerization initiator. is there. The "interaction" referred to here includes energy transfer and electron transfer from the excited present compound (sensitizer) to the photocurable resin or the photopolymerization initiator.

The photosensitive composition of the present invention can be produced by adding the compound of the present invention to a general-purpose photosensitive material containing a photopolymerization initiator. That is, as a photosensitizer, a visible light characterized by containing a 4-substituted carbonylcoumarin derivative of the present invention, a photopolymerization initiator, and a photocurable resin having a photosensitive group that can be crosslinked or polymerized by light irradiation. It is a photosensitive composition. Further, in the photosensitive composition of the present invention, if necessary, paradimethylaminobenzoic acid, N
-Auxiliary agents such as nitrogen-containing compounds such as phenylglycine and benzotriazole may be added. The photosensitive composition of the present invention can be diluted with a solvent in actual use.

The amount of the present compound used varies depending on the kind thereof and the kind of the photocurable resin and / or photopolymerization initiator to be interacted with, and it is difficult to specify exactly.
Generally speaking, a suitable range is 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. If the amount of the present 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 in terms of solubility. It tends to be difficult to keep. The photocurable resin having a photosensitive group that can be crosslinked or polymerized by light irradiation used in the present invention is not particularly limited as long as it is a commonly used photocurable resin, and for example, JP-A-3- No. 223759, page 2, lower right column, line 6 to page 6, lower left column, line 16, anionic photocurable resin containing a (meth) acryloyl group as a photosensitive group, and a cinnamoyl group as a photosensitive 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, and the like.
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 composition of the present invention will be described. The visible light-sensitive composition containing the present compound can be handled in the same manner as a known photosensitive material that is generally used. That is, a visible light-sensitive composition containing the sensitizer of the present invention is dissolved in a solvent (dispersed into fine particles when a pigment is used in combination with a colorant) to prepare a photosensitive liquid, which is, for example, a roller, a coater, A visible light-sensitive material can be obtained by a method of coating on a support and drying to form a photosensitive layer using a coating device such as a spin coater. Examples of the solvent used at this time include 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) , Trichlorethylene, dichloromethane, etc.),
Examples thereof include alcohols (ethyl alcohol, benzyl alcohol, etc.) and others (dimethylformamide, dimethylsulfone oxime, etc.). 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.

The visible light-sensitive composition of the present invention can be handled in the same manner as a usual 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.

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 or xylene; a ketone such as methyl ethyl ketone or methyl isobutyl ketone is used with respect to the photocurable resin. Esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added. The blending amount of these hydrophobic solvents can be usually up to 200 parts by weight, preferably 100 parts by weight or less, per 100 parts by weight of the resin solid component.

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 described above, a 4-substituted carbonylcoumarin derivative (sensitizer), 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 by adding. The composition thus prepared is further diluted with water by a conventional method, for example, in the pH range of 4 to 9,
Bath concentration (solid content concentration) 3 to 25% by weight, preferably 5 to
The electrodeposition paint (or electrodeposition bath) can be within the range of 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 thickness, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, 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.

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.

Further, in the case of the photocurable resin having no ionic group, the developing treatment is 1,1,1-trichloroethane,
It is performed by dissolving the unexposed area using a solvent such as trichlene, methyl ethyl ketone, and methylene chloride. The developed coating film is washed with water and then dried with hot air or the like to form a desired image on the conductor. In addition, if necessary, after performing etching to remove the exposed conductor portion,
It is also possible to manufacture the printed circuit board by removing the resist film. The composition of the present invention can be applied to a wide variety of applications such as photoresists, plate-making materials for flat plates and relief printing, PS plates for offset printing, information recording materials, relief image-forming materials and the like.

[0034]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. In the following examples, "part" means part by weight and% means% by weight. Example 1 200 parts of 4-diethylaminosalicylaldehyde and 2-
To 180 parts of ethoxycarbonylmethylbenzothiazole was added 10 parts of piperidine, and 1 part was added at room temperature in an ethanol solvent.
After reacting for 2 hours and separating by filtration, the crystals were thoroughly washed with ethanol and dried to give 3- (benzothiazo-2-yl) -7-
320 parts of diethylaminocoumarin were obtained. This compound 1
00 copies to "Dyes and Pigments 1
50, 315 (1980) ".
After suspending in 0 part of DMF, 90 parts of 30% NaCN aqueous solution was added dropwise thereto at room temperature and left to react for 1 hour, then 50 parts of bromine was added dropwise at 0-10 ° C. and stirred for 2 hours, After filtration, it was washed well with water and dried to obtain 3- (benzothiazo-2-yl) -4-cyano-7-diethylaminocoumarin. 90 parts of the above cyanide is replaced with 70 parts of 400 parts
Hydrolyzed in 100% sulfuric acid at 100 ° C. for 8 hours. After cooling down, 3
It was discharged into 000 parts of water for neutralization. The precipitated crystals were filtered off, washed well with water and dried to give 3- (benzazothiazo-2-yl) -7-diethylaminocoumarin-4-carboxylic acid 7
I got 0 copies. Next, 6 parts of the above-mentioned carboxylic acid and 9 parts of methoxyethoxyethyl-p-toluenesulfonate were mixed with 1.
80 in 30 parts DMF in the presence of 6 parts potassium carbonate
The reaction was carried out at ℃ for 5 hours. After cooling, it was discharged into 100 parts of water. The precipitated crystals are separated by filtration, washed well with water, and dried to give 3-
6 parts of (benzazothiazo-2-yl) -4-methoxyethoxyethoxycarbonyl-7-diethylaminocoumarin was obtained. Further, 5 parts of the above compound and 4.1 parts of Lawesson's reagent were refluxed in 50 parts of dry p-xylene for 5 hours. After cooling, the mixture was discharged into 100 parts of water, extracted with methylene chloride, washed with water, and the solvent was distilled off under reduced pressure. The reaction mixture was separated by column chromatography to obtain 2 parts of the carbonylcoumarin derivative (3) (Chemical Formula 10).

[0035]

[Chemical 10]

Electronic spectrum; absorption maximum [λ _max ] = 5
28 nm (in chloroform) ¹ H-NMR spectrum (δ / ppm): 1.27 (t, 6H), 3.29 (s, 3H), 3.3 in CDCl _3.
9 (t, 2H), 3.48 (t, 4H), 3.65
(T, 2H), 3.84 (t, 2H), 4.57 (t,
2H), 6.65 to 6.76 (m, 2H), 7.35
7.54 (m, 3H), 7.90 to 7.97 (m, 2
H) FDMS spectrum; m / z = 512 (M ⁺ ) Infrared absorption spectrum (KBr tablet); (FIG. 1). Elemental analysis _{(C 26 H 28 N 2 O} 5 S 2) C (%) H (%) N (%) S (%) Calculated 60.92 5.50 5.47 12.51 Found 60.96 5.61 5.62 11.85 5 parts of the above carbonylcoumarin derivative (3), 100 parts of polyvinylpyrrolidone as a binder polymer and 100 parts of pentaerythritol triacrylate, 3,3 ′, 4,4′-as a photopolymerization initiator. A photosensitive solution was prepared using 4 parts of tetra (t-butylperoxycarbonyl) benzophenone and 1000 parts of methyl cellosolve, and applied on a laminated copper plate using a spinner. Next, when the photosensitive layer was irradiated with light using an argon laser, it was confirmed that the resin was rapidly cured.

Example 2 3- (benzothiazo-2-yl) -obtained in Example 1
5 parts of 4-methoxyethoxyethoxycarbonyl-7-diethylaminocoumarin and 8.2 parts of Lawesson's reagent were refluxed in 50 parts of dry chlorobenzene for 5 hours. After cooling, the mixture was discharged into 100 parts of water, extracted with methylene chloride, washed with water, and the solvent was distilled off under reduced pressure. The reaction mixture was separated by column chromatography to obtain 1 part of the carbonylcoumarin derivative (4) (Chemical Formula 11).

[0038]

[Chemical 11]

Electronic spectrum; absorption maximum [λ _max ] = 5
38 nm (in chloroform) Elemental analysis value (C ₂₆ H ₂₈ N ₂ O ₄ S ₃ ) C (%) H (%) N (%) S (%) Calculated value 59.07 5.33 5.30 18.20 Measured value 59.16 5.41 5.37 17.95 Using the above carbonylcoumarin derivative (4), Example 1
A photosensitive solution having the same composition as in (1) was prepared. 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 a xenon lamp, it was confirmed that the resin was rapidly cured.

Example 3 3- (Benzothiaz-2-yl) obtained in Example 1
-7-diethylaminocoumarin-4-carboxylic acid 6 parts and ethyl-p-toluenesulfonate 7 parts in the presence of 1.6 parts potassium carbonate in 30 parts DMF at 80 ° C,
The reaction was carried out for 5 hours. After cooling, it was discharged into 100 parts of water.
The precipitated crystals were separated by filtration, washed well with water and dried to give 3- (benzazothiazo-2-yl) -4-ethoxycarbonyl-
6 parts of 7-diethylaminocoumarin were obtained. Further, 5 parts of the above compound and 4.8 parts of Lawesson's reagent were added to 50 parts.
Refluxed in 5 parts dry p-xylene for 5 hours. After cooling down,
It was discharged into 100 parts of water, extracted with methylene chloride, washed with water, and the solvent was distilled off under reduced pressure. The reaction mixture was separated by column chromatography and the carbonylcoumarin derivative (5)
2.5 parts of 2) were obtained.

[0041]

[Chemical 12]

Electronic spectrum; absorption maximum [λ _max ] = 5
25 nm (in chloroform) Elemental analysis _{(C 22 H 22 N 2 O} 3 S 2) C (%) H (%) N (%) S (%) Calculated 61.95 5.19 6.57 15.04 Measured value 61.82 5.25 6.62 14.89 Using the above carbonylcoumarin derivative (5), Example 1
A photosensitive solution having the same composition as in (1) was prepared. Using this, a photosensitive layer was formed in the same manner as in Example 1, and when the above photosensitive layer was irradiated with light by an argon laser, it was confirmed that the resin was rapidly cured.

Example 4 3- (Benzothiaz-2-yl) obtained in Example 1
6 parts of -7-diethylaminocoumarin-4-carboxylic acid and 9 parts of diethylene glycol monotosylate were added to give 1.6 parts.
In the presence of 30 parts of DMF in the presence of 30 parts of potassium carbonate,
The reaction was carried out for 5 hours. After cooling, it was discharged into 100 parts of water.
The precipitated crystals were separated by filtration, washed well with water, and dried to obtain 6 parts of 3- (benzazothiazo-2-yl) -4-hydroxyethoxyethoxycarbonyl-7-diethylaminocoumarin. Further, 5 parts of the above compound and 4.1 parts of Lawesson's reagent were refluxed in 50 parts of dry p-xylene for 5 hours. After cooling, the mixture was discharged into 100 parts of water, extracted with methylene chloride, washed with water, and the solvent was distilled off under reduced pressure. The reaction mixture was separated by column chromatography to obtain 1.5 parts of the carbonylcoumarin derivative (6) (Chemical Formula 13).

[0044]

[Chemical 13]

Electronic spectrum; absorption maximum [λ _max ] = 5
26 nm (in chloroform) Elemental analysis value (C ₂₅ H ₂₆ N ₂ O ₅ S ₂ ) C (%) H (%) N (%) S (%) Calculated value 60.22 5.25 5.62 12.86 Actual value 60.32 5.29 5.71 12.65 Using the above carbonylcoumarin derivative (6), Example 1
A photosensitive solution having the same composition as in (1) was prepared. Using this, a photosensitive layer was formed in the same manner as in Example 1, and when the photosensitive layer was irradiated with light by the second harmonic (532 nm) of a YAG laser, it was confirmed that the resin was quickly cured. Was done.

Examples 5 to 20 In the same manner as in Example 1, the photosensitizers shown in Table-1 (Table 1, Table 2 and Table 3) were synthesized. The absorption maximums (λ _max ) and elemental analysis values are shown in Table 1. Further, a photosensitive solution similar to that in Example 1 was prepared using these photosensitizers. Using this, a photosensitive layer was formed in the same manner as in Example 1, and when the above photosensitive layer was irradiated with light by an argon laser, it was confirmed that the resin was rapidly cured.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

INDUSTRIAL APPLICABILITY The 4-substituted carbonylcoumarin derivative of the present invention is a compound having extremely high usefulness as a photosensitizer. Conventionally, in the field of information recording using a photopolymerization reaction, a method in which an original document electronically edited by a computer is directly output by using a laser for recording and the time-dependent stability of the photosensitive layer is low and the sensitivity is low. However, there were problems in solubility, storage stability and the like. However, the 4-substituted carbonylcoumarin derivative of the present invention has good compatibility with the base resin,
Moreover, it can be dissolved in a general-purpose coating solvent and a uniform and smooth coating surface can be obtained on the support. Further, the 4-substituted carbonylcoumarin derivative of the present invention has 488 nm and 514.
The photosensitizer of the present invention is used because it has very high sensitivity to general-purpose visible lasers such as an argon laser having a stable oscillation line at 5 nm and a YAG laser having an emission line at 532 nm as a second harmonic. The obtained light-sensitive material can be subjected to high-speed scanning exposure with such a laser. Further, when an image is formed by high-speed scanning exposure, an extremely fine high-resolution image can be obtained.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the carbonylcoumarin derivative obtained in Example 1.

Front page continuation (72) Keisuke Soma Inventor Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa

Claims (4)

[Claims] 1. A 4-substituted carbonylcoumarin derivative represented by the general formula (1) (formula 1). [Chemical 1] [In the formula, R ¹ and R ² each independently or independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, a hydroxyalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, which may be bonded to each other; It may combine with a benzene nucleus substituted with an amino group in the skeleton to form a ring, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group or an alkoxyalkoxy. Group, an alkoxycarbonyl group, a sulfonic acid group, a halogenoalkyl group, X is a hydrogen atom, an alkyl group,
Cycloalkyl group, alkoxy group, cycloalkoxy group, hydroxyl group, aryl group, alkenyl group, aryloxy group, alkenyloxy group, aralkyl group, aralkyloxy group, alkoxycarbonylalkoxy group, alkylcarbonylalkoxy group, or the following substituents ( (Chemical formula 2) (Here, R ^{4 to} R ⁸ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, an alkoxyalkyl group, or an alkylcarbonyl group, and m, n, r, and s are each 1 to 5 represents an integer of 5) Y represents a hydrogen atom, an alkylcarbonyl group, an alkoxycarbonyl group, an aryl group, an arylcarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylalkylcarbonyl group, an alkoxycarbonylalkoxycarbonyl group, or a heterocyclic group. Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom, and Z ¹ and Z ²
At least one of them is a sulfur atom) 2. A 4-substituted carbonylcoumarin derivative represented by the general formula (2) (formula 3). [Chemical 3] [In the formula, R ⁹ and R ¹⁰ each independently represent a lower alkyl group having 1 to 4 carbon atoms, which may be the same or different, and R ¹¹ represents a hydrogen atom, a lower alkyl group, an alkoxyalkyl group, a hydroxyalkoxyalkyl group, or an alkoxy group. A carbonylalkyl group, Z ³ and Z ⁴ each independently represent an oxygen atom or a sulfur atom, and at least one of Z ³ and Z ⁴ is a sulfur atom] 3. A photosensitizer comprising the 4-substituted carbonylcoumarin derivative according to claim 1. 4. A photosensitive composition comprising the 4-substituted carbonylcoumarin derivative according to claim 1 or 2, which can be crosslinked or polymerized by irradiation with visible light.