JPH1184635A - Manufacturing method of photosensitive lithographic printing plate - Google Patents

Abstract

(57) [Problem] To provide a method for producing a photosensitive lithographic printing plate having good sensitivity and storage stability. SOLUTION: A method for producing a photosensitive lithographic printing plate by applying a photopolymerizable coating solution containing a photopolymerization initiation system and a solvent on a support, and drying the composition by adding an ethylenically unsaturated bond-containing compound capable of being polymerized on a support, A method for producing a photosensitive lithographic printing plate, characterized in that the solvent contains a solvent having a boiling point of 120 ° C. or more, and the coating solution is dried at a temperature of (the boiling point of the highest boiling solvent in the solvent −80) ° C. or less. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a photosensitive lithographic printing plate. More specifically, the present invention relates to a method for producing a photopolymerizable photosensitive lithographic printing plate suitable for exposure to a laser beam in the visible region.

[0002]

2. Description of the Related Art A photopolymerizable photosensitive lithographic printing plate can realize higher sensitivity than a printing plate using a diazo resin or a quinonediazide compound by utilizing a chain reaction of radical polymerization. In addition, the use of the sensitizing dye increases the degree of freedom in the photosensitive wavelength region. For this reason, 1990
It has been put into practical use as a plate (so-called CTP plate) for forming an image by directly exposing the plate surface with visible laser light since the age. However, this plate has a problem that the storage stability decreases as the sensitivity increases. Benzoquinone, p-toluquinone, quinone compounds such as p-xyloquinone, hydroquinone, p-methoxyphenol, hydroxy aromatic compounds such as p-tert-butylcatechol, phenyl-α-naphthylamine,
Addition of a radical polymerization inhibitor typified by amines such as N, N'-diphenyl-p-phenylenediamine, and addition of oximes, hydroxylamines and thiurams are disclosed in JP-B-60-53041. However, Japanese Patent Publication No. 60-21373 discloses the addition of thiurams, dithiocarbamates, and N-nitrosophenylhydroxylamine salts, but has the problem of lowering the sensitivity.

In the production of a photosensitive lithographic printing plate, the photosensitive composition is generally dissolved in an appropriate solvent and coated on a support. A single solvent or a mixed solvent is used as a coating solvent. Can be At this time, it is common to include a solvent having a boiling point of 120 ° C. or higher from the viewpoint of safety in order to prevent coating unevenness due to rapid drying, and the drying conditions at this time are to completely dry the solvent, for example, Relatively high temperatures are used as described below.

[0004]

[Table 1]

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable photosensitive lithographic printing plate having high sensitivity and good storage stability.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, although the reason is still unclear, the boiling point of the coating solvent and the drying of the coated photosensitive layer during the production of a lithographic printing plate. By controlling the relationship with humidity, it was found that both sensitivity and storage stability were compatible, and the present invention was reached. That is, the gist of the present invention is to apply a photopolymerizable coating solution containing an addition-polymerizable ethylenically unsaturated bond-containing compound, a photopolymerization initiation system and a solvent onto a support, and to dry the photosensitive lithographic printing plate. In the production method, the solvent is 12
A method for producing a photosensitive lithographic printing plate comprising a solvent having a boiling point of 0 ° C. or higher and drying the coating solution at a temperature of (the boiling point of the highest boiling point solvent in the solvent −80) ° C. or lower. .

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The ethylenically unsaturated bond-containing compound contained as an essential component of the photopolymerizable coating solution of the present invention is a photopolymerization initiation system which is a second essential component when the photopolymerizable composition is irradiated with actinic rays. A compound having an ethylenically unsaturated double bond which is addition-polymerized and cured by the action of, for example, the monomer having the double bond or the ethylenically unsaturated double bond in the side chain or main chain. It is a polymer having a heavy bond. The meaning of the monomer in the present invention is a concept corresponding to a so-called polymer substance, and therefore includes not only monomers in a narrow sense, but also dimers, trimers, and oligomers. is there. Examples of the ethylenic compound include various known compounds.
No. 35198 can be mentioned. Specifically, for example, unsaturated carboxylic acid, ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; unsaturated carboxylic acid and a polyvalent carboxylic acid; And an ester obtained by an esterification reaction with a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but specific examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, Acrylates such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and the acrylates of these exemplified compounds are replaced with methacrylates Methacrylic acid ester, itaconic acid ester similarly replaced with itaconate, Rotoneto some maleic acid ester, and was replaced with crotonic acid ester or maleate was replaced.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction between the unsaturated carboxylic acid and the polyhydric carboxylic acid and the polyhydric hydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid and ethylene glycol. Condensates, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.

Other examples of the ethylenically unsaturated bond-containing compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. . The polymer having an ethylenically unsaturated bond in the main chain is, for example, a polyester obtained by a polycondensation reaction between an unsaturated divalent carboxylic acid and a dihydroxy compound, a polycondensation reaction between an unsaturated divalent carboxylic acid and a diamine. And the like.

Further, as a polymer having an ethylenically unsaturated bond in the side chain, a dihydric carboxylic acid having an unsaturated bond in the side chain such as itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. Can also be used. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc., and acrylic acid, methacrylic acid, crotonic acid, etc. A polymer obtained by a polymer reaction with an unsaturated carboxylic acid of formula (I) can also be suitably used.

Next, as the photopolymerization initiation system, any system capable of initiating the polymerization of the addition-polymerizable compound can be used.
Among them, examples of the activator that generates an active radical by performing an action with the photoexcited sensitizer include hexaarylbiimidazole, metallocene compounds, halogenated hydrocarbon derivatives, onium salts, and organic peroxides. Can be mentioned. Among them, a system using a hexaarylbiimidazole or a titanocene compound is preferred because sensitivity, storage stability, adhesion of a coating film to a substrate, and the like are good.

As the hexaarylbiimidazole,
Various types can be used. For example, 2,2 '
-Bis (o-chlorophenyl) -4,4 ', 5,5'-
Tetra (p-carbethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-carbethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-fluorophenyl) bi Imidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4, 4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chlorophenyl) biimidazole , 2,2'-bis (o-
Bromophenyl) -4,4 ', 5,5'-tetra (p-
Chloro-p-methoxyphenyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dibromophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-
Dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole and the like.

These biimidazoles may optionally be
It can also be used in combination with other kinds of biimidazole. Biimidazoles are described, for example, in Bull. Chem.
Soc. Japan, 33, 565 (1960); Org. Chem. 36 [16] 2262 (197
It can be easily synthesized by the method disclosed in 1).

As the titanocene compound, various compounds can be used. For example, JP-A-59-1523
No. 96, and various titanocene compounds described in JP-A-61-151197 can be appropriately selected and used. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl,
Di-cyclopentadienyl-Ti-bis-2,4,6-
Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-
Yl, di-cyclopentadienyl-Ti-bis-2,4
-Di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti- Bis-2,6-difluorophenyl-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
6-difluoro-3- (pyr-1-yl) -phenyl-1
-Yl and the like.

Next, the sensitizer will be described. The sensitizer in the present invention is preferably a compound capable of effectively generating an active radical upon irradiation with visible light when coexisting with the above-mentioned activator. Examples of typical sensitizers include, for example,
US Pat. No. 3,479,185 discloses a triphenylmethane-based leuco dye such as leuco crystal violet and leucomalachite green, a photoreducing dye such as erythrosine and eosin Y, and the like. 3,549,367, U.S. Pat.
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat. No. 2,275, etc .; β-diketones disclosed in US Pat. No. 3,844,790; US Pat. No. 4,162 And indanones described in JP-A No. 52-112681.
Coumarins disclosed in JP-A-59-56403
No. 4,594,3, disclosed in US Pat. No. 4,594,311.
No. 10, aminophenyl heterocycles described in U.S. Pat. No. 4,966,830, and pyrromethene dyes described in JP-A-5-241338.

Of these, coumarins or pyromethene dyes are preferred for use with visible lasers. As the coumarins, those represented by the general formula [I] are preferable, and as the pyromethene dye, those represented by the general formula [II] are preferable.

[0018]

Embedded image

(Wherein R¹And R^TwoAre hydrogen sources
Group, an alkyl group, an alkoxy group or an alkylthio group
Represents, R^ThreeAnd R^FourEach represents an alkyl group;
¹And R ^ThreeAnd / or R^TwoAnd R^FourAre mutually connected
To form a ring structure, X is a cyano group or
Is

[0020]

Embedded image

Wherein ring A represents a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear or dinuclear aromatic heterocyclic residue, and Y represents a divalent atom or a divalent group. Represent. )

[0022]

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(Wherein, R ^{5 to} R ¹¹ are each a hydrogen atom,
Halogen atom, alkyl group, aryl group, aralkyl group, acyl group, alkoxycarbonyl group, substituted or unsubstituted hydrocarbon ring group, substituted or unsubstituted heterocyclic group or-
Represents SO ₃ —R ¹² , wherein R ¹² represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or a quaternary ammonium group. X ¹ and X ² each represent a halogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group. )

The photopolymerizable coating solution of the present invention preferably contains a polymer binder. This is a component that imparts a film-forming ability and a viscosity adjusting ability. Specific examples thereof include (meth) acrylic acid, their esterified products, maleic acid, acrylonitrile, styrene, vinyl acetate,
Examples thereof include homopolymers or copolymers such as vinylidene chloride, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyethylene terephthalate, acetylcellulose, and polyvinyl butyral. The photopolymerizable coating solution of the present invention may further contain other substances in addition to the above-mentioned components, depending on the purpose of use. Among them, the compounds represented by the general formulas (i) to (iii) are preferred for the purpose of improving the sensitivity.

[0025]

Embedded image

(Wherein Q ¹ , Q ² and Q ⁴ -Q ¹¹ are
Each represents an alkyl group having 1 to 4 carbon atoms, and Q ³ represents an alkyl group having 1 to 20 carbon atoms. Also, thermal polymerization inhibitors such as phenols, coloring agents composed of organic or inorganic dyes and pigments, plasticizers such as dioctyl phthalate, didodecyl phthalate and tricresyl phosphate, and sensitivity characteristics such as tertiary amines and thiols Improver,
Other additives such as a dye precursor can also be added.

Solvents for the photopolymerizable coating solution of the present invention include cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol ethers such as propylene glycol monomethyl ether. Propylene glycol monoalkyl acetates such as propylene glycol monomethyl ether acetate, diethylene glycol ethers such as diethylene glycol dimethyl ether, lactate esters such as methyl lactate and ethyl lactate, acetate esters such as ethyl acetate and butyl acetate, and dimethylformamide and the like. Amides, sulfoxides such as dimethyl sulfoxide, dioxane, cyclic ethers such as tetrahydrofuran, acetone, Methyl ethyl ketone and cyclohexanone, chloroform, methylene chloride,
Halogenated solvents such as trichloroethylene are exemplified. In the present invention, these solvents can be used alone or in combination of two or more, but it is necessary that the solvent contains a solvent having a boiling point of at least 120 ° C. or higher.
When the solvent is a mixed solvent, the proportion of the solvent having a boiling point of 120 ° C. or more is preferably 20% or more in all the solvents.

The ratio of each of the above constituents is based on 100 parts by weight of the ethylenically unsaturated bond-containing compound and 1 part of the photopolymerization initiator.
To 50 parts by weight, and when another component is used in combination, 0.1 to 10 parts by weight of a sensitizer, 200 parts by weight or less of a polymer binder, 1 to 20 parts by weight of a sensitivity enhancer, and 10 parts by weight of a colorant. Hereinafter, 2 parts by weight or less of a thermal polymerization inhibitor, 40 parts by weight or less of a plasticizer, 30 parts by weight or less of a sensitivity property improver, and 30 parts by weight or less of a dye precursor. The solvent has a total solid content concentration of 5 to 20.
It is prepared so as to be about weight%.

The photopolymerizable coating solution described above is coated on a support, dried and coated as a photosensitive layer. As the support in the present invention, metal, plastic, paper and the like are used, and an aluminum support is particularly preferably used.
When an aluminum plate is used as the support, surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment is performed. A known method can be applied to these processes.

Examples of the graining method include a mechanical method and an electrolytic etching method. Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material and the like.
A preferred method is electrolytic etching.

In the electrolytic etching, phosphoric acid, sulfuric acid, hydrochloric acid,
The reaction is carried out in a bath containing one or more inorganic acids such as nitric acid. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous solution of an alkali or an acid to neutralize and wash with water. The anodic oxidation treatment is performed by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, or the like as an electrolytic solution and performing electrolysis using an aluminum plate as an anode. The amount of anodic oxide film formed is 1-50mg
/ Dm ² is suitable, and preferably 10 to 40 mg / d
m ² . The amount of the anodic oxide film is, for example, as follows.
1, chromium oxide (VI): prepared by dissolving 20 g in 1 liter of water), dissolving the oxide film, and measuring the weight change before and after dissolving the film on the plate.

Examples of the sealing treatment include a boiling water treatment, a steam treatment, a sodium silicate treatment, a dichromate aqueous solution treatment and the like. In addition, the aluminum plate support may be subjected to an undercoating treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconic acid. Application methods include dip coating, coating rod,
It can be applied by a known method such as spinner coating, spray coating, roll coating and the like.

The drying method may be any method, and specific examples include a method of contacting with a heated substance such as a hot plate or a heating roll, and a method of blowing hot air. In the present invention, as described above, it is essential to include a solvent having a boiling point of 120 ° C. or more as a coating solvent, but it is further dried at a temperature of (the boiling point of the highest boiling point solvent in the solvent −80) ° C. or less. And If the temperature difference between the solvent and the boiling point of the solvent having the highest boiling point (the solvent having the highest boiling point among the solvents used) is less than 80 °, the sensitivity is inferior, and the change in sensitivity due to storage of the plate is large, which is not preferable. The lower limit of the drying temperature is about 40 ° C., and the drying time is appropriately selected from 30 seconds to 300 seconds.

Further, an oxygen-blocking layer can be provided on the above-mentioned photosensitive layer in order to prevent a polymerization inhibiting action by oxygen. Specific examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide,
Examples include water-soluble polymers such as cellulose. Of these, polyvinyl pyrrolidone, polyvinyl alcohol, and mixtures thereof are particularly preferred.

These can be coated and dried in the same manner as the photosensitive layer,
It can be provided by laminating. The exposure light source that can be applied to the photosensitive lithographic printing plate obtained by the method of the present invention is not particularly limited. A laser, an argon ion laser, a YAG laser, a helium neon laser and the like can be particularly preferably used.

After image exposure with such a light source, development is performed using, for example, an aqueous solution containing a surfactant and an alkali, whereby an image can be formed on the support. The aqueous solution may further contain an organic solvent, a buffer, a dye or a pigment. Suitable alkaline agents include
Inorganic alkaline agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, sodium carbonate, potassium carbonate, sodium bicarbonate and the like, and trimethylamine, diethylamine And organic amine compounds such as monoisopropylamine, n-butylamine, monoethanolamine, diethanolamine and triethanolamine, and these can be used alone or in combination. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonates And anionic surfactants such as alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates and sulfosuccinates; and amphoteric surfactants such as alkylbetaines and amine acids. Further, as the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenol cellosolve, propylene glycol, diacetone alcohol, and the like can be contained as required.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it exceeds the gist thereof. (Examples 1 to 7 and Comparative Examples 1 to 4) Aluminum plate 3
Degreased with 12% sodium hydroxide, and this was electrolytically etched in a 12 g / L hydrochloric acid bath at 25 ° C. and a current density of 80 ° / dm ² for 10 seconds. After desmutting for 2 seconds and washing with water, anodizing was performed in a 30% sulfuric acid bath at 30 ° C. and 10 ° / dm ² for 15 seconds. Next, hot water sealing treatment is performed at 90 ° C. and pH = 9,
After drying, an aluminum plate for a lithographic printing plate was obtained.

The following photopolymerizable coating solution was applied onto the aluminum plate using a wire bar to a dry film thickness of 1.5 g / m ² and dried. Further, an aqueous solution obtained by dissolving a surfactant (Liponox NC manufactured by Lion Corporation) at a ratio of 0.2% by weight in a 10% by weight aqueous solution of polyvinyl alcohol was similarly dried on a wire bar using a wire bar. The coating was performed at 3 g / m ² and dried at 90 ° C. Drying was performed by blowing warm air at 7 m / sec.

[Photopolymerizable coating solution] Ethylenic unsaturated bond-containing compound Urethane acrylate: U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts Dipentaerythritol hexaacrylate 20 parts Phosphate acrylate: PM -2 (manufactured by Nippon Kayaku Co., Ltd.) 15 parts Methyl methacrylate: isobutyl methacrylate: methacrylic acid = 5: 3: 2 (molar ratio) resin (Mw = 30,000) with glycidyl methacrylate to methacrylic acid 45 parts of polymer with 50 mol% added ● Polymerization initiation system 5 parts of photopolymerization initiator (titanocene compound)

[0040]

Embedded image

2 parts of sensitizers shown in Tables 1 and 2 ● Additives 10 parts of ethyl pN, N-dimethylaminobenzoate ● Solvent 1000 parts of solvents shown in Tables 1 and 2 The structure is shown.

[0042]

Embedded image

The obtained photosensitive lithographic printing plate was evaluated according to the following evaluation method. The results are shown in Tables 1 and 2. [Evaluation method] After exposing the photosensitive lithographic printing plate using a diffraction spectral irradiation apparatus (manufactured by Narumi Corporation, RM-23), 0.5% by weight of sodium carbonate and sodium alkylnaphthalenesulfonate (trade name: Perex NBL, Developed with a developer containing 5% by weight (Kao). From the height of the obtained cured image,
The amount of light energy (solid sensitivity) required for photocuring with light having a wavelength of 488 nm or 532 nm was determined. For the storage stability, the sensitivity after storage at 50 ° C. for 3 days under light shielding at room temperature was similarly measured.

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

According to the present invention, it is possible to achieve both sensitivity and preservability, which could not be achieved conventionally.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/031 G03F 7/031 7/20 505 7/20 505

Claims (5)

[Claims] 1. A method for producing a photosensitive lithographic printing plate by applying a photopolymerizable coating solution containing an addition-polymerizable ethylenically unsaturated bond-containing compound, a photopolymerization initiation system and a solvent onto a support and drying the solution. Wherein the solvent contains a solvent having a boiling point of 120 ° C. or more, and the coating solution is dried at a temperature of (the boiling point of the highest boiling solvent in the solvent −80) ° C. or less. Manufacturing method. 2. The method according to claim 1, wherein the photopolymerization initiation system contains a titanocene compound. 3. The photopolymerization initiation system according to the following general formulas (i) and (i)
3. The method according to claim 1, comprising at least one of the compounds represented by i) and (iii). Embedded image (In the formula, Q ¹ , Q ² and Q ^{4 to} Q ¹¹ each represent an alkyl group having 1 to 4 carbon atoms, and Q ³ represents an alkyl group having 1 to 20 carbon atoms.
Represents an alkyl group. ) 4. A photopolymerization initiation system represented by the following general formula [I]:
Comprising at least one of the coumarin compounds represented
The production method according to any one of claims 1 to 3, wherein: Embedded image(Where R¹And R^TwoAre hydrogen and alkyl
Group, an alkoxy group or an alkylthio group;^ThreeYou
And R^FourEach represents an alkyl group;¹And R ^Threeas well as
/ Or R^TwoAnd R^FourAre connected to each other to form a ring structure
X may be a cyano group orWherein ring A is a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon
Represents an aromatic residue or a mononuclear or dinuclear aromatic heterocyclic residue.
Y represents a divalent atom or a divalent group. ) 5. The method according to claim 1, wherein the photopolymerization initiation system contains at least one compound represented by the following general formula [II]. Embedded image (Wherein, R ^{5 to} R ¹¹ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a substituted or unsubstituted hydrocarbon ring group, a substituted or unsubstituted heterocyclic ring, Group or —SO ₃ —R
Represents ^12, R ¹² is a hydrogen atom, an alkyl group, an aryl group,
Represents an aralkyl group, an alkali metal atom or a quaternary ammonium group. X ¹ and X ² are each a halogen atom,
Represents an alkyl group, an aryl group, an aralkyl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group. )