JPH09118708A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having excellent sensitivity to light of a wide range of wavelengths and giving a cured product at small energy by mixing an ethylenically unsaturated polymerizable compound with a plurality of specified compounds. SOLUTION: This composition comprises an ethylenically unsaturated polymerizable compound desirably a (meth)acrylic ester, a carbazolyltriazine compound represented by formula I (wherein X is a halogen; R1 and R2 are each S, H or a 1-4 C alkyl; R3 is a 1-12 C alkylene; Y is a direct bond, O, O-CO or CO-O; and R4 is H, a 1-12 C alkyl, an aryl or aralkyl which may be substituted by a 1-12 C alkyl or X, a 5-12 C cycloalkyl or a 3-12 C alkoxyalkyl) and a coumarin compound represented by formula II [wherein R5 and R6 are each a 1-12 C alkyl or a 3-12 C alkoxyalkyl; (n) is 1 or 2; when (n) is 1, A is a group represented by formula III (wherein Z id S or NH) or a 2-12 C aliphatic, alicyclic, aromatic or heterocyclic acyl; and when (n) is 2, A is CO].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition in which two kinds of photopolymerization initiators are mixed with an ethylenically unsaturated polymerizable compound, and more specifically, it is excellent in light in a wide wavelength range. And a photopolymerizable composition having high sensitivity.

[0002]

2. Description of the Related Art A photopolymerizable composition is a composition in which a photopolymerization initiator is added to an ethylenically unsaturated polymerizable compound, and the photopolymerizable composition is irradiated with light. Since it can be polymerized and cured, it is used for photocurable inks, photosensitive printing plates, various photoresists and the like.

As a photopolymerization initiator used in this photopolymerizable composition, it is known to use a halomethyltriazine compound which decomposes upon irradiation with light to generate a halogen free radical. Among these halomethyltriazine compounds, 2-aryl-4,6-bis (trihalomethyl) -s-triazine is known to have relatively good sensitivity, and is disclosed in, for example, JP-A-53-133428. The publication proposes to use a compound using a bicyclic or polycyclic aromatic group or a heterocyclic aromatic group as the 2-position aryl group, and particularly uses a naphthyl group as the aryl group. It is described that good results can be obtained when there is.

However, the above-mentioned Japanese Patent Laid-Open No. 53-133.
The sensitivity of the compound described in Japanese Patent No. 428 is unsatisfactory in practice, and it is necessary not only to use a large amount or to irradiate light for a long time, but also to dissolve the compound having an ethylenically unsaturated bond. Is insufficient,
The photopolymerizable composition has a drawback of being poor in stability over time.

Further, Japanese Patent Laid-Open No. 63-70243 proposes to improve stability with time by introducing a substituent having an amide bond or an ester bond into the naphthyl group at the 2-position. Also in this case, the sensitivity as a photoinitiator was not satisfactory.

Therefore, the present inventors not only found that the halomethyltriazine compound having a carbazolyl group was excellent, but also that the sensitivity as a photopolymerization initiator was not only excellent, but that the photopolymerizable composition was used as well. We found that it has excellent stability over time, and filed an application for it in Japanese Patent Application No. 7-15705. However, after further study, we found that the halomethyltriazine compound having a carbazolyl group had a wavelength of about 400 nm.
Although it has excellent sensitivity to light in the following relatively short wavelength region, it has been found that the sensitivity to light in the longer wavelength region beyond that is insufficient and is not yet satisfactory in practical use. .

It is known that a coumarin compound substituted with a dialkylamino group polymerizes a compound having an ethylenically unsaturated bond even by light in a relatively long wavelength region, but its sensitivity is not sufficient at all. However, there is a drawback that it is necessary to use a large amount or to irradiate light for a long time. Also, the Chemical Society of Japan, January 1984, 192--19.
On page 8, it is reported that a combination of a coumarin compound and a radical generator such as a halomethyltriazine compound exhibits good sensitivity in the long wavelength region, but the effect is additive when these are used in combination. It was nothing but a practically unsatisfactory one.

Therefore, an object of the present invention is to provide a photosensitizer having excellent sensitivity to light in a wide wavelength range and capable of advancing the polymerization of an ethylenically unsaturated compound as needed by irradiating light for a short time. It is to provide a polymerizable composition.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a composition prepared by combining an ethylenically unsaturated compound with a specific halomethyltriazine compound and a specific coumarin compound is used. , It was found that the above object can be achieved.

The present invention has been made based on the above findings, and is based on an ethylenically unsaturated polymerizable compound represented by the following [Chemical Formula 3].
A carbazolyltriazine compound represented by the general formula (I) (same as the above [Chemical formula 1]) and a coumarin represented by the general formula (II) of the following [Chemical formula 4] (the same as the above [Chemical formula 2]) A photopolymerizable composition containing a compound is provided.

[0011]

Embedded image

[0012]

Embedded image

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable composition of the present invention will be described in detail below.

The carbazolyltriazine compound represented by the above general formula (I) used in the present invention (hereinafter sometimes simply referred to as "compound (I)") is represented by the above general formula (II). It is used as a photopolymerization initiator together with the coumarin compound (hereinafter sometimes simply referred to as “compound (II)”).

In the above compound (I), the alkyl group having 1 to 4 carbon atoms represented by R ₁ and R ₂ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. Groups of R ₁ ,
Examples of the halogen atom represented by R ₂ and X include atoms such as chlorine, bromine, fluorine and iodine, and examples of the alkylene group having 1 to 12 carbon atoms represented by R ₃ include, for example,
Examples include groups such as methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. , 1 to 12 carbon atoms represented by R ₄
Examples of the alkyl group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-butyl. Examples of the group include octyl, nonyl, decyl, undecyl, dodecyl and the like, and as the aryl group or aralkyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms represented by R ₄ or a halogen atom, for example, Examples of the alkyl group or phenyl, naphthyl, benzyl, phenylethyl and the like which may be substituted with a halogen atom may be mentioned. Examples of the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl,
Cyclohexyl, cyclooctyl, cyclododecyl, 4
Groups such as -methylcyclohexyl, and examples of the alkoxyalkyl group having 3 to 12 carbon atoms include, for example,
2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-octoxyethyl, 2-methoxy-1-
Methyl ethyl, 2-ethoxy-1-methyl ethyl, 2-
Butoxy-1-methylethyl, 2-methoxy-1-ethylbutyl, 3-methoxybutyl, 4-methoxybutyl,
Examples include groups such as 4-butoxybutyl, 4-octoxybutyl, 6-methoxyhexyl and the like.

Among the above compounds (I), particularly, a carbazolyltriazine compound in which X is a chlorine atom and /
Alternatively, it is preferable to use a carbazolyltriazine compound in which Y is —CO—O— because the sensitivity is particularly high and the synergistic action with the coumarin compound [compound (II)] is excellent.

Therefore, among the above compounds (I), particularly preferable compounds are compounds 1 to 18 shown below.
And the like.

Compound 1: 2- (Nn-butyl-3'-
Carbazolyl) -4,6-bis (trichloromethyl)-
s-triazine

Compound 2: 2- (Nn-octyl-3 ')
-Carbazolyl) -4,6-bis (trichloromethyl)
-S-triazine

Compound 3: 2- (N- (2 "-methoxyethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 4: 2- (N- (2 "-phenoxyethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 5: 2- (N- (2 "-p-tert-butylphenoxyethyl) -3'-carbazolyl) -4,
6-bis (trichloromethyl) -s-triazine

Compound 6: 2- (N- (2 "-p-chlorophenoxyethyl) -3'-carbazolyl) -4,6-
Bis (trichloromethyl) -s-triazine

Compound 7: 2- (N-ethoxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 8: 2- (Nn-butoxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 9: 2- (N-isoamyloxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 10: 2- (Nn-octoxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 11: 2- (N-benzyloxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 12: 2- (N-cyclohexyloxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 13: 2- (N- (2 "-methoxyethoxycarbonylmethyl) -3'-carbazolyl)-
4,6-bis (trichloromethyl) -s-triazine

Compound 14: 2- (N- (2 "-ethoxyethoxycarbonylmethyl) -3'-carbazolyl)-
4,6-bis (trichloromethyl) -s-triazine

Compound 15: 2- (N- (2 "-methoxy-
1 "-methylethoxycarbonylmethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-
Triazine

Compound 16: 2- (N- (2 "-ethoxy-
1 "-methylethoxycarbonylmethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-
Triazine

Compound 17: 2- (N- (2 "-acetoxyethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

Compound 18: 2- (N- (2 "-benzoyloxyethyl) -3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine

The above-mentioned compound (I) can be obtained by a known method for producing a halomethyltriazine compound, for example, 3-cyano-
It can be easily produced by reacting an N-substituted carbazole compound and trihaloacetonitrile in the presence of aluminum halide.

The above-mentioned 3-cyano-N-substituted carbazole compound used as a starting material for producing the above compound (I) is prepared, for example, by reacting an N-substituted carbazole compound with dimethylformamide and phosphorus oxychloride. It is prepared by preparing a -formyl-N-substituted carbazole and then using the well known means of converting an aldehyde group to a cyano group.

Next, specific synthesis examples of the carbazolyltriazine compound [compound (I)] used in the present invention will be shown, but the present invention is not limited by the following synthesis examples.

Synthesis Example [Compound 15: 2- (N- (2 "-methoxy-1" -methylethoxycarbonylmethyl)-
Production of 3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine (compound of the following [Chemical Formula 5]]

[0040]

Embedded image

Step a [Production of 3-formyl-N- (2'-methoxy-1'-methylethoxycarbonylmethyl) carbazole] 16.7 parts by weight of carbazole, monochloroacetic acid-2-methoxy-1-methylethyl ester 20 0.0 parts by weight, diethylene glycol dimethyl ether 66.8 parts by weight,
Take 10.2 parts by weight of sodium methoxide and add 150
After stirring at ℃ for 3 hours, it was cooled to room temperature. After diethylene glycol dimethyl ether was distilled off under reduced pressure, 83.5 parts by weight of toluene was added, and phosphorus oxychloride 6 was added thereto.
1.3 parts by weight and 29.2 parts by weight of dimethylformamide were added, and the mixture was stirred under reflux for 4 hours. A 10% aqueous sodium hydroxide solution was added dropwise until the aqueous layer was alkaline, the organic layer was collected, and the solvent was distilled off under reduced pressure to give 3-formyl-N-.
(2′-Methoxy-1′-methylethoxycarbonylmethyl) carbazole was obtained.

Step b [Production of 3-cyano-N- (2'-methoxy-1'-methylethoxycarbonylmethyl) carbazole] 3-formyl-N- (2'-methoxy-1) obtained in the above step a. '-Methylethoxycarbonylmethyl) carbazole 32.5 parts by weight, hydroxylamine hydrochloride 8.3
Parts by weight, sodium acetate 10.7 parts by weight and acetic acid 15
Part by weight was taken, and the mixture was stirred under reflux for 12 hours. After distilling off acetic acid, the residue was dissolved in chloroform and washed until the washing liquid became neutral, and then chloroform was distilled off. The obtained residue was recrystallized from isopropanol to obtain 3-cyano-N- (2'-methoxy-1'-methylethoxycarbonylmethyl) carbazole.

Step c (Production of Target Product) 32.2 parts by weight of 3-cyano-N- (2′-methoxy-1′-methylethoxycarbonylmethyl) carbazole obtained in the above step b, trichloroacetonitrile 72.
Take 2 parts by weight and 2.7 parts by weight of aluminum bromide,
The mixture was stirred at 20 to 30 ° C. for 3 hours while blowing hydrogen chloride gas until no absorption was observed. After that, the contents gradually solidified, so that the contents were left at room temperature for 15 hours. After adding 200 parts by weight of chloroform, washing with water and drying, the solvent was distilled off, and the obtained yellow solid was mixed with isopropanol /
Recrystallization from a mixed solvent of toluene (300/130) gave a pale yellow powder product having a melting point of 181 to 182 ° C and λmax of 379 nm. As a result of infrared absorption analysis, absorption based on an ester bond was observed at 1740 cm ⁻¹ , and 1540,
Since absorption based on the triazine ring was observed at 1390 and 770 cm ^-1 , it was confirmed that the above product was the desired product.

The coumarin compound [compound (II)] used in the present invention is a known compound. In the compound (II), the number of carbon atoms represented by R ₅ and R ₆ is 1 to
Examples of the alkyl group having 12 and the alkoxyalkyl group having 3 to 12 carbon atoms include R ₄ in the above compound (I).
Examples of the acyl group having 2 to 12 carbon atoms represented by A include, for example, aliphatic acyl groups such as acetyl, propionyl, butyroyl, octanoyl, decanoyl, dodecanoyl, and cyclopropa Alicyclic acyl groups such as noyl, cyclopentanoyl and cyclohexanoyl, aromatic acyl groups such as benzoyl, 4-dimethylaminobenzoyl, toluoyl and naphthoyl, nicotinoyl, benzofuranoyl, 2-thenoyl,
Heterocyclic acyl groups such as 3-thenoyl can be mentioned.

Therefore, typical examples of the above compound (II) include the following compounds A to J.

Compound A: 3- (2'-benzothiazolyl) -7-diethylaminocoumarin

Compound B: 3- (2'-benzothiazolyl) -7-dibutylaminocoumarin

Compound C: 3- (2'-benzimidazolyl) -7-diethylaminocoumarin

Compound D: 3-acetyl-7-diethylaminocoumarin

Compound E: 3,3'-carbonylbis (7
-Diethylaminocoumarin)

Compound F: 3,3'-carbonylbis (7
-Dibutylaminocoumarin)

Compound G: 3,3'-carbonylbis (7
-Bis (N, N-butoxyethyl) aminocoumarin

Compound H: 3,3'-carbonylbis (7
-Bis (N-ethyl-N-butoxyethyl) aminocoumarin

Compound I: 3-benzoyl-7-diethylaminocoumarin

Compound J: 3- (2-benzofuranoyl)
-7-Diethylaminocoumarin

The above compound (I) and compound (II) are
It is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the ethylenically unsaturated polymerizable compound described below. The weight ratio [compound (I): compound (II)] of both is appropriately selected according to the purpose, but is usually 1:10 to 10: 1.

If the content of each of the compound (I) and the compound (II) is less than 0.1 parts by weight, the effect may be hardly recognized, and if the content exceeds 20 parts by weight, the amount may be too small. Not only is it useless because a comparable effect is not obtained, but the physical properties of the cured product may be adversely affected. Also,
If the ratio of the two is out of the above range, the effect of the combined use becomes small, and it becomes difficult to provide excellent sensitivity over a wide wavelength range.

As the ethylenically unsaturated polymerizable compound used in the present invention, those conventionally used in photopolymerizable compositions can be used as they are, but acrylic acid or acrylic acid or It is preferable to use an ester compound of methacrylic acid.

Examples of the ethylenically unsaturated polymerizable compound include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, and trimethylolpropane di (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) Compounds obtained by esterifying polyhydric alcohols such as acrylate and dipentaerythritol hexa (meth) acrylate with α, β-unsaturated carboxylic acids; trimethylolpropane triglycidyl ether acryl Acid adduct (1/3), bisphenol A diglycidyl ether acrylic acid adduct (1/3)
Compounds obtained by adding (meth) acrylic acid to glycidyl group-containing compounds such as 2); phthalic acid diesters of β-hydroxyethyl (meth) acrylate, toluene diisocyanate adducts of β-hydroxyethyl (meth) acrylate, etc. Addition product of ester compound of polyhydric carboxylic acid with compound having hydroxyl group and ethylenically unsaturated bond or polyisocyanate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Examples thereof include acrylates and (meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate.

By using a thermoplastic organic polymer together with the ethylenically unsaturated polymerizable compound, the properties of the cured product can be improved. As the thermoplastic organic polymer, for example, a copolymer of a (meth) acrylic acid ester compound and (meth) acrylic acid, a (meth) acrylic acid ester compound, a (meth) acrylic acid and a copolymerizable with these Examples thereof include copolymers with other vinyl monomers.

Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate tetrahydrofurfuryl (meth) acrylate, tert-butyl (meth)
Acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and the like.
Examples of the other vinyl monomer include diacetone acrylamide, styrene, vinyltoluene and the like.

Further, the photopolymerizable composition of the present invention can be used in combination with other photopolymerization initiators if necessary, and by using it in combination with other photopolymerization initiators. In some cases, a significant synergistic effect is achieved.

As the above-mentioned other photopolymerization initiator which can be used in combination with the photopolymerizable composition of the present invention, conventionally known compounds can be used, for example, benzophenone, phenyl biphenyl ketone, 1-hydroxy-1. -Benzoylcyclohexane, benzyl, benzyl dimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-
Morpholinobenzoyl) propane, 2-morpholyl-2
-(4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4 '.
-Methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-
Hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-
Phenoxybenzoyl dichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-4,6 −
Examples thereof include bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine and 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine.

In the photopolymerizable composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol and phenothiazine; a plasticizer; an adhesion promoter; Conventional additives such as fillers, pigments, dyes and the like can be added.

The photopolymerizable composition of the present invention is usually
A solvent capable of dissolving or dispersing each of the above components as necessary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methylocerosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene,
It is used as a solution-like composition to which xylene, methanol, ethanol and isopropanol are added.

The photopolymerizable composition of the present invention comprises a roll coater, a curtain coater, a spin coater, various types of printing,
It is applied onto a supporting substrate made of metal, paper, plastic or the like by a known means such as dipping. Also, once applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and there is no limitation on the application method.

The photopolymerizable composition of the present invention can be used in various applications such as photocurable coatings, photocurable inks, photocurable adhesives, printing plates and photoresists for printed wiring boards. There are no particular restrictions on its use.

Further, since the photopolymerizable composition of the present invention is excellent in sensitivity to light in a wide wavelength region, a light source of active light used for polymerizing and curing the composition has a wavelength of 3
A light source that emits light of 00 to 600 nm can be used, and conventionally known light sources such as an argon laser, a mercury vapor arc, a carbon arc, and a xenon arc can be used.

[0069]

【Example】

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples. Compounds 1 to 18 and compounds A to J used in the following examples are the compounds exemplified as the above-mentioned compound (I) and compound (II), respectively.

Example 1 10 parts by weight of trimethylolpropane triacrylate Polyethylene glycol (molecular weight 300) diacrylate 10 Allyl methacrylate / methacrylic acid copolymer (molar ratio 8/2) 30 Compound E: carbonylbis (7-diethylaminocoumarin) 1 Halomethyltriazine compound (see the following [Table 1]) 1 Methyl ethyl ketone 150 A photopolymerizable composition was prepared by thoroughly mixing the above-mentioned formulation, and this solution was dried on a surface-treated aluminum plate to give a dry film thickness of 10 μm. Was uniformly applied and dried in a dryer for 2 minutes, and then a polyethylene terephthalate (PET) film was adhered thereto to form a photopolymerizable element.

This photopolymerizable element was exposed to light of each wavelength shown in the following [Table 1] by a spectral irradiation device using a xenon lamp as a light source, and then the PET film was removed and developed with a 1 wt% sodium carbonate aqueous solution. Then, the minimum irradiation energy (mJ / cm ² ) required for curing was determined by the number of remaining cured films. The results are shown in Table 1 below.

The above-mentioned spectroscopic irradiation device is provided with a diffraction grating for separating the irradiation light, a shutter capable of controlling the irradiation time in 13 steps, and a moving stage linked with this shutter, and the photopolymerizable element is set on this moving stage. As a result, it is possible to form a continuous image by irradiating different energies in 13 steps, and the irradiation energy in each step can be measured from the light amount and the irradiation time (shutter opening / closing time).

Further, an example of using only 2 parts by weight of the compound E and not using the triazine compound (Comparative Example 1-1), an example of using 2 parts by weight of only the triazine compound and not using the compound E (Comparative Example 1-2) and the present invention The same test was performed also on the examples (Comparative Examples 1-3) using the triazine compound other than the compound (I) according to the invention.

[0075]

[Table 1]

Example 2 The same test as in Example 1 was carried out except that 1 part by weight of Compound 15 was used as the halomethyltriazine compound, and the type and blending amount of the coumarin compound were changed as shown in Table 2 below. went. The results are shown in Table 2 below.

[0077]

[Table 2]

Example 3 Pentaerythritol trimethacrylate 100 parts by weight Chlorinated polyethylene (chlorine content 66%) 90 Sample compound 1 1,2-dichloroethane 400 shown in the following [Table 3] 400 A photopolymerizable composition was prepared by the above formulation. The solution was prepared, and this solution was applied on an aluminum plate so as to have a dry film thickness of 10 μm and dried, and then a polyethylene terephthalate film was adhered thereto to obtain a photopolymerizable element.

This photopolymerizable element has a wavelength of 488 nm.
And an argon laser that emits visible light of 514.5 nm, the light amount on the surface of the photosensitive layer is 10 mW to 500 mW.
Scanning was performed at 10 cm / sec by gradually changing so that

After removing the polyethylene terephthalate film, the uncured portion was removed with trichloroethane,
A photocured image formed on an aluminum plate was formed. The minimum scanning light quantity with which an image is formed in this way is shown in [Table 3] below. It is indicated that the light sensitivity is higher as the image is formed with a smaller amount of light.

[0081]

[Table 3]

From the above results, the photopolymerizable composition of the present invention containing the ethylenically unsaturated polymerizable compound, the compound (I) and the compound (II) (Examples 1-1 to 1-
18,2-1 to 2-12,3-1 to 3-4) have excellent sensitivity.

[0083]

INDUSTRIAL APPLICABILITY The photopolymerizable composition of the present invention has excellent sensitivity to light in a wide wavelength range, and can give a cured product with a small amount of energy.

Claims (6)

[Claims] 1. An ethylenically unsaturated polymerizable compound, a carbazolyltriazine compound represented by the general formula (I) of the following [Chemical formula 1] and a general formula (II) of the following [Chemical formula 2]. A photopolymerizable composition containing a coumarin compound. Embedded image Embedded image 2. The photopolymerizable composition according to claim 1, wherein X in the general formula (I) is a chlorine atom. 3. Y in the general formula (I) is —CO—.
The photopolymerizable composition according to claim 1, which is O-. 4. The carbazolyl triazine compound,
The photopolymerizable composition according to claim 1, which is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the ethylenically unsaturated polymerizable compound. 5. The coumarin compound is 0.1 to 2 with respect to 100 parts by weight of the ethylenically unsaturated polymerizable compound.
The photopolymerizable composition according to claim 1, which is contained in an amount of 0 part by weight. 6. The photopolymerizable composition according to claim 1, wherein the ethylenically unsaturated polymerizable compound is an ester compound of acrylic acid or methacrylic acid.