JPH023052A - Photosettable composition - Google Patents

Abstract

PURPOSE:To obtain a photosettable compsn. having susceptibility for light in a relatively long wavelength region by incorporating a photopolymn. initiator comprising a cationic dye having boron anion and a cationic polymerizable compd. into the compsn. CONSTITUTION:A photopolymn. initiator comprising a cationic dye having boron anions and a cationic polymerizable compd. are incorporated in the title compsn. Said cationic dye has a capacity for initiating cation polymn. of the polymerizable compd. by the irradiation with light having relatively long wavelength so long as 600-900nm or longer. Such cationic dye having boron ion and having susceptibility in a desired light absorption wavelength region is selected from a wide range and incorporated. Thus, superior susceptibility for light in a long wavelength region so long as >=600nm is attained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a photosensitive material 1 which is an optical recording medium,
Relatively sensitive to light in the long wavelength range (11; with 1;
Light hardness 1'l is also less susceptible to inhibition by oxygen.

Concerning polyhydric acid compounds.

[Conventional technology]

Conventionally, it is an optical recording medium and contains a photocurable composition.
In the photosensitive material, the photopolymerization initiator contained in the photocurable composition includes, for example, an azo compound, an organic sulfur compound, a carbonyl compound, or a redox system using ferric ions. Among these compounds, organic carbonyl compounds are generally used because of their good stability over time and sensitivity to light, and because they are easy to synthesize.

However, with the remarkable progress in laser technology in recent years, there has been a demand for various recording operations such as resist patterning and plate making using laser light, especially semiconductor laser light, which is inexpensive and compact. Moreover, since this semiconductor laser light does not have a wavelength of 650 nm or less, instead of the conventional photopolymerization initiator, which has a photosensitive wavelength range of 450 nm or less, it is sensitive to light in a relatively long wavelength range of 650 nm or more. Research has been conducted on new photopolymerization initiators with Up to now, for example, systems combining biryllium dyes and peroxides have achieved longer wavelengths in the photosensitive wavelength range;
43044, as a photopolymerization initiator, 500n
A photocurable composition comprising a cationic dye-borate anion complex having a photosensitive wavelength range of m or more and a polymerizable compound capable of radical polymerization is disclosed.

However, in the photocurable composition of the prior invention, since the polymerization reaction is radical polymerization, the polymerization reaction is inhibited by oxygen and the curing of the composition does not proceed.

Alternatively, problems such as a decrease in sensitivity may occur. Therefore, in order to solve the above problems, when producing a photosensitive material, an oxygen barrier layer is usually provided to cover the photocurable composition.

However, providing an oxygen barrier layer in this way is not only time-consuming, but also prevents oxygen molecules from entering from the outside. It has the disadvantage that the above-mentioned inhibition by oxygen cannot be prevented.

On the other hand, as another method for preventing inhibition by oxygen without providing a blocking layer, it is known to use diazonium salts as a photopolymerization initiator.

However, the sensitive wavelength range of these diazonium salts is in the ultraviolet region, and it is extremely difficult to make them sensitive to a long wavelength range of 500 nm or more, and cannot meet the needs of using a long wavelength light source such as a semiconductor laser.

[Problems to be Solved by the Invention] The object of the present invention is to provide an optical recording medium, in which a photosensitive material containing a photocurable composition is particularly suitable for relatively long-wavelength light such as semiconductor laser light. It is an object of the present invention to provide a photocurable composition that is sensitive to light in the range of 300 to 3000 nm, has excellent stability over time, and is less susceptible to inhibition of curability and sensitivity by oxygen.

[Means for solving problems]

The above object is achieved by the present invention as follows.

That is, the present invention is a photocurable composition characterized by using a cationic dye having a boron anion as a photopolymerization initiator, and containing the photopolymerization initiator and a polymerizable compound capable of cationic polymerization.

The photopolymerization initiator contained in the photocurable composition of the present invention, that is, the cationic dye having a boron anion, includes:
At least one kind of compounds represented by the following general formula (I) is used.

R2K However, in the above formula (1), DyeΦ represents a cationic dye moiety, and R1, R2, R3 and R4 are the same or different,
It is selected from the group consisting of a halogen atom, an alkyl group, an aryl group, an aralkyl group, an aryloxy group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a heterocyclic group. or,
R, and R2 or R2 and R3 may be combined to form a ring compound.

Here, the above halogen atoms include fluorine, chlorine, bromine,
All iodine atoms are suitable; as alkyl groups, substituted or unsubstituted straight-chain or branched alkyl groups, such as, among others, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl,
hexyl, octyl, trifluoromethyl, methoxyethyl, methoxyisopropyl, ethoxypropyl, N,
N-dimethylaminoethyl, N,N-dimethylaminopropyl and the like are preferred.

The aryl group is a substituted or unsubstituted aryl group, such as phenyl, naphthyl, chlorophenyl, dichlorophenyl, methoxyphenyl, tolyl, xylyl, ethylphenyl, N,N-dimethylaminophenyl,
Chloronaphthyl, methoxynaphthyl, diphenylaminophenyl and the like are preferred. The aralkyl group is a substituted or unsubstituted aralkyl group, such as benzyl,
Preferred are phenethyl, α-naphthylmethyl, β-naphthylmethyl, p-methoxybenzyl, p-chlorobenzyl and the like. The aryloxy group is preferably a substituted or unsubstituted aryloxy group, such as phenoxy, phenyldioxy, naphthoxy, p-tolyloxy, and the like. Preferred examples of the alkenyl group include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecynyl, and prenyl groups. Preferred examples of the alkynyl group include an acetyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, and a heptenyl group.

Preferred examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cyclohebutyl, and cyclooctyl groups, and those substituted with alkyl groups, halogen atoms, and the like. As a heterocyclic group,
For example, pyridyl group, quinolyl group, lepidyl group, methylpyridyl group, furyl group, thienyl group, indolyl group, pyrrole group, carbazolyl group, N-ethylcarbazolyl group, etc. are preferred.

Preferred specific examples of the cationic dye having a boron anion represented by the general formula (1) as described above will be described in more detail. Examples of the boron anion include tetramethylborate, tetraethylborate, tetrabutylborate, and tributylborate. Isobutyl methylborate, di-t-butyl-dibutylborate, trifluoromethyltrifluoroborate, tetra-n-butylborate, tetraphenylborate, triphenylmethylborate, triphenylethylborate, triphenylpropylborate, triphenyl-n -butylborate, triphenylhexylborate, trimeditylbutylborate, tritolylisopropylborate, triphenylbenzylborate, tetrabenzylborate, triphenylphenethylborate, triphenyl-p-chlorobenzylborate,
Trimethallylphenylborate, tricyclohexylbutylborate, tri(phenylelanyl)butylborate, di(α-naphthyl)dipropylborate, diisopinocamphenyldiamylborate, etc.

On the other hand, examples of cationic dyes include aniline dyes, cyanine dyes, rhodamine dyes, etc., which can stably bond with the boron anion, and particularly preferred aniline dyes include, for example, 1,3-bis (p
-diethylaminophenyl)propanium, l, 1
．． 3. 3-tetrakis(p-diethylaminophenyl)propenium, 1,1゜3.3-tetrakis(p-
morpholinophenyl)propenium, 1,3-bis(p
-diethylaminophenyl)-2-methylpropenium, 1. 2. 3 Tris(p-diethylaminostyryl)carbonium, 1,3-bis(p-diethylaminophenyl)1-(p-tolyl)propenium, 1,1,5
．． 5-tetrakis(p-diethylaminophenyl)pentadienium, 1. 1.5. 5-tetrakis (p-
dipropylaminophenyl) pentadienium, 115
-bis(p-diethylaminophenyl)-1,5-diphenylbentadienium, 1,5-bis(p-dimethylaminophenyl)-1,5-bis(p-anisyl)pentadienium, 1-[γ- (p-dimethylaminophenyl)propenylidene]-guaiazulenium, 1.
l, 5. Examples of cyanine dyes include 1, 1', 3. 3.3
', 3'-hexamethyl-2゜2'-indocarbocyanine, 1. 1', 3. 3゜3',
3'-hexamethyl-2,2'-indodicarbocyanine, 1. 1' 3. 3. 3', 3'
-hexamethyl-2,2'-tricarbocyanine,
l, 1-diethyl-3,3,3', 3'-tetramethyl-2,2'-indocarbocyanine, 1,1'
-dipropyl-3,3,3'3'-tetramethyl-2,2'-indocampodianine,1.1'-jethoxyethyl-3,3,3',3''-tetramethyl-2,2'-indodicarbocyanine, [[3-(
1゜3.3-)rifthyl-2-indolidene)methylidene)-2-700-1-cyclopentateylcomethylidene-1,3,3-trimethyl-2-indolium,
[(3-Ethyl-benzo-1-thiazolium)methylidene-2-700-1-cyclobentateyl]-methylidene-3-ethylbenzo-1-thiazolium, 3.3'-
Diethyl-2,2'-thiacyanine, 3,3'-diethyl-2,2'-thiacarbocyanine, 3,3'-diethyl-2,2'-thiadicarbocyanine, (1-methyl-4-quinolino) -(1,3,3-)samethyl-3H-
Examples of rhodamine dyes such as 1,fu-diaza-2-indentutrimethine cyanine include 2-(6-
Amino-3-imino-3H-xanthy9-yl)benzoic acid, 2-(6-danitylamino-3-diethylimino-3H-xanthy9-yl)benzoic acid, methyl-2-
(6-methylamino-3-methylimino-3H-xanthi-9-yl)benzoic acid, ethyl-2-(6-danitylamino-3-diethylimino-3H-xanthi-9-yl)benzoic acid, and the like.

By arbitrarily combining the above-mentioned cationic dyes and boron anions, or by combining a cationic dye sensitive to a desired light absorption wavelength range and a boron anion that can stably bind to the cationic dye, A cationic dye having a boron anion can be obtained by a known method such as salt exchange.

The above boron anion can be obtained by reacting a boron compound such as triarylboron or boron trifluoride with a nucleophilic reagent such as a lithium compound or Grignard reagent, and an example of its synthesis can be found in the Journal of Practical Chemistry. Volume 26 (1964) page 15,
Journal of the American Chemical Society Vol. 93 (1971') 1816 pages, Journal of the American Chemical Society Vol. 90 (196')
8 years), 5280 pages, Annalene der Chemie-618
Volume (1958) p. 31, Annalen der Chemie-5
Vol. 63 (1949) p. 110, Inorganic Chemistry Vol. 1 (1962) p. 738, Journal
Of Organic Chemistry (1964) 197
1 page, etc., and this method was also followed in the present invention.

In addition, the term "cationic dye having a boron anion" used in this application refers to the compound of the above general formula (1),
General formula (I) is a simplified structure, and this term and formula mean a compound obtained by combining a boron anion and a cationic dye.

Examples of the cationically polymerizable compounds contained in the photocurable composition of the present invention include compounds having an epoxy group, a vinyl ether group, a vinyl group, a thiirane group alone or two or more different groups, and tetrahydrofurans; Examples include compounds such as trimethylene oxides, trioxanes, trimethylene sulfides, ζ-valerolactones, spiroorthoesters, spiroorthocarbonates, and bicycloorthoesters. Among the above compounds, compounds having an epoxy group, a thiirane group, or a vinyl ether group, which have particularly high reactivity, are preferably used. First, specific examples of compounds having an epoxy group include glycidyl methyl ether, glycidyl-n-butyl ether, glycidyl vinyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycidyl acrylic acid, glycidyl methacrylic acid, ethylene diglycidyl diether, and propylene diether. Crisidyl diether, bisphenol A epoxy resin, bisphenol S epoxy resin, novolak epoxy resin, 1, 4-di(glycidyloxycarbamoyl)cyclohexane, di(4)
-glycidyloxycarbamoylcyclohexyl-1-
) Methane; and oligomers or homopolymers of glycidyl acrylic acid or glycidyl methacrylic acid, as well as copolymers with other polymerizable compounds having unsaturated double bonds.

Further, as the compound having a thiirane group, all compounds obtained by substituting the epoxy group part of the above-mentioned epoxy group-containing compound with a thiirane group are preferably used.

Furthermore, as compounds having a vinyl ether group, vinyloxyethoxybenzene, vinyloxyethoxy-ph
toluene, vinyloxypropoxybenzene, vinyloxyethoxy-p-cumene, di(vinyloxyethoxy)benzene, p,p'-di(vinyloxyethoxy)biphenyl,
Bis(p-vinyloxyphenyl) sulfide, bis(p-vinyloxyphenyl)
-vinyloxyethoxyphenyl) ether, di(vinyloxyethoxy)bisphenol-A1 di(vinyloxyethoxy)bisphenol S1 vinyloxyethyl-p1 vinyloxyethyl benzoate, and the like.

The mixing ratio of the above polymerizable compound and photopolymerization initiator is 0.0 parts by weight of the photopolymerization initiator per 100 parts by weight of the polymerizable compound.
The amount is 5 to 30 parts by weight, more preferably 0.5 to 15 parts by weight. In this mixing ratio, the photopolymerization initiator is
If it exceeds 0 parts by weight, the degree of polymerization of the polymerizable compound will not increase. Further, if the amount of the photopolymerization initiator is less than 0.105 parts by weight, problems such as substantially no polymerization reaction will occur.

The present invention provides that a cationic dye having a boron anion has 6
This was achieved by discovering that the above-mentioned polymerizable compound has the ability to initiate cationic polymerization by irradiation with light having a relatively long wavelength of 00 to 900 nm or more. In this case, as mentioned above, based on the general knowledge that polymerizable compounds do not polymerize with radicals and the fact that no change in sensitivity is observed even if an autooxidant is added to this system, the present invention It is believed that the initiating species involved in the cationic polymerization reaction is not the radical group released by the cationic dye.

In the present invention, the polymerization initiating species is DyeOeBR4, to quote the radical generation mechanism (formula 11 formula 2) described in JP-A No. 62-143044, which is a prior invention.
→DyeΦ-+BR3+R-In the above formula, DyeΦ・
Alternatively, it is thought to be a complex involving BR3 or these.

Furthermore, it is possible to add a suitable resin as a binder to the photocurable composition of the present invention; in this case,
Suitable binders can be selected from a wide range of resins, including, for example, nitrocellulose,
Cellulose phosphate, cellulose sulfate, cellulose acetate,
Cellulose esters such as cellulose propionate, cellulose butyrate, cellulose myristate, cellulose bartimitate, cellulose acetate/propionate, cellulose acetate/butyrate; cellulose ethers such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose; e.g. polystyrene, Vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone; for example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer Copolymer resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile; Polyesters such as polyethylene terephthalate; (4,4-isopropylidene, diphenylene-co-1
, 4-cyclohexylene dimethyllene carbonate),
Poly(ethylene dioxy-3,3' phenylene thiocarbonate), poly(4,4' isopropylidene diphenylene carbonate coated terephthalate), poly(4,
4'-isopropylidene diphenylene carbonate)
, polyarylate resins such as poly(4,4-sec-butylidene diphenylene carbonate) and poly(4,4'-isopropylidene diphenylene carbonate-protoxyethylene); polyamides; polyimides; epoxy resins; Examples include phenolic resins; for example, polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene; and natural polymers such as gelatin.

In the photocurable composition, the above binder resin may contain 1 to 9
It is contained in a proportion of 5% by weight, preferably 10 to 70% by weight, and when it exceeds 95% by weight, during image formation,
Due to the difference in physical properties between cured and uncured products, if the amount is less than 1% by weight, problems such as a large amount of energy required for curing may occur.

As mentioned above, in addition to the above, the photocurable composition of the present invention may include a coloring material, an antifoggant, a photodiscoloration inhibitor, a solid solvent,
A surfactant, an antistatic agent, etc. may be added.

The photocurable composition of the present invention includes resist materials, plate-making materials,
In addition to adhesives and the like, it is suitably used mainly as a recording material. Furthermore, although the curability and sensitivity are less likely to be affected even if no oxygen barrier layer is provided, an oxygen barrier layer may be provided.

〔effect〕

As explained above, in the photocurable composition of the present invention, a cationic dye having a boron anion that is sensitive to a desired light absorption wavelength range can be selected from a wide range,
By containing it, it has excellent sensitivity to light in a long wavelength range of 600 nm or more. Moreover, as with conventional methods (without providing an oxygen barrier layer, the curing properties and sensitivity are less likely to be inhibited), but if an oxygen barrier layer is provided, it is even better in terms of preventing the above-mentioned inhibition caused by oxygen. .

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples. In addition, unless otherwise specified, parts and parts in the text are based on weight.

Synthesis Example 1> Synthesis of sodium diphenyldibutylborate A Grignard reagent was prepared from magnesium (5 g) and butyl bromide (34 g) in dry tetrahydrofuran (170 ml), and diphenylchloroboron (3
Gradually drop a solution of 5g) of dry citrahydrofuran (50ml) into the mixture. After reacting for 1 hour, add a 2N aqueous sodium hydroxide solution (500mf) and continue stirring for 10 minutes. After separating the organic layer, dehydrate with calcium chloride. And furthermore,
Distill the reagent under reduced pressure and dry.

Distilled water (600 mf) is added to this, filtered, and then salted out. Filter and dry the white precipitate. Yield was 46g.

Synthesis Example 2> Synthesis of lithium trianisbutylborate Trianisboron (40 g) was mixed with dry benzene (250 m
j7). While stirring, a butyllithium-tetrahydrofuran solution (1 to 2 equivalents) was slowly added dropwise. After continuing stirring for 2 hours, the solvent was distilled off under reduced pressure and concentrated. After standing for 2 to 3 hours, the white precipitate is filtered and dried. Yield was 37g.

<Synthesis Example 3> Synthesis of 1.1,3.3-tetrakis(p-diethylaminophenyl)propenium, diphenyldibutylborate 1, 1.3.3-tetrakis(p-diethylaminophenyl)propenium,
- diethylaminophenyl) propenium, 2 parts of iodide are partially dissolved in 40 parts of methanol, and an equimolar amount of sodium diphenyldibutylborate is added thereto,
The mixture was stirred for 1 hour while heating from 45°C to 50°C while shielding from light. Thereafter, the mixture was allowed to cool, and a blue-purple precipitate was collected by filtration, washed with methanol and then with water, and dried under reduced pressure.

The amount obtained was 0.9 parts.

<Synthesis Example 4>1.1'-diethyl-3,3,3'
, Synthesis of 3'-tetramethyl-2,2'-indotricarbocyanine trianebutylborate 1 part of NK-1414 (Japanese photosensitive dye type) was mixed with 1 part of ethanol.
0 parts, and an equimolar amount of lithium trianisbutylborate was added thereto, and the mixture was stirred for 30 minutes while heating from 45°C to 50°C while shielding from light. It was then cooled under a water bath.

The green precipitate was collected by filtration, washed with methanol and then water, and dried under reduced pressure. The amount obtained was 0.5 part.

Example 1゜ A photosensitive solution having the following composition was prepared in a dark room.

Glycidyl n-butyl ether 3 parts diglycidyl hexamethylene diether 1 part! , 1.3.3-
Tetrakis(p-diethylaminophenyl)propenium diphenyl dibutylborate 0.3 parts Kayaset Red (Nikkayaku) 0.5 parts Polymethyl methacrylate 2 parts Dichloroethane
35 parts The above photosensitive solution was coated on an anodized aluminum plate to a dry film thickness of 2 μm, and a PVA layer was further provided as an oxygen barrier layer on top of this to a dry film thickness of 2 μm. A sexual medium was prepared.

In the photosensitivity test, the photosensitive medium was exposed to light for 50 seconds through a mask using a 370 W xenon lamp with a sharp cut filter 0-54 (manufactured by Optline ■). After exposure, the PVA layer was washed with water and etched in ethanol for 1 minute. As a result, only the unexposed areas were removed, and the exposed areas remained in the form of an image on the substrate.

Example 2 A photosensitive medium similar to Example 1 was prepared except that the PVA layer (oxygen barrier layer) was not provided.
As a result of conducting the same photosensitivity test as above, a polymerized image was formed with an exposure time of 80 seconds.

Example 3゜Example 1-1. 1.3.3-Tetrakis(p-diethylaminophenyl)propenium diphenyldibutylborate 0.3 part was dissolved in 1,1'-diethyl-3°3,3
', 3'-Tetramethyl-2,2'-indotricarbocyaninetrianisbutylborate was used in the same manner as in Example 1, except that 0.4 part of the photosensitive medium was prepared, and the same photosensitive medium as in Example 1 was prepared. As a result of a property test, a polymerized image was formed with an exposure time of 50 seconds.

Example 4 A photosensitive layer having the following composition was formed on an anodized aluminum plate to have a dry film thickness of 2 μm.

Bisphenol A epoxy resin 2 parts glycidyl acrylic acid 3 parts polymethyl methacrylate 3 parts 3.3'-jethoxyethyl-
0.4 parts of 2,2' thiadicarbocyanine trifluoromethyl trifluoroborate Kayaset Red (manufactured by Nikkayaku Co., Ltd.) 0.4 parts Furthermore, a PVA layer with a dry film thickness of 2 μm was added thereon as an oxygen barrier layer. A photosensitive medium was prepared in which the following conditions were established. A photosensitivity test was conducted in the same manner as in Example 1, and a polymerized image was obtained with an exposure time of 50 seconds.

Example 5 The photosensitive medium prepared in Example 4 was irradiated with a single beam line of a 150 mW semiconductor laser having a spot diameter of 100 μm. As a result, a polymerized image was obtained with an irradiation time of 90 seconds or more.

Example 6 A photosensitive medium was prepared in the same manner as in Example 4, except that 2 parts of bisphenol A epoxy resin and 3 parts of glycidyl acrylic acid in Example 4 were replaced with 6 parts of di(vinyloxyethoxy)bisphenol A. As a result of conducting the same photosensitivity test as in Example 1, a polymerized image was obtained with an exposure time of 60 seconds.

Example 7 A photosensitive medium was prepared and carried out in the same manner as in Example 4, except that 2 parts of bisphenol A epoxy resin and 3 parts of glycidyl acrylic acid in Example 4 were replaced with 5 parts of di(vinyloxypropoxy)benzene. As a result of conducting the same photosensitivity test as in Example 1,
A polymerized image was obtained with an exposure time of 50 seconds.

Example 8 In preparing the photosensitive medium of Example 4, the photosensitive layer and PV
Two types of photosensitive media were prepared in which the drying conditions during coating of layer A were (a) 75°C for 15 minutes (b) 40°C for 20 minutes, and the amount of oxygen mixed during coating was different.

As a result of conducting the same photosensitivity test as in Example 1 on the above two types of photosensitive media, there was no difference in the exposure time required to form a polymerized image.

Comparative example! .

A photosensitive solution having the following composition was prepared in a dark room.

Pentaerythritol triacrylate 4 parts 1.1'
-diethyl-3,3,3',3'-tetramethyl-2,2'-indotricarbocyanine tricaya set blue (manufactured by Nikkayaku)
0.4 part polymethyl methacrylate
2 parts dichloroethane 35 parts A photosensitive medium was prepared by coating the above photosensitive solution on an anodized aluminum plate to a dry film thickness of 2 μm, and the same photosensitivity test as in Example 1 was conducted. It did not cure after 3 minutes of exposure.

Comparative Example 2 In producing a photosensitive medium in which a PVA layer was further provided on the photosensitive medium of Example 1, the drying conditions during coating of the photosensitive layer and PVA layer were (a) 70°C for 5 minutes (b) The coating was carried out at 40° C. for 20 minutes, and two types of photosensitive media were prepared with different amounts of oxygen mixed in each layer during coating.

As a result of conducting the same photosensitivity test as in Example 1 on the above two types of photosensitive media, in case (a), a polymerized image was obtained with exposure for 50 seconds, but in case (b), a polymerized image was obtained with exposure for 50 seconds. It was not possible to obtain a polymerized image with sufficient intensity through exposure.

Claims (2)

[Claims] (1) A photocurable composition characterized by using a cationic dye having a boron anion as a photopolymerization initiator, and containing the photopolymerization initiator and a polymerizable compound capable of cationic polymerization. (2) The photocurable composition according to claim 1, wherein the cationic dye having a boron anion is represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, in the above formula (I), Dye^■ indicates a cationic dye moiety, and R_1, R_2, R_3 and R_4 are the same or different, and are halogen atoms, alkyl groups. , an aryl group, an aralkyl group, an aryloxy group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a heterocyclic group. Further, R_1 and R_2 or R_2 and R_3 may be combined to form a ring compound.