JPS5928206B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable composition, and particularly to the composition of a photopolymerization initiator in a photopolymerization initiator composition in a photopolymerizable composition.

Conventionally, unsaturated compounds that can be cured by radiation are used as components of compositions such as paints, printing inks, and adhesives.
When such a composition is exposed to electromagnetic waves such as visible light, ultraviolet rays, and X-rays, or particle beams such as electron beams, neutron beams, and alpha rays, the above-mentioned compounds in the composition are polymerized and hardened, and the above-described effects are further activated to initiate polymerization. It is widely known that the rate of polymerization increases significantly when polymerization is carried out in the presence of an agent composition.

These techniques are described in, for example, U.S. Pat. No. 35,512.
No. 35, No. 3551246, No. 3551311 and No. 3558387, Perky National Patent No. 808
No. 179 and Japanese Unexamined Patent Publication No. 110781/1987, the products obtained by this technique have features such as excellent flexibility, chemical resistance, gloss, adhesiveness, and color. However, on the other hand, the curing sensitivity of the composition is low, so it takes a long time for image exposure during image formation, so in the case of detailed images, it is difficult to reproduce images of good quality even if there is slight vibration in the operation. Moreover, since the amount of energy emitted by the exposure light source or particle beam source must be increased, it is necessary to consider the accompanying large amount of heat dissipation, and furthermore, the deformation and deterioration of the composition film due to heat must be considered. There were problems such as the possibility that The present inventors have conducted extensive research to solve the above-mentioned problems by increasing the sensitivity of photopolymerizable compositions. The inventors have discovered that the photopolymerization rate of polymerizable compounds having a bond can be significantly increased, leading to the present invention. That is, the present invention uses a compound having an ethylenically unsaturated bond as a polymerizable component, and further uses a compound having an aromatic 6-membered heterocycle in which two of the atoms forming the ring structure are nitrogen atoms as a photopolymerization initiator; At least one compound (component 4) of a compound having a fused heterocycle having a structure in which four or less benzene rings are fused to a six-membered heterocycle in which one or two of the atoms constituting the ring are nitrogen atoms; This is a photopolymerizable composition in which a composition comprising a compound containing an element belonging to Group V of the Periodic Table (component 5) and a halogen-containing organic compound (component 5) which is optionally used. The present invention will be explained in detail below. The compound having an ethylenically unsaturated bond in the composition of the present invention is defined as having at least one ethylenically unsaturated bond in its chemical structure.
Compounds with ethylenically unsaturated bonds in chemical forms such as monomers, prepolymers, i.e. dimers, trimers and other caligomers, mixtures thereof and copolymers thereof. It is.

Examples thereof include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric polyol compounds, and the like. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid,
There is maleic acid.

Salts of unsaturated carboxylic acids include the sodium and potassium salts of the aforementioned acids. Examples of the aliphatic polyol compounds mentioned above include ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, neopentyl glycol, 1,10-decanediol, trimethylolethane, trimethylolpropane, and 1,2-butanediol. , 1,3-butanediol, propylene glycol, pentaerythritol,
dipentaerythritol, tripentaerythritol,
Other multimeric pentaerythritol, sorbitol, d-
These include mannitol and dihydroxymaleic acid.

Specific examples of esters of aliphatic polyhydric polyol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol triacrylate, and diacrylic acid 1.
3-butanediol ester, tetramethylene glycol diacrylate ester, propylene glycol diacrylate ester, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate ester ,
diacrylic acid tetraethylene glycol ester, diacrylic acid pentaerythritol ester, triacrylic acid pentaerythritol ester, tetraacrylic acid pentaerythritol ester, diacrylic acid dipentaerythritol ester, triacrylic acid dipentaerythritol ester, tetraacrylic acid dipentaerythritol ester, Dipentaerythritol pentaacrylate ester, dipentaerythritol hexaacrylate ester, tripentaerythritol octaacrylate ester, dipentaerythritol tetraacrylate ester, dipentaerythritol pentaacrylate ester, dipentaerythritol hexaacrylate ester, octaacrylate Examples include acid tripentaerythritol ester, triacrylic acid sorbitol ester, tetraacrylic acid sorbitol ester, pentaacrylic acid sorbitol ester, hexaacrylic acid sorbitol ester, and polyester acrylate oligomer.
As the methacrylic acid ester, dimethacrylic acid tetramethylene glycol ester, dimethacrylic acid triethylene glycol ester, dimethacrylic acid pentaerythritol ester, trimethacrylic acid pentaerythritol ester, dimethacrylic acid dipentaerythritol ester, dimethacrylic acid pentaerythritol ester, Pentaerythritol trimethacrylate ester, dipentaerythritol dimethacrylate ester, dipentaerythritol tetramethacrylate ester, tripentaerythritol octamethacrylate ester, ethylene glycol dimethacrylate ester, dimethacrylic acid 1 and 3-butanediol ester, Examples include tetramethylene glycol methacrylate ester and sorbitol tetramethacrylate ester. Itaconic acid esters include diitaconic acid ethylene glycol ester, diitaconic acid propylene glycol ester, diitaconic acid 1,3-butanediol ester, diitaconic acid 1,4
-butanediol ester, diitaconate tetramethylene glycol ester, diitaconate pentaerythritol ester, triitaconate dipentaerythritol ester, pentitaconate dipentaerythritol ester, hexitaconate dipentaerythritol ester, tetraitaconate sorbitol ester, and the like. Examples of crotonate esters include cyclotonate ethylene glycol ester, cyclotonate propylene glycol ester, cyclotonate tetramethylene glycol ester, cyclotonate pentaerythritol ester, and tetracrotonate sorbitol ester. Isocrotonic acid esters include diisocrotonic acid ethylene glycol ester, diisocrotonic acid pentaerythritol ester, tetraisocrotonic acid sorbitol ester, and the like. Examples of maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Other examples include modified diacrylic acid tetramethylene glycol ester, modified triacrylic acid trimethylolpropane ester, modified triacrylic acid pentaerythritol ester, and methacrylated epoxy resin. Furthermore, mixtures of the aforementioned esters may also be mentioned. Next, regarding the photopolymerization initiator, which is the most characteristic component in the photopolymerizable composition of the present invention, at least one compound selected from each of Component 5, Component 5, and Component D is used as the photopolymerization initiator. It is also a composition containing.

Component 5 in such a photopolymerization initiator is a compound having an aromatic 6-membered heterocycle in which two of the atomic groups constituting the ring are nitrogen atoms, and one to two of the atomic groups constituting the ring. At least one compound has a fused heterocycle in which not more than 4 benzene rings are fused to a 6-membered heterocycle, each of which is a nitrogen atom. Aromaticity 6 above
Specific examples of compounds having a membered heterocycle include pyridazine, pyrimidine, and pyrazine, and compounds in which the basic structure is substituted with an amino group, a lower alkylamino group having 1 to 4 carbon atoms, or a halogen atom, such as 3-chloro Pyridazine, 3-aminopyridazine, 2-aminopyrimidine, 4-aminopyrimidine, 4,5-diaminopyrimidine, 2,4-bis(dimethylamino)pyrimidine, 2-
Examples include chloropyrimidine, 2-aminopyramidine, and 2-chloropyramidine.

In addition, examples of compounds having the above-mentioned fused heterocycle include quinoline, naphtho[1.2-g]quinoline, dibenzo[f-h]
quinoline, isoquinoline, benzo[h]isoquinoline,
naphtho [2,3-g] isoquinoline, dibenzo [f-h
]isoquinoline, naphtho[2.1-h]isoquinoline,
Acridine, benzo[a]acridine, benzo[b]acridine, benzo[c]acridine, phenanthridine, benzo[a]phenanthridine, benzo[j]phenanthridine, cinnoline, naphtho[2,3-g] Cinnoline, dibenzo[f/h]cinnoline, benzo[c]cinnoline, benzo[g]cinnoline, benzo[h]cinnoline, quinazoline, benzo[f]quinazoline, benzo[g]quinazoline, benzo[h]quinazoline, naphtho[
1,2-h] quinazoline, naphtho[2,31f]quinazoline, quinoxaline, benzo[f]quinoxaline, benzo[g]quinoxaline, naphtho[2,3-g]quinoxaline, dibenzo[f/h]quinoxaline, phenazine,
Benzo[a]phenazine, benzo[b]phenazine, dibenzo[ac]phenazine, tribenzo[a-c-h
] Phenazine, phthalazine, benzo[f]phthalazine,
Benzo[g]phthalazine, dibenzo[c-f]phthalazine, naphtho[2,3-f]phthalazine, naphtho[2,3
-g] phthalazine, etc., and this basic structure is substituted with an amino group, a lower alkylamino group having 1 to 4 carbon atoms, or a halogen atom, such as 9-chloroacridine,
3,6-diaminoacridine, 3,6-bis(dimethylamino)acridine, 1-aminophenazine, 2,3-
Diaminophenazine, 2-(dimethylamino)phenazine, 6-aminophenanthridine, 3-aminocinnoline, 2-aminoquinazoline, 2,4-diaminoquinazoline, 4-(dimethylamino)quinazoline, 2-(dimethyl amino)quinoxaline, 1-aminobenzo[c]cinnoline, 2-(diethylamino)benzo[c]cinnoline, 4-(dimethylamino)benzo[e]cinnoline,
Examples include 3,8-bis(dimethylamino)benzo[c]cinnoline. One or a mixture of two or more of these can be used. Preferred compounds among these are pyridazine, 3,6-bis(dimethylamino)acridine, 9-chloroacridine, quinoxaline,
They are cinnoline, benzo[c]cinnoline, phenazine, and dibenzo[8.c]phenazine. Particularly preferred compounds are 3,6-bis(dimethylamino)acridine, 9-
These are chloroacridine and quinoxaline. Next, component 5, which together with component 5 constitutes a photopolymerization initiator, has the general formula R1-Q-
Bi (wherein Q is a nitrogen or phosphorus atom, R.R' and Bi each represent the same or different alkyl group, aryl group, aralkyl group or hydroxyalkyl group).

), and specific examples thereof include tertiary amines such as triethylamine and tri-n-decylamine, hydroxyalkylamines such as diethanolamine and triethanolamine, triethylenetetramine, and hexylamine. Polyamino compounds such as methylenetetramine and hexamethylene diamine 1, N
- At least one compound selected from aromatic amines such as benzyl-N-ethylaniline and N-N-dimethylaniline, and phosphorus compounds such as triphenylphosphine and trimethylphosphine. Or there are two mixtures. Examples of (c) include halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, and halogenated aromatic hydrocarbons, and halogens include chlorine,
Bromine, fluorine or iodine, specific examples of which include polyhalogenated hydrocarbons such as polychlorinated triphenyl and polyfluorinated phenyl, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene,
Chlorinated rubber, copolymers of vinyl chloride and vinyl isobutyl ether, chlorinated aliphatic waxes, mono- and polychlorinated benzenes, mono- and poly-brominated benzenes, mono- and polychlorinated xylenes, mono- and polybrominated xylene, dichloromaleic anhydride, 1-chloro-2-
Methylnaphthalene, 2,4-dimethylbenzenesulfochloride, 1-bromo-3-(m-J-Gnoxy) 3benzene, methyl 2-bromoethyl ether, chloreneditsic acid anhydride and mono- and dialkyl esters of chloreneditsic acid ( Alkyl groups include methyl, ethyl and propyl groups), chloromethylbenzene, chloromethylnaphthalene, 4β-promoethylphenanthrene, short methylanthracene, hexachlorocyclobenzene, hexachlorobenzene, hexachloro-p
- at least one compound or mixture selected from xylene, etc.; The proportion of the component weight of the photopolymerization initiator composition is such that 5 is in the range of 3% to 90%, 5 is in the range of 3% to 90%, and 5+5 is in the range of more than 66%, and 5 is the balance. , preferably 5 is 10% to 80
%, where 5 is from 10% to 70% and 5+5 is over 50%, D is the remainder.

The weight ratio of the photoinitiator composition to the aforementioned monomers can range from about 1:1 to about 1,000:1;
Preferably, a range of about 10:1 to about 100:1 is used.

The photocurable polymerizable composition of the present invention containing the above-mentioned monomer and photopolymerization initiator composition further contains a known thermal polymerization inhibitor, a plasticizer, a colorant, a wetting agent for the colorant, and a surface smoothing agent. Additives such as the following can be included as necessary.

Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or ajnol-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2.6 Examples include -di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, and organic acid copper (such as copper acetate).

These thermal polymerization inhibitors are preferably contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the above-mentioned monomers. A thermal polymerization inhibitor can be included for the purpose of improving the stability of the composition of the present invention over time before exposure. Examples of coloring agents include pigments such as titanium oxide, carbon black, iron oxide, phthalocyanine pigments, and azo pigments; methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, and azo dyes;
Although there are dyes such as anthraquinone dyes, it is preferable that the coloring agent used does not absorb light at the absorption wavelength of the photopolymerization initiator composition.

Such a coloring agent has a total amount of binder and monomer of 100
0.1 to 30 parts by weight for pigments, 0.01 to 10 parts by weight for dyes, preferably 0.1 to 3 parts by weight
It is preferable to contain it in a range of parts by weight. Wetting agents for colorants include dichloromethyl stearate and other chlorinated fatty acids;
It can be used in a range of 0.05 parts by weight to 0.5 parts by weight. However, if a plasticizer is included in the photopolymerizable composition, a colorant wetting agent is not necessary. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, synchhexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and dimethyl glycol. Glycol esters such as phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, triethylene glycol dicaprylate, phosphate esters such as tricresyl phosphate, triphenyl phosphate , diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, diothyl azelate, dibutyl maleate and other aliphatic dibasic acid esters, triethyl citrate, glycerin triacetyl ester, and butyl laurate. Surface smoothing agents include lanolin, paraffin wax and natural wax. The above-mentioned various modifiers, which can be included in the composition of the present invention if necessary, can be used in an amount of up to 3% by weight, preferably up to 1% by weight, based on the total weight of the composition.

The photopolymerizable composition of the present invention is dissolved in a solvent to form a coating solution, which is applied to glass, wood, paper, cloth, metal plates and foils, screen cloth, plastic films (e.g. polyethylene terephthalate, nylon, polyethylene, etc.). It is generally applied to a support such as polypropylene, cellulose triacetate) and dried to form a film.

Examples of the solvent for the coating solution include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Ketones such as diisobutyl ketone, esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc., toluene, xylene, benzene, ethylbenzene, etc. Aromatic hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroformate, 1,1,1-trichloroethane, monochlorobenzene, halogenated hydrocarbons such as chlornaphthalene, etc.
Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate,
Examples include dimethylformamide and dimethyl sulfoxide.

゛On the surface of the support, that is, under the photopolymerizable composition, other coating layers, antihalation layers, ultraviolet absorbing layers, and visible light absorbing layers may be provided as necessary to facilitate bonding. good. Furthermore, the composition of the present invention is disclosed in US Pat. No. 3,060,026 in order to prevent a decrease in sensitivity due to oxygen.
Exposure is carried out using a vacuum printing frame as described in the specification of the above patent, or a removable transparent cover is provided, or the photosensitive layer is exposed as described in Japanese Patent Publication No. 40-17828. It is desirable to provide a coating layer with low oxygen permeability thereon.

Factors that determine the rate at which the photocurable composition of the present invention photopolymerizes, cures, and dries include the properties of the substrate, specific components in the composition, and the total photopolymerizable composition of the photoinitiator composition. , the thickness of the layer of the photopolymerizable composition, the nature of the light source (characteristics of the irradiation spectrum), the intensity and distance from the photopolymerizable composition, the presence or absence of oxygen, and the ambient temperature. The light irradiation may be performed using any one of various methods or a combination thereof. For example, the composition may be exposed to actinic radiation from any source and type of light so long as it provides an effective exposure dose. This is because the photopolymerizable compositions of the present invention generally have wavelengths from about 180 nm to about 4 nm.
This is because it exhibits maximum sensitivity in the ultraviolet and visible light regions up to 50 nm. However, the composition of the present invention is also sensitive to short-wavelength electromagnetic waves in the range of vacuum ultraviolet rays, can be used. Examples of suitable light sources in the ultraviolet and visible range include carbon arc lamps, mercury vapor lamps, xenon lamps, fluorescent lamps, argon glow discharge tubes, photographic flat lamps, and Van de Graaf accelerators. The light exposure time must be sufficient to provide an effective amount of light. Light irradiation may be carried out at any convenient temperature, but for practical reasons it is optimally carried out at room temperature, ie in the range from 10°C to 30°C. The composition of the present invention cured by light is dry and elastic, exhibits abrasion resistance and chemical resistance, and also exhibits excellent ink receptivity, hydrophilic-hydrophobic balance, stain release properties, initial roll-up, etc. It is particularly suitable for use in pre-photosensitized printing plate materials for lithographic printing and photoresistors. This composition can also be used as a printing ink; as an adhesive for metal foils, films, papers, textiles, etc.; for metals, plastics, paper,
It is useful as a photocurable paint for use on wood, metal boxes, textiles, glass, cardboard, box-making cardboard, etc., as well as signs for roads, parking lots, airports, etc. When the compositions of the present invention are used, for example, as vehicles for printing inks, they can be colored with known amounts of dyes and simultaneously coated with various known organic pigments, such as molybdate orange, titanium white, chrome yellow, phthalocyanine blue, and carbon black. Can be colored.

The usable amount of vehicle is approximately 20% of the total weight of the composition.
Range from 99.9% to 99.9%, colorant weight approximately 0.1%
It can be used in a range from 80% to 80%. Printing material quantities also include paper, clay-coated paper and boxboard. The compositions of the invention are further suitable for the treatment of natural and synthetic textiles, for example as vehicles for textile printing inks, or to provide waterproof, oil, stain, crease, etc. It can be used in vehicles for special treatments.

When using the composition of the invention as an adhesive, at least one of the substrates to be adhered must be translucent to ultraviolet or visible light.

Typical examples of laminates obtained by adhering substrates using the composition of the present invention include polymer-coated cellophane,
Examples include cellophane coated with polypropylene, metals such as aluminum or copper coated with polyethylene terephthalate film, and aluminum coated with polypropylene. The photocurable composition of the present invention can be used as a coating for coating or printing on metal, glass and plastic surfaces by roller and spray methods.

Also glass, polyester and vinyl polymer films, polymer-coated cellophane, treated and untreated polyethylene used in disposable pots and bottles, for example;
Colored coating systems may be used for treated and untreated polypropylene, etc. Examples of metals that may be painted include:
Also includes tinplate with or without sizing.
A photopolymerizable photosensitive imaging material prepared from the photocurable composition of the present invention has a layer comprising the composition of the present invention as a photosensitive element on the surface of a sheet-like or plate-like support. It is the material.

Examples of supports include plates or thin foils of iron, stainless steel alloys, aluminum, copper, zinc, bronze, chromium, silver, gold, platinum, etc., plates of glass and ceramics, cellulose nitrate, cellulose acetate, cellulose acetate butyl, etc. rate, cellulose acetate propionate, polystyrene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride vinylidene chloride copolymer, vinyl chloride monovinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer, polyethylene terephthalate, polycarbonate, Polyethylene, polypropylene, 6-nylon, 6.6-
Examples include films such as nylon and 6/10-nylon, paper, and laminates thereof. These supports are selected from transparent or opaque depending on the purpose of the photosensitive image forming material. When it is transparent, it is not only colorless and transparent.
J. As described in SMPTEL Vol. 67, p. 296 (1958), dyes or pigments may be added to make the material colored and transparent. In the case of opaque supports, in addition to those that are inherently opaque such as paper and metal, there are also those that are transparent materials with pigments such as dyes and titanium oxide added, and those that are surface-treated by the method described in Japanese Patent Publication No. 19068/1983. It is also possible to use paper, plastic film, etc., which have been made completely light-shielding by adding plastic film, carbon black, etc. It is also possible to use a support whose surface has been provided with fine depressions by graining, electrolytic etching, anodic oxidation, chemical etching, etc., and a support whose surface has been pretreated by corona discharge, ultraviolet irradiation, flame treatment, etc. . Furthermore, it is also possible to use a plastic support whose strength is increased by incorporating reinforcing agents such as glass fibers, carbon fibers, boron fibers, various metal fibers, and metal whiskers. One form of a photosensitive image forming material using the composition of the present invention is one in which a layer of the composition of the present invention is provided on the surface of a support, and a transparent plastic film is further provided on the layer. .

Materials with this structure can be used by peeling off the transparent plastic film just before the image exposure described below, or by passing the film through the transparent plastic film with the transparent plastic film still present, or when the support is transparent. imagewise is exposed through the support, and then the transparent plastic film is peeled off to leave the layer of the exposed and hardened portion on the support;
Leaving the unexposed and uncured layer on the transparent plastic film (or leaving the exposed and hardened layer on the transparent plastic film and leaving the unexposed and uncured layer on the transparent plastic film) It can be particularly advantageously used as a so-called peel-and-develop type material, in which a layer of 100% is left on the support. A photosensitive imaging material using the composition of the present invention is prepared by using a specific portion of the layer of the photopolymerizable composition until the addition polymerization reaction in the irradiated portion reaches a desired thickness and is completed. Exposure to light completes the image exposure.

The unexposed parts of the composition layer are then removed, for example by using a solvent that dissolves only the monomer or prepolymer without dissolving the polymer, or by so-called peel development. When used in photosensitive image reproduction materials, the optimal solvent removal thickness of the photocurable composition is:
It ranges from 20 μm to 50 μm. The flexibility decreases as the layer thickness increases, and the abrasion resistance decreases as the layer thickness decreases. When used as printing inks, coating compositions and adhesives, the compositions of the invention can be used without volatile solvents.

They have several advantages over known oleoresin-based and solvent-based inks or coatings. The present invention will be described below in detail and concretely based on Examples and Comparative Examples.

The samples in each example were prepared according to the following methods and operations. (1) Preparation of sample Polymerizable compound 1, photopolymerization initiator 2, and binder were used as a solvent, and 450 parts (by weight) of dichloroethane were used.

same as below. ) in a container and stirred for 3 hours to dissolve, then apply the resulting solution to a spinner (rotary coating machine).
This was applied on an aluminum plate at a temperature of 80℃ for 10 minutes.
A photosensitive layer was formed by drying for a minute. The thickness of the photosensitive layer after drying was about 10 μm. (2) Measurement of sensitivity of sample An optical wedge (the number of optical density steps is 0 to 15 steps) is placed on the photosensitive layer of the sample.

) and from the light source (mercury lamp, output 2KW) 50? After exposure for 30 seconds at a distance of
-Developed by treatment with trichloroethane for 30 seconds. The highest number of optical wedges corresponding to the image that appears is expressed as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity. Examples and Comparative Examples were carried out according to the above-mentioned methods and operations, and the compositions of the photosensitive layers were as shown in the table below.

The sensitivity of the sample was also as indicated. From the results shown in the table above, it can be seen that when the essential components of the present invention are used individually as in the case of the comparative example, no sensitivity is shown at all, but in the case of each example using the required combination of components. Each showed sensitivity, and particularly when triethanolamine was used as components 2 to 6, as seen in Examples 1, 7, 13, and 16, there were many cases in which the sensitivity was extremely high.

Claims (1)

[Claims] 1 (1) A polymerizable compound having an ethylenically unsaturated bond and (2) (a) 2 of the atomic groups constituting the ring
A compound having an aromatic 6-membered heterocycle in which each of the atoms is a nitrogen atom, and a 6-membered heterocycle in which 1 or 2 of the atoms constituting the ring are nitrogen atoms, and 4 or less benzene rings are fused to the 6-membered heterocycle. A photopolymerization initiator consisting of at least one compound selected from the group consisting of compounds having a fused heterocycle structure, (b) a compound containing an element belonging to Group V of the periodic table, and (c) a halogen-containing organic compound. A photopolymerizable composition comprising: