JPS62143043A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition showing spectral sensitivity over the ultraviolet and visible light regions by using a photopolymn. initiator consisting of a xanthene or thioxanthene dye, a sensitization accelerator and an org. peroxide. CONSTITUTION:When an addition-polymerizable compound having an ethylenic unsatd. double bond is blended with a photopolymn. initiator to obtain a photopolymerizable composition, the photopolymn. initiator is composed of a xanthene or thioxanthene dye (a) represented by the formula, N-phenylglycine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine or a mixture of isobenzyl p- dimethylaminobenzoate with 2,4-diisopropylthioxanthone as a sensitization accelerator (b), and an org. peroxide (c). The resulting composition shows superior sensitivity over the ultraviolet and visible light regions and can form an image with low energy laser because of the high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photopolymerizable composition that can be cured using a general-purpose light source including ultraviolet rays and visible rays.

[Prior Art] To reproduce images by photographic methods, photosensitive compositions are used that contain diazonium salts, diazides, or quinone diazides as photosensitive components and compounds with photocrosslinking ability as curing components. There is. All of the above-mentioned photosensitive components have a problem in that they are sensitive to ultraviolet rays but are hardly sensitive to visible light. It has long been desired to form images using visible light instead of ultraviolet light, but this has been difficult to achieve.

In recent years, with advances in scanning exposure technology using laser light sources, photosensitive materials that are highly sensitive to visible laser light, such as argon ray, have become less expensive than laser light sources that use ultraviolet light, due to equipment and energy costs. development was desired.

[Problems to be Solved by the Invention] Photopolymerizable compositions that are sensitive to visible light (wavelengths of 400 nm to 700 nm) are disclosed, for example, in JP-A-57-1.
Pigments and photosensitizers as shown in Japanese Patent Application No. 14139 and Japanese Patent Application No. 170599/1988 are known.

In these cases, the sensitivity is not necessarily sufficient, and even if recording by laser beam scanning exposure is possible, it requires a fairly high-angle laser, which is not economical. The inventors have found that the material has extremely high photosensitivity and is highly stable over time.
Furthermore, the present invention was completed by studying relatively inexpensive photopolymerizable compositions.

[Means for solving the problem] A composition containing a certain xanthene or thioxanthene dye, a photosensitizer, and an organic peroxide is blended with an addition polymerizable compound having an ethylenically unsaturated double bond. It has been found that the photocured product exhibits excellent photosensitivity in the ultraviolet to visible light range, and that the photocured product has excellent physical properties for the uses shown in the section on industrial applications.

The gist of the present invention is to provide a photopolymerizable composition comprising an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the photopolymerization initiator has the following formula: (a) Formula: [Formula where A is an oxygen or sulfur atom, X is a hydrogen atom or a halogen atom, and Y is a carbon or nitrogen atom (however, if Y is a carbon atom, there is a ) is a double bond, and if Y is a nitrogen atom, the bond with the adjacent carbon atom is a single bond.), Z is the oxygen atom (in this case, the bond with the adjacent carbon atom is a double bond). ), lower alkoxy group or lower alkanoyloxy group, R' is a lower alkyl group, hydroxy lower alkyl group, lower alkoxy lower alkyl group, di-lower alkylamino lower alkyl group or aryl group, R2 is a lower alkoxy group or It is a di-lower alkylamino group. In addition, Z and R1 together are -Z-R'
It is also sometimes expressed as −. xanthene or thioxanthene dye represented by (b) N-phenylglycine, 2,4.6-)lis(trichloromethyl)-1,3,5-triazine, or p-dimethylaminobenzoic acid isopentyl ester and 2,4-noisopropylthioxanthone.

(c) Provide a photopolymerizable composition characterized in that it contains a peroxide.

The photopolymerizable composition contains as essential components an addition polymerizable compound having an ethylenically unsaturated double bond (hereinafter referred to as double bond-containing compound J) and a photopolymerization initiator.

Double bond-containing compounds are monomers that have ethylenically unsaturated double bonds that undergo addition polymerization and cure under the action of a photopolymerization initiator, resulting in substantial insolubilization, or monomers containing ethylene in the side chain or main chain. It is a polymer having a sexually unsaturated double bond, and generally has a boiling point of 100°C or higher. Specific examples include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroquine compounds, unsaturated carboxylic acids and polyhydric carboxylic acids, and aliphatic polyhydroxy compounds. Examples include esters obtained by esterification reaction with polyhydric hydroxy compounds such as polyhydroxy compounds and aromatic polyhydroxy compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid. Aromatic polyhydroxy compounds include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, and 1,2-butanediol, trimethylolethane, trimethylolpropane, and glycerol. Examples include trihydric alcohols such as pentaerythritol, alcohols of tetrahydric or higher valence such as tripentaerythritol, and polyhydric hydroxycarboxylic acids such as dihydroxymaleic acid. Examples of aromatic polyhydroxo compounds include hydroquinone, resorcinol, catechol, and pyrogallol. Examples of polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, maleic acid, fumaric acid, malonic acid, geltaric acid, adipic acid, and sebacic acid. ,
Examples include tetrahydrophthalic acid.

Specific examples of esters of aliphatic polyhydroquine compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritolone acrylate. , acrylic acid esters such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, noventaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, tripentaerythritol octaacrylate, glycerol diacrylate, triethylene glycol diacrylate, Tetramethylene glycol diacrylate, trimethylolethane triacrylate, trimethylolethane trimethafrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetra Methacrylic acid esters such as methacrylate, tripentaerythritol octamethacrylate, ethylene glycol dimethacrylate, 1,2-butanediol dimethacrylate, trubitol tetramethacrylate, ethylene glycol shitaconate, propylene glycol shitaconate, l,
Itaconic acid esters such as 2-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol triitaconate, crotonic acid esters such as ethylene glycol dicrotonate, diethylene glycol dicrotonate, pentaerythritol tetracrotonate, ethylene glycol Maleic acid esters include dimaleate, triethylene glycol dimaleate, and pentaerythritol dimaleate. Examples of the ester of aromatic polyhydroxy compound and unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The esters obtained by the esterification reaction of unsaturated carboxylic acids with polyhydric carboxylic acids and polyhydric hydroxy compounds are not necessarily single, but typical examples are shown below (however, Zo is an acryloyl group or a methacryloyl group). group): Z' 0Cdl--00C-C6H4-Coo-CJ
40-Z'Z'-(QC, lL shore 00cm (CH2 shore C
oo(C21L■T2/2'-ωC21L square 00C-C
JI=Ct(-Coo(CJ40 juice 2'Z~QC,H,
-00C-C,H4-Coo-C,H,-0Hz'
0CJ4-00C-(CHt)4-Coo-CHtZ'
-QC2H4-00C-(CHff1), -Co
o -CH2' 0C3l14-00C-(CHz)
Examples of double bond-containing compounds used in the invention include acrylamide, acrylamides such as ethylenebisacrylamide and hexamethylenebisacrylamide, methacrylamides such as ethylenebismethacrylamide and hexamethylenebisacrylamide, and phthalates. Examples thereof include allyl esters such as noallyl acid, allyl malonate, diallyl fumarate, and triallylysone annurate, and vinyl-containing compounds such as divinyl adipate, dihinyl phthalate 1-, and ethylene glycol divinyl ether.

Examples of polymers having ethylenically unsaturated bonds in the main chain include polyesters obtained by the polycondensation reaction of unsaturated dicarboxylic acids and dihydroxy compounds, and polyamides obtained by the polycondensation reaction of unsaturated dicarboxylic acids and diamines. etc. Examples of unsaturated dihydric carboxylic acids include maleic acid and fumaric acid. Polymers having ethylenically unsaturated bonds in their side chains are divalent carboxylic acids having unsaturated bonds in their side chains, such as itaconic acid, α-methylitaconic acid, γ-methylitaconic acid, propylidenesuccinic acid, α-edithic acid, etc. Examples include polyester obtained by polycondensation reaction of lydenglutaric acid, ethylidenemalonic acid, propylidenemalonic acid, etc. with a dihydroquine compound, and polyamide obtained by polycondensation reaction with diamine. Polymers obtained by a polymer reaction between a polymer having a reactive functional group such as a hydroquine group or a halogenated methyl group in the side chain and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or crotonic acid are also available. It can be suitably used. Examples of polymers having functional groups having reactive activity include polyvinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, copolymers of vinyl alcohol and acrylonitrile, styrene, vinyl chloride, vinylidene chloride, etc., polyepichlorohydrin, 2-
hydroxyethyl methacrylate and acrylonitrile,
Copolymers with methyl methacrylate, butyl methacrylate, styrene, vinylidene chloride, vinyl acetate, etc., polyethers obtained by reaction of epichlorohydrin and 2,2-bis(4-hydroxyphenyl)-propane,
Examples include poly(4-hydroxystyrene) and poly(N-medyloacrylamide).

Among the double bond-containing compounds described above, monomers of acrylic esters or methacrylic esters can be particularly preferably used.

As the photopolymerization initiator, xanthene or thioxanthene compound (I) is used. In the above formula (I), specific examples of the halogen atom represented by X include chlorine,
There are bromine, etc. Further, examples of the lower alkoxy group represented by Z include methoxyno, ethoxy, propoquino, etc., and examples of the lower alkanoyl ookine group include acedyluoquine, propionyl okino, butyryloquino, etc. Furthermore, specific examples of the lower alkyl group represented by R1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, pendel, octyl, nonyl, and denyl, and specific examples of the hydroxy lower alkyl group include hydroxymethyl, Specific examples of lower alkoxy lower alkyl groups include methoxymethyl, methoxymethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxyethyl, propoxypropyl, etc., while di-lower alkyl Specific examples of amino lower alkyl groups include dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, diethylaminobutyl, diethylaminopropyl, diethylaminobutyl, etc. Specific examples of aryl groups include phenyl, xylyl, tolyl,
Specific examples of the lower alkoxy group represented by R2 include methoxy, ethoxy, propoxy, etc., and specific examples of the di-lower alkylamino group include dimethylamino, diethylamino, etc. Note that the xanthene or thioxanthene dye (I) is a substance generally known in the literature.

In addition to the above-mentioned xanthene or thioxanthene dye (I), a photosensitivity accelerator is blended in order to further improve the sensitivity to light and complete curing in a shorter time. As photosensitizers, N-phenylgrin, 2,4,6-tris (
(trichloromethyl)-1°3.5-triazine, and a mixture of 2,4-diisopropylthioxanthone and p-dimethylaminobenzoic acid isopendel ester.

As peroxides, those selected from ketone peroxides, peroxyketals, hydroperoxides, noalkyl peroxides, dianolperoquinides, peroxydicarbonates, peroxyesters, etc. Preferred examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3.3.5-trimethylhexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1.1-bis(t-butylperoxy)- 3,3,5-trimethylisoclohexane,
1, l-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-butylperoxy)
valerate, 2,2-his(butylperoxy)butane, butyl hydroperoxide, cumene hydroperoxide, diisoprobylhensen hydroperoxide, paramenthane hydroperoxide, 2,5-dimethyl Hexane-2,5-ene hydroperoxide, 1,1,3.3-tetramethylbutylhydrobarogizite, not-t-butyl peroxide, butylcumyl peroxide, tsucumyl peroxide, α, α° -His(butylperoxyisopropyl)henzen, 2,5-dimethyl-2,5-no(
t-butylperoxy)hexane, 2,5-dimethyl-
2,5-di(i-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide,
Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5.5-)limethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-t- ruoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-nitoxyethyl peroxydicarbonate, dimethoxyisobrobyl peroxycarbonate, di(3-methyl-3-methoxybutyl) Peroxydicarbonate, t-butylperoxypivalate, t-butylperoxyneodecanoate, L-butylperoxyoctanoate, t-butylperoxy-3,5,5-)dimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylmaleic peroxide, t-
Examples include butylperoxyisopropyl carbonate.

The amount of each substance used above is a double bond-containing compound! For heavy nails, xanthene or thioxanthene pigment 0.00
The amount is 5 to 0.3 parts by weight, preferably 0.02 to 0.1 parts by weight. Photosensitivity accelerator formulation ff1 (in the case of a mixed system of p-dimethylaminobenzoic acid isopentyl ester and 2,4-diisopropylthioxanthone, it is the sum of both).

) is 0.005 to parts by weight of the double bond-containing compound.
The amount is 0.3 parts by weight, preferably 0.02 to 0.1. p
-dimethylaminobenzoic acid isopentyl ester and 2.
The mixture of 4-shiitubuvirthioxanthone is 0.1 to 1.5 parts by weight, preferably 0.1 to 1.5 parts by weight of the latter to 1 part by weight of the former.
It is 3 to 1 part by weight. Peroxide is a double bond-containing compound.
The amount is 0.005 to 0.2 parts by weight, preferably 0.01 to 0.08 parts by weight. If the proportion of any of these three components used is below their respective lower limits, sufficient sensitivity cannot be obtained.

Moreover, if it exceeds the upper limit, the cured film will have a low molecular weight, resulting in a decrease in film strength, solvent solubility resistance, etc.

The photopolymerizable composition according to the present invention contains the above monomers and photopolymerization initiator as essential components, but if necessary, a polymeric binder, a thermal polymerization inhibitor, a plasticizer, a colorant, etc. may also be used in combination. This makes it possible to prepare compositions suitable for the above-mentioned uses.

The polymeric binder has various purposes for improving compatibility, film-forming properties, developability, adhesion, etc., and an appropriate type may be selected depending on the purpose.

Specifically, for example, to improve developability with an aqueous solvent, acrylic acid copolymers, methacrylic acid copolymers, itaconic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose modified with carboxyl groups in side chains are used. To improve film strength and adhesion, shrimp chlorohydrin and phenol A are used.
polyether, polyamide, polymethyl methacrylate, polyalkyl methacrylate or polyalkyl acrylate, alkyl methacrylate and acrylonitrile,
Copolymers with acrylic acid, methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc., copolymers with acrylonitrile and vinyl chloride, vinylidene chloride, vinylidene chloride, chlorinated polyolefins, copolymers with vinyl chloride and vinyl acetate. , polyvinyl acetate, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile and butadiene, styrene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose polyvinyl butyral, etc. can be mentioned. These binders are usually used in an amount of 10 parts by weight or less, preferably 0 parts by weight, per 1 part by weight of the double bond-containing compound.
．． It is blended in a proportion of 5 to 3 parts by weight.

Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2.6-
-[-Butyl-p-cresol, β-naphthol, etc. Examples of colorants include phthalocyanine pigments,
There are pigments such as azo pigments, carbon black, and titanium oxide, triphenylmethane dyes, azo dyes, and anthraquinone dyes. The amount of these thermal polymerization inhibitors and coloring agents added is 0.000. O1-3 shield amount%, colorant 0.001
-10% by weight is preferred. Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, dibutyl phthalate, butylbenzyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate,
Examples include dibutyl adipate, dibutyl sebacate, dibutyl maleate, triacetylglycerin, etc., and they can be blended in an amount of 5% by weight or less based on the total weight of the double bond-containing compound and binder.

The photopolymerizable composition of the present invention is suitable for use as a lithographic printing plate, a resist for producing a printed circuit board, or an original plate for producing a mother mold for a rainbow hologram.

In order to form the photosensitive resin layer, the composition containing the above-mentioned essential components and optional components may be applied as it is or dissolved in a suitable solvent, coated on a support, and dried. Examples of solvents include methyl ethyl ketone, acetone, cyclohexanone, ethyl acetate, butyl acetate, aluminum acetate, ethyl propionate, toluene, quinolene, benzene, monochlorohenzene, chloroporum, carbon tetroxide, trichloroethane, trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve, tetrahydrofuran,
Examples include pentoquinone, methanol, ethanol, and propatool.

Note that the photosensitive resin layer may further be subjected to known techniques for preventing adverse effects such as a decrease in sensitivity and deterioration of storage stability due to oxygen. For example, a peelable transparent cover silt may be provided on the photosensitive layer, or a coating layer made of a waxy material with low oxygen permeability, a water-soluble or alkali water-soluble polymer, or the like may be provided.

The photosensitive resin layer obtained in this way can be used for ultraviolet rays of 180 nm or more, visible light such as carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, krypton laser Can this be cured using a general purpose light source including
In particular, image formation and curing can be performed simultaneously by irradiation with a laser light source. Note that development after irradiation may be carried out using an appropriate developer capable of dissolving the photosensitive resin layer, depending on the composition of the photosensitive resin layer.

[Examples] Preparation of Photopolymerizable Composition The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Methyl methacrylate/methacrylic acid copolymer (BR-77 manufactured by Mitsubishi Rayon)1. Og to methyl ethyl ketone I
After dissolving in OH, add pentaerythritol triacrylate (Osaka Organic Chemical Industry Division) 1. A first liquid is obtained by dissolving Og.

Thioxanthene dye (T:A=S;X=,)(,
Y=C: Z=OC2Hs; R'=CaHs: R'
A second solution is obtained by dissolving 60+ ng of di-L-butylbaroxyisophthalate, 30 mg of N-phenylglycine, and IO mg of methquinone (p-methoxyphenol) in 3 g of methyl sorosolve. The above two liquids are mixed and stirred well to obtain a photopolymerizable composition.

Preparation of photosensitive resin layer (test plate) 2g/m on aluminum support using bar coater
Apply the above photosensitive liquid to a coating amount of 2, and heat at 60°C.
and dried for 3 minutes. A photosensitive resin layer with a thickness of 20 μm was obtained. On this photosensitive resin layer, using a bar coater,
5% borihinyl alcohol (20μ thick)
An overcoat layer was prepared by coating an aqueous solution with a degree of saponification of 88% and a degree of polymerization of 500.

Sensitivity measurement Kodak Step Tablet No. 2 (21ste
P) and the above test plate were stacked together, and light with a wavelength of 49 Onm (light intensity 4.0 mW) was extracted from the light of a xenon lamp (manufactured by Uno Electric, 150 W) through a filter.
/cm was irradiated from above for 10 seconds. When developed with a developer (10 parts by weight of anhydrous sodium carbonate, 50 parts by weight of butyl cellosolve and 3 parts by weight of an activator dissolved in 1000 parts by weight of water), the number of photocured stages was 15.

This revealed that it was possible to form an image on this test plate with an exposure amount of about 0.3 mJ/cm'.

Argon ion laser - recording property Argon ion laser light with a beam diameter of 1.25+nm (
488 nm) was spot-exposed on the test plate while varying the intensity and irradiation time, and developed with the developer. If the exposure energy required to obtain a spot with a diameter of 1.25+nm is defined as laser sensitivity, the laser sensitivity of this test plate was 0.65 mJ/Cm2.

Next, a laser beam (
The test plate was cylindrical scanned (1000 rpm, 600 lines/1 nch) while modulating the wavelength (488 nm) with a modulator. Next, when this was developed with the above developer, a clear image was obtained.

Comparative Example 1-1 A photopolymerizable composition was obtained in the same manner as in Example 1 except that 30 mg of N-phenylglycine in Example 1 was removed.

Example! When photosensitivity was measured under the same conditions as above, the number of photocured stages was 11. This revealed that it was possible to form an image on this test plate with an exposure amount of about 1.1 mJ/cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
, 80 mJ 7cm2. Furthermore, the sharpness of the image obtained by cylindrical scanning with an argon ion laser under the same conditions as in Example 1 was inferior to that obtained in Example 1.

Comparative Example 1-2 A photopolymerizable composition was obtained in the same manner as in Example 1, except that 60 mg of di-t-butyl peroxyisophthalate in Example 1 was removed. When sensitivity was measured under the same conditions as in Example I, the number of photocured stages was 10. This revealed that it was possible to form an image on this test plate at a distance of 1.6 m with an exposure amount of about J/cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
, 94. mJ/cm'. In addition, Example 1
The sharpness of the image obtained by cylindrical scanning with an argon ion laser under the same conditions was inferior to that obtained in Example 1.

Example 2 As a dioxanthene dye (■・A=O;
; Y = N; Z = O: R+= C2H5
A test plate was obtained in the same manner as in Example 1 except that 60 mg of 0(CH2)3:R2=N(C3Hs)z) was used. When photosensitivity was measured under the same conditions as in Example 1, the number of photocured steps was 16. From this, this test board is 0.2
It has become clear that image formation is possible with an exposure amount of approximately mJ/cm'.

Next, when we measured the laser sensitivity of the test plate written in "-",
0,60 mJ 7cm2. In addition, Example 1
In a second cylindrical scan using an argon ion laser under the same conditions as in Example I, a clear image similar to that obtained in Example I was obtained.

Comparative Example 2-1 A photopolymerizable composition was obtained in the same manner as in Example 2, except that 30 mg of N-phenylglycine in Example 2 was removed.

When sensitivity was measured under the same conditions as in Example 2, the number of photocured stages was 12. This revealed that images could be formed on this test plate with an exposure dose of about 0.8 mJ/cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
, 52 m, I 7 cm". Also, Example 2
The sharpness of the image obtained by cylindrical scanning with an argon ion laser under the same conditions was inferior to that obtained in Example 2.

Comparative Example 2-2 A photopolymerizable composition was obtained in the same manner as in Example 2, except that 60 mg of di-t-butyl peroxyisophthalate in Example 2 was removed. When sensitivity was measured under the same conditions as in Example 2, the number of photocured stages was 11. This revealed that this test plate was capable of forming an image with an exposure amount of about I, I mJ/cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
, 80 mJ 7 cm''. Further, the sharpness of the image obtained by cylindrical scanning with an argon ion laser under the same conditions as in Example 2 was inferior to that obtained in Example 2.

Example 3 and Comparative Example 3 2°4.6- instead of 30 mg of N-phenylglycine
A test plate was obtained in the same manner as in Example 1 except that 30 mg of tris(trichloromethyl)-1,3,5-triazine was used. When sensitivity was measured under the same conditions as in Example 1, the number of photocured stages was 15. This revealed that this test plate was capable of forming an image with an exposure amount of about 0.3 mJ/cm2.

Next, when the laser sensitivity of the above test plate was measured, it was found to be 0.
, 72 mJ/cm'. In addition, in cylindrical scanning with an argon ion laser under the same conditions as in Example I,
A clear image similar to that obtained in Example 1 was obtained.

For comparison, peroxide (di-1-
A composition containing no (butyl peroxyisophthalate) was formed and similar measurements were performed. The number of stages of photocuring is 11.
It was a step. This test plate is now I, 12 m
It has become clear that image formation is possible with an exposure amount of about J2/cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
, 80 mJ 7 cm''. Furthermore, in cylindrical scanning with an argon ion laser under the same conditions as in Example 3, the sharpness of the image obtained was inferior to that obtained in Example 3.

Example 4 and Comparative Example 4 30 mg of P-dimethylaminobenzoic acid impentyl ester instead of 30 mg of N-phenylglycine, 2.4
A test plate was obtained in the same manner as in Example I except that 15 mg of -diisopropylthioxane was used. When photosensitivity was measured under the same conditions as in Example 1, the number of photocured stages was 14. From this, this test plate is 0.4 mJ/cm2
It has become clear that image formation is possible with an exposure amount of about

Next, when we measured the laser sensitivity of the above test plate, we found that
1.08 mJ 7cm". Also, Example 1
In cylindrical scanning with an argon ion laser under the same conditions, the sharpness was slightly lower than that obtained in Example 1, but it was sufficient as an image obtained by laser scanning exposure. .

For comparison, peroxide (di-1-
A composition containing no (butyl peroxyisophthalate) was formed and similar measurements were performed. The number of stages of photocuring was nine. As a result, this test plate has a power of 2.24 mJ
It has become clear that image formation is possible with an exposure amount of about /cm2.

Next, we measured the laser sensitivity of the above test plate and found that it was 4.
, 35 mJ 7cm2. Alternatively, the sharpness of the image obtained by cylindrical scanning with an argon ion laser under the same conditions as in Example 4 was inferior to that obtained in Example 4.

Example 5 and Comparative Example 5 Same as Example 1 except that 60 mg of 2,5-dimethyl-2,5-no(hensilveroxy)hexane was used instead of 60 mg of di-t-butylperoxyisophthalate. A test plate was obtained. When sensitivity was measured under the same conditions as in Example 1, the number of photocured stages was 16.

This revealed that it was possible to form an image on this test plate with an exposure dose of about 0.2 mJ/cm2.

Next, when the laser sensitivity of the above test plate was measured, it was found to be 0.
, 65 mJ 7cm2. In addition, in cylindrical scanning with an argon ion laser under the same conditions as in Example 1,
A clear image similar to that obtained in Example 1 was obtained.

For comparison, a composition was prepared in which the photosensitizer (N-phenylglycine) was not added in Example 5, and the same measurements were performed. The number of stages of photocuring was 12. This revealed that it was possible to form an image on this test plate at a distance of 0.80 m with an exposure of approximately J/cm 2 of 1 n.

Next, we measured the laser sensitivity of the above test plate and found that it was 2.
．． 41 mJ/am''. Also, in cylindrical scanning with an argon ion laser under the same conditions as in Example 5, the sharpness of the image obtained was inferior to that obtained in Example 5.

Example 6 A test plate was obtained in the same manner as in Example I except that N-phenylglinone was used in an amount of 30 mg and less than 60 mg. When sensitivity was measured under the same conditions as in Example 1, the number of photocured stages was 15. From this, this test board is 0,3
It has become clear that image formation is possible with an exposure amount of mJ/cm''a degrees.

Next, when the laser sensitivity of the above test plate was measured, it was found to be 0.
．． 83 mJ/cm''. In addition, in cylindrical scanning with an argon ion laser under the same conditions as in Example 1, Example 1
A clear image similar to that obtained was obtained.

[Effects of the Invention] The photopolymerizable composition of the present invention is characterized by containing a xanthene or dioxanthene dye as a photopolymerization initiator, a photosensitivity accelerator, and an organic peroxide.

As a result, it exhibits spectral sensitivity that extends not only to the ultraviolet region but also to the visible light region. The high photosensitivity also allows imaging with low energy output lasers.

When photosensitivity was measured under similar conditions, the number of photocured steps was 11. As a result, the number of tests is l,
Image formation is possible with an exposure amount of about l mJ/cm2, and δ
It's obvious that it's scales.

Next, when the laser sensitivity of the number of tests listed in -1- was measured, it was found to be 2.95 m, I/cm2. Furthermore, when the argon ion laser was used to run the cylinder under the same conditions as in Example 1, the sharpness of the image obtained was inferior to that obtained in Example 1.

Le Mawari 1-4 Example! excluding 60 mg of L-butyl peroxyisophthalate and 30 mg of N-phenylglinone.
A photopolymerization composition was obtained in the same manner as in Example 1, except that 90 mg of the photopolymerization composition was used. When photosensitivity was measured under the same conditions as in Example 1, the number of photocured stages was 10 to 11. This revealed that it was possible to form an image with an exposure amount of about 1.4 mJ/am'' in this number of tests.

Next, when we measured the laser sensitivity of the number of tests in the Book of Yu,
2,90 m, 1/cm't)7 Also, when the argon ion laser was moved in a cylinder under the same conditions as in Example 1, the sharpness of the image obtained was compared with that obtained in Example I. and was inferior. ” Hereinafter [Attachment] Claim 1, ``A photopolymerizable composition comprising a compound capable of addition polymerization having a -thyrenically unsaturated double bond and a photopolymerization initiator; The initiator is of the formula (a).

In the formula F, A is an oxygen atom or a sulfur i atom, X is a hydrogen atom or a hydrogen atom, and Y is a carbon atom or a nitrogen atom.
f'-(Tatashi, if Y is a carbon atom, the adjacent 4-
There is a double bond between Y and the carbon atom (indicated by the dotted line), and when Y is a nitrogen atom, there is a single bond between it and the adjacent -4-carbon atom. ), Z is an acid radical r- (in this case, there is a double bond between adjacent carbon atoms), lower alkokene 11 (or lower alkanoyl oxyne group, R
1 is a lower alkyl group, a hydroxy lower alkyl group, a lower alkyl group, a di-lower alkylamino lower alkyl group or an aryl group, and R2 is a hydrogen atom, a lower alkokino group or a di-lower alkylamino group. In addition, Z and R1 may be expressed together as -Z-R'-. ] Xanthene or thioxanthene dye represented by (b) N-phenylglinone, 2.11.6-1-
Lis(trichloromethyl)-1,3,5i-rianone,
or a photosensitizer which is either a mixture of p-tmethylaminobenzoic acid isopentyl ester and 2,4-diisopropylthioxanthone.

(c) Peroxide A photopolymerizable composition comprising:

2. The photopolymerizable composition according to claim 1, wherein the photosensitizer is N-phenylglinone.

3. The photopolymerizable composition according to claim 1, wherein the photosensitizer is 2.4.6-tris(trichloromethyl)-1,3,5-triazine.

4. The photopolymerizable composition according to claim 1, wherein the photosensitizer is a mixture of 2,4-diisobrovirdiogisanthone and p-dimethylaminobenzoic acid isopentyl ester.

5. The compound according to claim 1, wherein the ratio of the addition-polymerizable compound having an ethylenically unsaturated double bond and the xanthene or thioxanthene dye is 0.005 to 0.03 parts by weight to 1 part by weight of the former. Photopolymerizable composition.

6. The ratio of the addition-polymerizable compound having an ethylenically unsaturated double bond and peroxide is 1 part by weight of the former to 0.00 parts by weight of the latter.
The photopolymerizable composition according to claim 1, wherein the amount is 0.05 to 0.2 parts by weight.

7. The photopolymerizable composition according to claim 1, wherein the addition-polymerizable compound having ethylenically unsaturated double bonds has at least two ethylenically unsaturated double bonds in one molecule.

8. The photopolymerizable composition according to claim 7, wherein the compound capable of addition polymerization is a substance having a boiling point of 00° C. or higher.

Procedural amendment IO month 9th, 1985

Claims (1)

[Claims] 1. A photopolymerizable composition comprising an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator, wherein the photopolymerization initiator has the formula (a): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is an oxygen atom or a sulfur atom, X is a hydrogen atom or a halogen atom, and Y is a carbon atom or a nitrogen atom (however, if Y is a carbon atom, the adjacent There is a double bond between the carbon atom (indicated by the dotted line), and if Y is a nitrogen atom, there is a single bond between the adjacent carbon atom. ), lower alkoxy group or lower alkanoyloxy group, R^1 is lower alkyl group, hydroxy lower alkyl group, lower alkoxy lower alkyl group, di-lower alkylamino lower The alkyl group or aryl group, R^2, is a lower alkoxy group or a di-lower alkylamino group. In addition, Z and R^1 together are -Z-
As R^1-, there are ▲mathematical formulas, chemical formulas, tables, etc.▼ is also sometimes expressed. ] xanthene or thioxanthene dye represented by (b) N-phenylglycine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, or p
-dimethylaminobenzoic acid isopentyl ester and 2,
A photosensitizer that is either a mixture with 4-diisopropylthioxanthone. (c) A photopolymerizable composition containing a peroxide. 2. The photopolymerizable composition according to claim 1, wherein the photosensitivity accelerator is N-phenylglycine. 3. The photopolymerizable composition according to claim 1, wherein the photosensitizer is 2,4,6-tris(trichloromethyl)-1,3,5-triazine. 4. The photopolymerizable composition according to claim 1, wherein the photosensitizer is a mixture of 2,4-diisopropylthioxanthone and p-dimethylaminobenzoic acid isopentyl ester. 5. Claim 1, wherein the ratio of the addition-polymerizable compound having an ethylenically unsaturated double bond and the xanthene or thioxanthene dye is 0.005 to 0.3 parts by weight to 1 part by weight of the former. The photopolymerizable composition described in . 6. The ratio of addition-polymerizable compound having an ethylenically unsaturated double bond and peroxide is 1 part by weight of the former to 0.
0.005 to 0.2 parts by weight of the photopolymerizable composition according to claim 1. 7. The photopolymerizable composition according to claim 1, wherein the addition-polymerizable compound having an ethylenically unsaturated double bond has at least two ethylenically unsaturated double bonds in one molecule. 8. The photopolymerizable composition according to claim 7, wherein the addition-polymerizable compound having an ethylenically unsaturated double bond is a substance having a boiling point of 100°C or higher.