JPH04330445A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition high in sensitivity to active rays from ultraviolet rays to visible light and insusceptible of polymeriza tion inhibition by oxygen in the air. CONSTITUTION:The photopolymerizable composition is characterized by containing (a) a cation polymerizable compound having at least 2 vinyl ether groups, (b) a compound to be decomposed by irradiation with active rays or radiation and to be allowed to generate an acid, and (c) a solvent or an alkali- soluble polymer.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to photopolymerizable compositions, more specifically, photopolymerizable compositions for use in lithographic printing plates, resin relief plates, resists or photomasks for producing printed circuit boards, monochrome or color transfer coloring sheets, coloring sheets, etc. The present invention relates to a highly sensitive photopolymerizable composition that can be used for various purposes.

0002

2. Description of the Related Art Conventionally, various photographic image forming systems applying photopolymerization technology have been known. There are systems that typically use a curable organic component containing an ethylenically unsaturated group and undergo a photoinduced addition reaction, such as either polymerization or crosslinking, to cure and form an image.

[0003] In other photographic image forming systems, systems are also known in which a leuco dye that develops color through oxidation reaction or reaction with an acid is combined with a radical generator that functions as an oxidizing agent or an acid. Examples of these are Phot
．． Sci. Eng. 598 (1961), U.S. Patent No. 3,042,515, U.S. Patent No. 3,615,568
It is stated in the specification of the No.

Among the image forming methods using a photosensitive composition containing a curable organic component containing an ethylenically unsaturated group, a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and a suitable A method of photographically duplicating images using a photosensitive composition containing a linear high molecular weight polymer having film-forming ability, a thermal polymerization inhibitor, etc. is now widely known. That is, as described in Japanese Patent Publication No. 35-5093, Japanese Patent Publication No. 35-8495, etc., the photosensitive composition undergoes photopolymerization and becomes insolubilized by irradiation with actinic rays. A desired photopolymerized image is formed by forming a suitable film, irradiating actinic rays through the negative of the desired image, and removing only the unexposed areas with a suitable solvent (hereinafter simply referred to as development). Can be done.

This type of photosensitive composition is extremely useful for use in lithographic printing plates, and research has been carried out to increase the sensitivity or expand the photosensitive range to visible light.
4-20189, JP 48-84183, JP 45-37377, JP 47-2528, JP 54-155292, and JP 54-151024. Polymerization initiation systems have been developed.

Three reaction modes are known for photopolymerization: photo-radical polymerization, photo-cationic polymerization, and photo-anionic polymerization, but as mentioned above, most of the polymerization modes used for photographic image formation are photo-radical polymerization. . This is thought to be due to the high sensitivity of radical polymerization and the good stability of the monomer over time. However, in photo-radical polymerization, oxygen in the atmosphere has a strong polymerization inhibiting effect, so by providing an overcoat layer on the photosensitive layer or arranging long-chain alkyl-containing compounds such as behenic acid on the surface of the photosensitive layer, It is necessary to block oxygen from the atmosphere. Adding an overcoat not only takes time and effort, but also reduces resolution due to light scattering of the layer. One possible way to solve these drawbacks of radical polymerization systems is to use cationic polymerization systems, which have less polymerization inhibiting effects due to oxygen, but cationic polymerizations generally have low sensitivity, and there are very few examples of them being used for photographic image formation. few.

On the other hand, cationic polymerization systems have been developed in various ways as a mainstay of UV curable resins, and as monomers for cationic polymerization, J. V. Crivello, J.
L. Lco, D. A. Conlon, Mac
romol. Chem. Macromol. Sy
mp. , 13/14, 145 (1988), A. Hu
lt, S. A. MacDonald, C. G.
Willson, Macromolecules,
18, 1804 (1985), M. Tsunooka
, S. Tanaka, M. Tanaka, J.
．． Polym. Sci. Polym. Chem
．． Ed. 23, 2495 (1985), F. J.
Vara, J. A. Dougherty. Pr
oc. Conf. Radiation Curing
, Asia, p. 491 (1988); Y., Yamamoto, K.;
Hayashi, Macromolecules, 2
0,2703 (1987); Lohse, H. Zweitel. Ad
v. Polym. Sci. , 78 (61) (198
6), the thioglycidyl monomer described in T. S.
Bal. A. Cox, T. J. Kemp,
P. P Moira, Polymer, 21,
423 (1980), Ao Yamaoka, Japan Adhesive Association Journal, 25
(4), 144 (1989) and the like are known. Further, as photocationic polymerization initiators, diazonium salts, sulfonium salts, iodonium salts, pyrilinium salts, thiopyrilinium salts, etc. are known. Combinations of these monomers and photoinitiators produce photocationically polymerizable compositions, but none of them have sufficient sensitivity, and their use for photographic image formation is not described. Also St
ephenC. Lapin, Polymers P
aint Color Journal, 179 (
4237), 321 (1989), there are descriptions of highly sensitive photocationic polymerizable monomers, but there is no report on photographic image formation.

[0008]

[Problems to be Solved by the Invention] An object of the present invention is to provide a photopolymerizable composition that is highly sensitive to light of any wavelength in the ultraviolet and visible regions and that does not inhibit polymerization due to oxygen in the air. It's about doing.

Another object of the present invention is to provide a photopolymerizable photoreceptor having no overcoat layer and having high resolution.

0010

[Means for Solving the Problems] As a result of extensive research to achieve the above object, the present inventors have discovered that by combining a specific vinyl ether compound with a photoacid generator and a solvent or alkali-soluble polymer, oxygen The inventors have discovered that it is possible to produce highly sensitive and clear photographic image reliefs without polymerization inhibition caused by the use of polyurethane, and have thus arrived at the present invention.

The present invention comprises (a) a cationically polymerizable compound having at least two vinyl ether groups;
) A photopolymerizable composition characterized by containing a compound that decomposes and generates an acid upon irradiation with actinic rays or radiation, and (c) a solvent- or alkali-soluble polymer, and which is resistant to ultraviolet rays, visible light, and electron beams. Alternatively, it is a negative photosensitive composition having high sensitivity to X-rays.

The vinyl ether compound (a) capable of photocationic polymerization used in the present invention is a compound containing at least two terminal vinyl ether groups and having a boiling point of 100° C. or higher at atmospheric pressure.

Such compounds include, for example, monomers,
It has a chemical form such as a prepolymer, that is, a dimer, a trimer, an oligomer, and a copolymer thereof. Preferred examples of component (a) include compounds represented by the following general formula (I) or (II).

R-[-O-(-R″-O-)n
-CH=CH2]m
(I) R'
- [-CO-O-R ″-O-CH=CH2 ]m
(II)R
and R' is a polyhydric alcohol residue, and R'' has 1 to 10 carbon atoms.
represents a linear or branched alkylene group, n is 0 or 1,
m represents an integer of 2 to 6.

The compound represented by the general formula (I) can be produced by the reaction of a polyhydric alcohol and acetylene or the reaction of a polyhydric alcohol and a halogenated alkyl vinyl ether.

Specific examples include ethylene glycol divinyl ether, triethylene glycol divinyl ether,
1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol Divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, Methylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether,
Examples include, but are not limited to, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, and pentaerythritol tetraethylene vinyl ether.

The compound represented by the general formula (II) can also be produced by reacting a polyhydric carboxylic acid with a halogenated alkyl vinyl ether.

Specific examples include terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, terephthalic acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, Examples include, but are not limited to, itaconate diethylene vinyl ether.

The photocationic polymerizable vinyl compound used in the present invention includes a reaction product of a vinyl ether compound containing active hydrogen and a compound having two or more isocyanate groups. The vinyl ether compound containing active hydrogen has the following general formula (III),
It is a compound represented by (IV) or (V).

CH2=CH-O-R''-OH
(III) CH2 = C
H-O-R''-COOH
(IV) CH2 = CH-O-R''-NH
2 (V) Here, R'' represents a linear or branched alkylene group having 1 to 10 carbon atoms.

Compounds containing two or more isocyanate groups include, for example, Crosslinking Agent Handbook (published by Taiseisha, 1.
(published in 1981) can be used. Specifically, triphenylmethane triisocyanate,
Dimer of diphenylmethane diisocyanate, tolylene diisocyanate, 2,4-tolylene diisocyanate,
Polyisocyanate types such as naphthylene-1,5-diisocyanate, o-tolylene diisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, adducts of tolylene diisocyanate and trimethylolpropane, hexamethylene Examples include polyisocyanate adducts such as an adduct of diisocyanate and water and an adduct of xylene diisocyanate and trimethylolpropane.

Urethane oligomers having vinyl ether groups at various ends can be produced by reacting the above-mentioned isocyanate compound with an active hydrogen-containing vinyl ether compound.

These vinyl ether group-containing compounds used in the present invention are described, for example, by Stephen C.; La
pin, Polymers PaintColour
Journal, 179(4237), 321(1
It can be synthesized by the method described in 989). In addition, the ingredients (
The amount of a) used is from 5 to 80% by weight, preferably from 10 to 60% by weight, based on the total weight of the composition.

Next, the compound (b) used in the present invention, which decomposes to generate acid upon irradiation with actinic rays or radiation, will be explained.

The photoacid generator used in the present invention can be arbitrarily selected and used as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation.

For example, onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, and thiapyrylium salts, halogenated compounds such as tris(trihalomethyl)-s-triazine, and sulfonylimides. Preferably, iodonium salts,
Sulfonium salts are used. Among them, iodonium salts and sulfonium salts represented by the following general formula (1) or (2) whose counter ion is an aromatic sulfonate can be effectively used for various light sources by changing the structure of the counter ion. Ru.

[0027]

[Chemical formula 1]

In the formula, Ar1 and Ar2 may be the same or different and represent a substituted or unsubstituted aryl group. Preferred substituents are alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl,
These include alkylcarbonyl, alkoxycarbonyl, hydroxy, mercapto group, and halogen atom, and more preferably alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, nitro group, and chlorine atom.

R1, R2 and R3 may be the same or different and represent a substituted or unsubstituted alkyl group or aryl group. Preferably an aryl group having 6 to 14 carbon atoms, 1 to 14 carbon atoms
Eight alkyl groups and substituted derivatives thereof.

Preferred substituents for the aryl group include alkoxy having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms, nitro, carboxyl, alkylcarbonyl, hydroxy group, and halogen atom; For alkoxy, carboxyl having 1 to 8 carbon atoms,
They are alkylcarbonyl and alkoxycarbonyl groups.

[0031] Also, two of R1, R2, R3 and
Ar1 and Ar2 may each be bonded via a single bond or a substituent.

X- represents an aromatic sulfonic acid anion. Specifically, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, anthracene-1-sulfonic acid, 9
-Nitroanthracene-1-sulfonic acid, 9,10-dichloroanthracene-2-sulfonic acid, 9,10-dimethoxyanthracene-2-sulfonic acid, 9,10-diethoxyanthracene-2-sulfonic acid, anthracene-
2-sulfonic acid, phenanthrene-2-sulfonic acid, 9
-bromophenanthrene-3-sulfonic acid, 1-methyl-7-isopropylphenanthrene-3-sulfonic acid,
Pyrene-2-sulfonic acid, benz[a]anthracene-
4-sulfonic acid, triphenylene-2-sulfonic acid, chrysene-6-sulfonic acid, 5,6-dichloroanthracene-3-sulfonic acid, 6-nitroacenaphthene-5-sulfonic acid, 2-t-butylnaphthalene-7 - Condensed polynuclear aromatic sulfonic acid anions such as sulfonic acid, 9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid, 1-bromo-9,10-dioxo-9,10-dihydroanthracene-2- Sulfonic acid, 2-chloro-9
,10-dioxo-9,10-dihydroanthracene-
2-sulfonic acid, anthraquinone sulfonic acid such as 9,10-dioxo-9,10-dihydrophenanthrene-3-sulfonic acid, phenanthraquinone sulfonic acid anion, 1,2-naphthoquinone-4-sulfonic acid, 1 , 2-naphthoquinonediazide-4-sulfonic acid, naphthoquinonesulfonic acid anions such as 1,2-naphthoquinonediazide-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, phenol red, methyl orange, alizarin. Examples include, but are not limited to, sulfonic acid group-containing dyes such as S, indigo carmine, patent blue, chlorophenol red, and chrysophenine.

Specific examples of the compounds represented by the general formula (1) or (2) are shown below.

[0034]

[Case 2]

[0035]

[C3]

[0036]

[C4]

[0037]

[C5]

[0038]

[C6]

[0039]

[C7]

[0040]

[Chemical formula 8]

[0041]

[Chemical formula 9]

[0042]

[Chemical formula 10]

[0043]

[Chemical formula 11]

[0044]

[Chemical formula 12]

[0045]

[Chemical formula 13]

[0046]

[Chemical formula 14]

The above-mentioned compound represented by the general formula (1) or (2) is described, for example, in J. W. Knapczyk et al., J. Am. Chem. Soc. , Vol. 91, p. 145 (1969), A. L. Mayc
ock et al., J. Org. Chem. , 35th
Vol. 2532 (1970), E. Goeth
als et al., Bull. Soc. Chem. B
elg. , Volume 73, Page 546 (1964), H
．． M. By Leicester, J. Am. Ch
em. Soc. , Volume 51, Page 3587 (1929
), J. V. Crivello et al., J.
Polym. Soc. Polym. Chem.
Ed. , Volume 18, Page 2677 (1980),
U.S. Patent Nos. 2,807,648 and 4,24
No. 7,473, F. M. Beringer
et al., J. et al. Am. Chem. Soc. , Volume 75, Page 2705 (1953), Japanese Patent Application Publication No. 1983-1
An aromatic sulfonic acid or sodium salt aqueous solution or alcohol solution is added to an aqueous or alcoholic solution of a halogen, bisulfate or perhalogenate of an onium compound produced by the procedure shown in Publication No. 01,331 etc. Obtained by filtering the precipitate.

The amount of the photoacid generator used in the present invention is 100% of the photocationically polymerizable vinyl ether compound.
0.01 to 50 parts by weight, particularly preferably 0.
．． It ranges from 1 to 20 parts.

[0049] Furthermore, by adding a hydrogen donating compound such as N-phenylglycine, 2-mercaptobenzothiazole, or N,N-dialkylbenzoic acid alkyl ester to the photopolymerizable composition of the present invention, the photopolymerizable composition can be further photopolymerized. Polymerization initiation ability can be increased. Also, pyrene, perylene, dimethoxyanthracene, which promotes the photodecomposition of onium salts,
Electron-donating substances such as diethoxyanthracene, diethoxynaphthalene, and dimethoxynaphthalene can also be added as necessary. Such a compound is preferably added in an amount of 1 to 30% by weight based on the total weight of the photopolymerizable composition.

The solvent- or alkali-soluble polymer (c) used in the present invention is a linear organic polymer, arbitrarily selected from those having compatibility with the photopolymerizable vinyl ether compound. can be used.

Examples of organic solvent-soluble polymers include styrene resin, alkyd resin, vinyl chloride resin, polyvinylidene chloride resin, vinyl acetate resin, polymethyl acrylate, polymethacrylate resin, isobutylene resin, polyester resin, ketone resin, and epoxy resin. Examples include, but are not limited to, resins, phenoxy resins, polycarbonate resins, and the like. Among these, when a resin having an epoxy group at the end of its molecular chain, such as epoxy resin or phenoxy resin, is used, a clear relief image can be obtained.

[0052] Effective epoxy resins include, for example, EP
ON-812, -815, -820, -828, -83
4, -836, -1001, -1002, -1004,
-1007, -1009, -1031 (manufactured by Shell),
Araldite-252, -260, -280, -5
02, -6005, -6071, -6700, -608
4, -6097, -6099 (manufactured by Ciba Geigy),
Dow-331, -332, -661, -664, -
667 (manufactured by Dow Chemical Company), Bakerite
-2774, -2795, -2002, -2053, -
2003, -3794 (manufactured by Barcalite), Epo
xide-201 (manufactured by Union Carbide Chemical Co.),
Epicote 828, Epicote 1001 (manufactured by Asahi Denka)
etc. can be mentioned.

As the alkali-soluble polymer, addition polymers having carboxylic acid in the side chain, such as JP-A-59-4
No. 4615, Special Publication No. 34327, Special Publication No. 1982-
No. 12577, Japanese Patent Publication No. 1972-25957, Japanese Patent Publication No. 1973
-92723, JP-A-59-53836, JP-A-5
9-71048, namely, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers,
Examples include partially esterified maleic acid copolymers. Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. In addition to these, addition polymers having hydroxyl groups to which a cyclic acid anhydride is added are useful. In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as necessary] copolymers and [allyl (meth)acrylate/(meth)acrylic acid/as necessary and other addition-polymerizable vinyl monomers] copolymers are preferred. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. Alcohol-soluble nylon and polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin are also useful in order to increase the strength of the cured film. Any amount of these linear organic high molecular weight polymers can be mixed into the photosensitive composition. However, if it exceeds 90% by weight, favorable results will not be obtained in terms of the strength of the formed image. Preferably it is 30 to 85% by weight. Further, the weight ratio of the photopolymerizable vinyl ether compound and the linear organic polymer is preferably in the range of 1/9 to 7/3. A more preferable range is 3/7 to 5/5.

[0054] When the photopolymerizable composition of the present invention is applied onto a support, it is used after being dissolved in various organic solvents. The solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethanol , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, Examples include methyl lactate and ethyl lactate. These solvents can be used alone or in combination. The appropriate concentration of solids in the coating solution is 2 to 50% by weight.

[0055] The coating amount is approximately 0.1 g/dry weight.
A range of from m2 to about 10 g/m2 is suitable. More preferably, it is 0.5 to 5 g/m2.

As the support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), and materials such as aluminum (including aluminum alloys), zinc, steel, etc. Metal plates, furthermore, for example cellulose diacetate, cellulose triacetate, cellulose propionate,
Examples include plastic films such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.

In the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodizing treatment, etc. It is preferable that the

Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Patent Publication No. 47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The above-mentioned anodizing treatment can be carried out using an electrolytic solution, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more of them. This is carried out by passing an electric current through the aluminum plate as an anode.

Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

[0060] Furthermore, a surface obtained by combining electrolytic grains as disclosed in Japanese Patent Publication No. 46-27481, Japanese Patent Application Publication No. 52-58602, and Japanese Patent Application Publication No. 52-30503, and the above-mentioned anodizing treatment and sodium silicate treatment. Treatment is also useful.

[0061] Further, it is also preferable to perform mechanical roughening, chemical etching, electrolytic graining, anodic oxidation treatment, and sodium silicate treatment in this order as disclosed in JP-A No. 56-28893.

Furthermore, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in their side chains, polyacrylic acid, and water-soluble metal salts (such as zinc borate) are added. ) or undercoated with yellow dye, amine salt, etc. are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is performed for purposes such as improving sexual performance.

The photopolymerizable composition of the present invention can also be used in conventional photopolymerization reactions. Furthermore, it can be applied in many ways, such as as a photoresist in the production of printing plates, printed circuit boards, and the like. In particular, due to the high sensitivity and wide spectral sensitivity characteristics up to the visible light region, which are the characteristics of the photopolymerizable composition of the present invention,
Good effects can be obtained when applied to photosensitive materials for visible light lasers such as Ar+ lasers.

A photosensitive material using the photopolymerizable composition of the present invention is imagewise exposed, and the unexposed areas of the photosensitive layer are removed with a developer to obtain an image. Preferred developing solutions for using these photopolymerizable compositions as lithographic printing plates include those disclosed in Japanese Patent Publication No. 57-7
Examples include developers such as those described in No. 427, including sodium silicate, potassium silicate, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate,
Aqueous solutions of inorganic alkaline agents such as diammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkaline agents such as monoethanolamine or diethanolamine are suitable. The concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.1% by weight.
It is added in an amount of 5 to 5% by weight.

The alkaline aqueous solution may also contain a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol, if necessary. For example, U.S. Patent No. 3,37
5,171 and 3,615,480.

[0067] Furthermore, Japanese Patent Application Laid-open No. 50-26601 and No. 58
-54341, Special Publication No. 56-39464, 56-
The developing solutions described in each publication of No. 42860 are also excellent.

[0068]

[Effects of the Invention] The photopolymerizable composition of the present invention has high sensitivity to active light in a wide range from ultraviolet light to visible light, and polymerization is not inhibited by oxygen in the air. .

Light sources used for exposing the photopolymerizable composition of the present invention include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps;
Examples include chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight.

[0070]

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[Example 1] The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water. After etching by immersing in 10% sodium hydroxide at 70°C for 60 seconds, washing with running water, and then etching.
It was neutralized and washed with 0% nitric acid, and then washed with water. This was calculated using a sinusoidal alternating waveform current under a voltage of 12.7V.
% nitric acid aqueous solution, electrolytic surface roughening treatment was performed at an anode electricity amount of 160 coulombs/dm2. When the surface roughness was measured, it was 0.6μ (expressed as Ra). Subsequently, it was anodized for 2 minutes in a 30% sulfuric acid aqueous solution at a current density of 2 A/dm2 to a thickness of 2.7 g/m2.

A photosensitive solution having the composition shown below was coated onto the aluminum plate thus treated so that the dry weight was 1.5 g/m 2 and dried at 80° C. for 2 minutes to form a photosensitive layer.

Photosensitive liquid triethylene glycol divinyl ether
0.125g
Phenoxy resin (product name Epicote #1009
(manufactured by Shell) 0.2g 9,10-diethoxyanthracene diphenyl sulfonate 0.
015g Iodonium salt dioxane/methanol
1
0g/5g

The photosensitivity test was evaluated using an eye rotary exposure machine (light source: metahalogen lamp). Sensitivity measurements were performed using the Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd., with a transmission optical density of 0.05 at the first stage and 0.
Evaluation was made using a step tablet with 15 increments and up to 15 steps, and image sharpness was evaluated using a negative original with a 200 lines/inch dot image printed on lithographic film.

[0075] When the illuminance on the surface of the sensitive material film is 200lux, 20
It was exposed to light for a second, and then developed by immersing it in dioxane for 1 minute and 30 seconds.

The obtained image was clear, and the number of clear steps of the PS step guide was 4 steps.

[Example 2] The photosensitive material used in Example 1 was used with an eye rotary exposure machine, and the illuminance on the surface of the photosensitive material was 200.
lux for 20 seconds, and then heated at 80° C. for 5 minutes (hereinafter abbreviated as “post-bake”). As a result of immersion in dioxane for 1 minute and 30 seconds for development, the resulting image was clear and the number of clear steps of the PS step guide was 14 steps. It can be seen that sensitivity is increased by post-baking.

[Examples 3 to 7] In the photosensitive liquid composition described in Example 1, the photoinitiator shown in Table 1 was used in place of 0.015 g of 9,10-diethoxyanthracenesulfonic acid diphenyliodonium salt. The sensitivity of the sensitive material was evaluated in the same manner as described in Example 1 and Example 2, except that the sensitive material was prepared. The obtained images were clear regardless of the presence or absence of post-baking, and the number of clear stages of the PS step guide listed in Table 1 was obtained.

[0079]
Table 1────────────────
──────────────────────Example
Initiator Sensitivity (Number of clear steps of step guide)

Without postbake With postbake────
──────────────────────────
────── 3 Compound (1-8)
0.015 g 5
13 4 Compound (1-
11) 0.015 g 4
13 5 Compound (2-4) 0.015 g 4
14 6
Compound (2-20) 0.015 g
3 12 7
CF3SO3Ag 0.02g
1
2 Parabromoacetate
Phenone 0.01g──
──────────────────────────
────────

[Examples 8 to 10] In the photosensitive liquid composition described in Example 1, a photosensitive material was prepared using a photocationically polymerizable monomer shown in Table 2 in place of 0.125 g of triethylene glycol divinyl ether. The sensitivity of the light-sensitive material was evaluated in the same manner as described in Example 1, except for the above. The obtained image was clear, and the number of clear stages of the PS step guide listed in Table 2 was obtained.

[0081]
Table 2──────────────
──────────────────────Example
Photo-cationic polymerizable monomer
Sensitivity (step guide)

Clear stage)────────────────────────
──────────── 8 Trimethylolpropane 0.25g
5 Trivinyl ether
9 Pentaerythritol 0
．． 125g 4
Tetravinyl ether 10 Triethylene glycol 0.125 g
4 Reactant of monovinyl ether and diphenylmethylene diisocyanate
──────────────────────────
─────────

[Example 11, 12]
In the photosensitive liquid composition described in Example 1, 0.2 g of phenoxy resin (trade name Epicote #1009 manufactured by Shell Co., Ltd.)
The sensitivity of the sensitive material was evaluated in the same manner as described in Example 1, except that a sensitive material was prepared using the binder shown in Table 3 and 15 g of methyl ethyl ketone instead of 10 g/5 g of dioxane/methanol. . The obtained image was clear, and the number of clear steps of the PS test guide shown in Table 3 was obtained.

[0083]
Table 3──────────────
──────────────────────Example
Binder sensitivity (
Clear step number of step guide) ──────────
──────────────────────────
11 EPON #1002

5 (manufactured by Shell) 12 Araldite-502

6 (manufactured by Ciba Geigy)─
──────────────────────────
─────────

[Examples 13 to 20]
A photosensitive solution having the following composition was coated on an aluminum plate treated in the same manner as in Example 1 so that the dry weight was 1.5 g/m 2 and dried at 80° C. for 2 minutes to form a photosensitive layer. Photosensitive liquid triethylene glycol divinyl ether
0.125g
Binders listed in Table 4
0.2g
Photoinitiators listed in Table 4

0.02g dioxane/methanol

10g/5g

In the photosensitivity test, an eye rotary exposure machine was used, and sensitivity and image clarity were evaluated using a Fuji PS step guide and a negative film having a halftone image of 200 lines/inch as originals. Development was carried out by immersion in the following developer solution at 25° C. for 1 minute. Developer solution 1K potassium silicate
30g
potassium hydroxide
1
5g Dodecylphenoquine sodium benzenesulfonate 3g Water

1000g

0086
] The sharpness of the images obtained was good for all of the photosensitive materials. Table 4 shows the sensitivity (the number of clear steps of the PS step guide).

[0087]
Table 4──────────────
──────────────────────Example
Binder Photoinitiator Sensitivity (step guide)

number of stages)
──────────────────────────
────────── 13 Allyl methacrylate/Compound (1-3)
4 Methacrylic acid copolymer (80/20 weight ratio) 14
〃
Compound (2-4)
5 15 Benzyl methacrylate/
Compound (1-3) 5
Acrylic acid copolymer (
80/20 weight ratio) 16
〃 Compound (2
-4) 4──────────
──────────────────────────

[0088] This example revealed that the photopolymerizable composition of the present invention exhibits high sensitivity even in a photoreceptor without an overcoat (oxygen blocking layer) and can produce clear relief images.

Claims (4)

[Claims] Claim 1: (a) a cationically polymerizable compound having at least two vinyl ether groups; (b) a compound that decomposes to generate an acid upon irradiation with actinic rays or radiation; and (c) a solvent- or alkali-soluble polymer. A photopolymerizable composition comprising: 2. The photopolymerizable composition according to claim 1, wherein the component (a) is a compound represented by general formula (I) or (II). R-[-O-(-R″-O-)n
-CH=CH2]m
(I) R'
- [-CO-O-R ″-O-CH=CH2 ]m
(II)R
and R' is a polyhydric alcohol residue, and R'' has 1 to 10 carbon atoms.
represents a linear or branched alkylene group, n is 0 or 1,
m represents an integer of 2 to 6. 3. The photopolymerizable composition according to claim 1, wherein the component (a) is a reaction product of an active hydrogen-containing vinyl ether compound and a compound having two or more isocyanate groups. . 4. The photopolymerizable composition according to claim 1, wherein component (c) is a solvent-soluble polymer containing an epoxy group.