JPH1062998A - Photosensitive composition and photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To uniformly disperse mist of an aq. silver halide emulsion, to integrate a curable layer and a photosensitive layer into a single layer and to obtain a photosensitive material suitable for use as an original plate for printing by dispersing the mist in an oil phase contg. a polymerizable compd., a hydrophobic polymer having a specified amt. of acidic groups in a salt state and an org. solvent. SOLUTION: Mist of an aq. silver halide emulsion is dispersed in an oil phase contg. a polymerizable compd., a hydrophobic polymer and an org. solvent. The hydrophobic polymer has acidic groups which are partially or entirely in a salt state and the amt. of the acidic groups in the salt state is 5×10<-3> -3×10<-3> mol per 1g of the polymer. The polymer preferably has an ethylenic unsatd. bond in each molecule. The pref. amts. of the polymerizable compd., the hydrophobic polymer and the aq. silver halide emulsion are 0.2-20 pts.wt., 1-30 pts.wt. and 0.5-25 pts.wt., respectively, based on 100 pts.wt. of the org. solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition in which droplets of an aqueous silver halide emulsion are dispersed in an oil phase, and a photosensitive material produced using the same.

[0002]

2. Description of the Related Art A photosensitive material having a photosensitive curable layer containing a silver halide, a reducing agent and a polymerizable compound on a support is image-exposed, and the silver halide is developed. A method of polymerizing a compound to form a polymer image is disclosed in Japanese Patent Publication Nos. 3-12307 and 3-1230.
No. 8 (U.S. Pat. No. 4,629,676 and European Patent No. 0174634). In this method, polymerization is initiated by an oxidant radical of a reducing agent that has reduced silver halide (which may be a radical generated by decomposition of an oxidant of the reducing agent; hereinafter, simply referred to as an oxidant radical). . Specifically, the photosensitive material is heated to develop the silver halide to form a cured image of the polymerizable compound. Japanese Patent Publication No. 3-12308 also describes a photosensitive microcapsule containing silver halide and a polymerizable compound.

[0003] For the production of photosensitive microcapsules, a photosensitive composition in which droplets of an aqueous silver halide emulsion are dispersed in an oil phase containing a polymerizable compound is used. Specifically, the photosensitive composition is further emulsified in an aqueous medium to form an outer shell around droplets of the photosensitive composition, thereby producing photosensitive microcapsules. The polymerizable compound is generally a lipophilic liquid and functions as an oil phase as it is. Tokuhei 6-
23844 (U.S. Pat. No. 4,820,610 and European Patent No. 0223261) and Japanese Patent Publication No.
Japanese Patent No. 21632 describes a dispersing polymer for dispersing droplets of an aqueous silver halide emulsion in a polymerizable compound. In the invention described in Japanese Patent Publication No. 23844/1994, a main chain substantially consisting of a hydrocarbon chain is provided, and a part of the main chain is replaced by a hydrophilic group containing a nitrogen atom having -0H or a lone electron pair. Is used as a dispersing polymer. In the invention described in Japanese Patent Publication No. Hei 7-21632, there is a main chain substantially consisting of a hydrocarbon chain,
A polymer in which a part of the main chain is substituted by a hydrophilic group containing an ether bond, a carboxyl group or a sulfonic acid group (the carboxyl group and the sulfonic acid group may be in the form of an alkali metal salt or an ammonium salt). Is used as a dispersing polymer. The hydrophilic group of the dispersing polymer has an affinity for silver halide grains, and the main chain substantially composed of a hydrocarbon chain has an affinity for an oil phase containing a polymerizable compound. The dispersing polymer functions as a type of surfactant, and finely and uniformly disperses droplets (finally, silver halide particles) of the aqueous silver halide emulsion in the oil phase.

[0004] The image forming method described above can be applied to the production of a printing plate. In a photosensitive material used for manufacturing a printing plate, generally, components of the photosensitive material are uniformly dispersed in the photosensitive curable layer without using photosensitive microcapsules. The photosensitive curable layer without using photosensitive microcapsules is formed by coating a photosensitive composition containing silver halide, a reducing agent and a polymerizable compound on a support. In the production of printing plates, the strength of the resulting polymer image is very important. In the polymer image of the cured portion obtained by the image forming method described in each of the above-mentioned publications, the durability (printing durability) as a printing plate was insufficient. Therefore, in a photosensitive material (printing plate) used for manufacturing a printing plate, it has been considered that a hydrophobic polymer is added as a binder to reinforce the strength of a cured portion. In Japanese Patent Publication No. Hei 7-21634 (U.S. Pat. No. 4,985,339 and European Patent No. 0267037), a crosslinkable polymer having an ethylenically unsaturated bond in a side chain is used as a binder to polymerize a polymerizable compound. At the same time, there is described an invention in which a polymer is crosslinked to further strengthen a cured portion. In addition, it is generally difficult to dissolve a hydrophobic or crosslinkable polymer in an oil phase composed of a polymerizable compound, and even if it is dissolved, the viscosity of the photosensitive composition (coating solution for the photosensitive curable layer) is extremely low. Get higher. Therefore, in a photosensitive composition containing a hydrophobic or crosslinkable polymer, an organic solvent is used in addition to the polymerizable compound to dissolve the polymer and adjust the viscosity of the oil phase.

As described above, even if a hydrophobic or crosslinkable polymer is used as a binder, the strength of the cured portion obtained is not sufficient. As a cause thereof, it was found that the dispersion of the silver halide aqueous emulsion droplets in the photosensitive composition was insufficient, and that aggregation of silver halide grains occurred. In the examples of JP-B-7-21634, a dispersing polymer described in JP-B-6-23844 is used in addition to the crosslinkable polymer. Tokuhei 6-238
As described in JP-B-44, in a photosensitive composition for producing a photosensitive microcapsule, the dispersing polymer sufficiently functions to disperse fine and uniform droplets of the aqueous silver halide emulsion. Have been. However, for some reason, in the photosensitive composition for producing a printing original plate as described in JP-B-7-21634, the dispersing polymer did not function sufficiently. Until recently, the cause remained completely unknown. Photosensitive material (printing plate) manufactured from a photosensitive composition in which silver halide particles are aggregated due to insufficient dispersion of silver halide aqueous emulsion droplets
In this case, the curing reaction for image formation does not proceed sufficiently.

As means for solving all of the above-mentioned problems relating to the strength of the hardened portion, Japanese Patent Application Laid-Open No. 5-249667 (US Pat. No. 5,122,443 and European Patent No. 042) has been proposed.
No. 6192) and JP-A-4-191856.
In the publication (US Pat. No. 5,290,659),
A photosensitive material has been proposed in which a conventional single photosensitive curable layer is separated into a curable layer containing a polymerizable compound and a hydrophobic polymer, and a photosensitive layer containing silver halide and a hydrophilic polymer. When the curable layer and the photosensitive layer are separated, the hydrophobic component is contained in the curable layer and the hydrophilic component is contained in the photosensitive layer, and each component is easily and uniformly dispersed in each layer. can do. Image formation (manufacture of printing plates)
Then, after the image exposure, the curable layer of the exposed portion is cured by heat development, then the hydrophilic layer such as the photosensitive layer is removed from the photosensitive material, and the uncured portion of the curable layer is removed using an alkaline eluate. Is removed, and the remaining cured image is used as a printing plate image. Even when the curable layer and the photosensitive layer were separated, no problem was observed in image formation because oxidant radicals moved from the photosensitive layer to the curable layer during thermal development.

[0007]

The separation of the curable layer and the photosensitive layer has solved various problems relating to the strength of the cured portion.
However, for practical use of the printing original plate, it is desirable to reduce the number of layers as much as possible. When the number of layers is large, the number of manufacturing steps of the printing original plate (photosensitive material) increases, which is disadvantageous in terms of manufacturing cost. Further, when the curable layer and the photosensitive layer are separated, it is necessary to add a step of removing the photosensitive layer also in the image forming process. The present inventor has reviewed the photosensitive material used as the printing original plate and tried to integrate the curable layer and the photosensitive layer into a single photosensitive curable layer again.

In the case of integrating a curable layer and a photosensitive layer into a single photosensitive curable layer in a photosensitive material for a printing original plate,
The biggest problem is the insufficient strength of the cured image described above. In particular, in a photosensitive composition for producing a printing original plate, it is necessary to prevent fine particles of an aqueous silver halide emulsion from being dispersed finely and uniformly to prevent aggregation of silver halide grains. The present inventor has again examined the photosensitive composition for producing a printing original plate described in Japanese Patent Publication No. 21634/1995 and found the cause of the insufficient function of the dispersing polymer. In the examples described in the publication, the crosslinkable polymer is used in an amount of 33.5 times by weight the dispersing polymer. According to the study of the present inventor, it has been found that the crosslinkable polymer which is predominantly present in a large amount inhibits the function of the dispersing polymer. If the amount of the crosslinkable (or hydrophobic) polymer used is reduced, the function of the dispersing polymer is considerably recovered, but the crosslinked (or hydrophobic) polymer function as a binder is reduced, so that the strength of the cured image is reduced. Little improvement.

An object of the present invention is to provide a liquid photosensitive composition in which droplets of an aqueous silver halide emulsion are uniformly and finely dispersed in an oil phase containing a polymerizable compound, a hydrophobic polymer and an organic solvent. To provide. It is another object of the present invention to provide a photosensitive material in which a curable layer and a photosensitive layer are integrated into a single photosensitive curable layer, and which is suitable for use as a printing original plate.

[0010]

The present inventors have further studied and found that the problem can be solved by adding the function of a dispersing polymer to a hydrophobic (or crosslinkable) polymer. The above object has been achieved by the following photosensitive compositions and photosensitive materials (1) to (6). (1) A liquid photosensitive composition in which droplets of an aqueous silver halide emulsion are dispersed in an oil phase containing a polymerizable compound, a hydrophobic polymer, and an organic solvent, wherein the hydrophobic polymer is one of A part or all of the polymer has an acidic group in a salt state, and 1 g of the hydrophobic polymer contains 5 × 10 ^{-5 to} 3 × 10 ^-3 mol of the acidic group in a salt state. A photosensitive composition comprising:

(2) The photosensitive composition according to (1), wherein the hydrophobic polymer has an ethylenically unsaturated bond in the molecule. (3) The polymerizable compound is contained in an amount of 0.1 per 100 parts by weight of the organic solvent.
The photosensitive composition according to (1), comprising 2 to 20 parts by weight, 1 to 30 parts by weight of a hydrophobic polymer, and 0.5 to 25 parts by weight of an aqueous silver halide emulsion. (4) The photosensitive composition according to (1), further comprising a reducing agent. (5) A photosensitive material having a photosensitive curable layer formed by applying the photosensitive composition according to (4) on a support. (6) A photosensitive curable layer formed by applying the photosensitive composition according to (1) on a support, and an overcoat layer containing a hydrophilic polymer thereon, further comprising a reducing agent. A photosensitive material contained in a photosensitive curable layer or an overcoat layer.

[0012]

According to the study of the present inventors, a hydrophobic polymer having an acidic group partially or entirely in a salt state functions as a polymer for dispersing droplets of an aqueous silver halide emulsion. And a function as a binder for reinforcing the strength of the cured portion. A similar polymer is described in JP-B-7-21632 as a dispersed polymer for a photosensitive composition for producing a photosensitive microcapsule. Another similar polymer is disclosed in Japanese Patent Application No. 6-339.
No. 654 describes a binder for the curable layer for enhancing the adhesive strength between the curable layer and the photosensitive layer. However, the dispersing polymer and the binder of the curable layer are polymers used for completely different purposes, and have different timings (the dispersing polymer functions during the production of the photosensitive material, and the binder acts during the use of the photosensitive material. Function), so each was studied independently. Therefore, it has not been studied at all to use one type of polymer together.

According to the present invention, by using both the dispersing polymer and the binder with one kind of polymer, the problem that the function of the dispersing polymer is hindered by the binder can be solved. Therefore, the droplets of the aqueous silver halide emulsion can be uniformly and finely dispersed in the oil phase containing the polymerizable compound, the hydrophobic polymer and the organic solvent. When a photosensitive composition in which an aqueous silver halide emulsion is uniformly and finely dispersed is used, a photosensitive material (printing plate) having a single photosensitive curable layer in which aggregation of silver halide particles is hardly observed is obtained. Can be manufactured. When an image is formed by using such a photosensitive material (printing plate is manufactured), the curing reaction sufficiently proceeds by fine and uniformly dispersed silver halide particles, and the polymer functions as a binder, and the strength is increased. A high cured image can be formed. As a result, when the photosensitive composition of the present invention is used, a photosensitive material having a single photosensitive curable layer and suitable for use as a printing original plate can be produced. In the photosensitive material of the present invention, since the curable layer and the photosensitive layer are integrated into a single photosensitive curable layer, the steps for production and image formation can be reduced, which is important for practical use. This is very advantageous in terms of production and running costs. And, although the photosensitive material of the present invention employs a single photosensitive curable layer, an image of the same or higher quality as the photosensitive material in which the photosensitive layer and the curable layer are separated can be obtained. Forming (producing a printing plate).

The light-sensitive material of the present invention also has the effect that the sharpness of the obtained image is extremely excellent. The reasons are considered to be that the silver halide grains are finely and uniformly dispersed in the photosensitive curable layer and that a single photosensitive curable layer is employed.
Compared with the conventional printing original plate employing a single photosensitive curable layer, such as the photosensitive material described in JP-B-7-21634, the photosensitive material described in JP-A-5-249667 is more preferable. The printing original plate in which the photosensitive layer and the curable layer were separated had better image sharpness. However, the present inventor further studied, the reason is that the latter is because the silver halide grains are finely and uniformly dispersed than the former, and when the grains are uniformly dispersed to the same extent,
From the viewpoint of image sharpness, it has been found that a photosensitive material having a single photosensitive curable layer is more advantageous than a photosensitive material in which the photosensitive layer and the curable layer are separated. When the photosensitive layer and the curable layer are separated, the oxidant radical generated in the photosensitive layer diffuses almost freely in the photosensitive layer in the lateral direction, and lowers the sharpness of the image. On the other hand, oxidant radicals generated in a single photosensitive curable layer are surrounded by substances that react with radicals, such as a polymerizable compound and a binder. Therefore, within a single photosensitive curable layer,
The radical is hardly diffused and used for the curing reaction. For the above reasons, the photosensitive material of the present invention in which silver halide grains are finely and uniformly dispersed in a single photosensitive curable layer can form a sharp image with extremely excellent sharpness. .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION

[Photosensitive Composition and Production Thereof] The photosensitive composition of the present invention comprises a polymerizable compound, a hydrophobic polymer (having an acidic group partially or entirely in a salt state), an organic solvent, and silver halide. It is a mixture (emulsion) of an aqueous emulsion. Details of each component will be described later. The preferred composition ratio of each component is such that the polymerizable compound is contained in an amount of 0.1 to 100 parts by weight of the organic solvent.
2 to 20 parts by weight, 1 to 30 parts by weight of a hydrophobic polymer, and 0.5 to 25 parts by weight of an aqueous silver halide emulsion (0.1 to 5 parts by weight in terms of silver halide grains)
It is. More preferably, the polymerizable compound is 0.3 to 15 parts by weight, the hydrophobic polymer is 1.5 to 20 parts by weight, and the silver halide aqueous emulsion is 1 to 20 parts by weight (100 parts by weight of the organic solvent). 0.2 to 4 parts by weight in terms of silver particles). Most preferably, the polymerizable compound is 0.4 to 10 parts by weight, the hydrophobic polymer is 2 to 15 parts by weight, and the aqueous silver halide emulsion is 1.5 to 15 parts by weight (100 parts by weight of the organic solvent). 0.3 to 3 parts by weight in terms of silver particles).

The photosensitive composition is prepared by dissolving (1) a hydrophobic polymer having an acidic group and a polymerizable compound in an organic solvent,
(2) An alkaline compound (or a solution thereof) is added to the solution to neutralize a part or all of the acidic groups to form a salt, and (3) an aqueous silver halide emulsion is added and mixed. Can be manufactured. If the concentration of silver halide in the aqueous silver halide emulsion is high, silver halide grains may aggregate in the step (3). In order to prevent agglomeration, it is preferable to dilute the aqueous silver halide emulsion to an appropriate concentration with water. Alternatively, (1) the hydrophobic polymer having an acidic group is neutralized in advance with an alkaline compound, and a part or all of the acidic group is neutralized to form a salt, and (2) the hydrophobic polymer and the polymerizable compound are neutralized. The photosensitive composition may be produced by dissolving in an organic solvent, adding (3) an aqueous silver halide emulsion and mixing.

Further, (1) a hydrophobic polymer having an acidic group is neutralized in advance with an alkaline compound, and a part or all of the acidic group is neutralized to form a salt (with the result that some hydrophilicity is added). (2) A hydrophobic polymer is added to and mixed with an aqueous silver halide emulsion, and (3) An aqueous silver halide emulsion containing a hydrophobic polymer is added to a solution in which a polymerizable compound is dissolved in an organic solvent. And then mixing to produce a photosensitive composition. A hydrophobic polymer having an acidic group may be added to a solution of the polymerizable compound in the step (3) dissolved in an organic solvent. In this case, even if the amount of the hydrophobic polymer added to the aqueous silver halide emulsion is relatively small, it can function sufficiently as a dispersing polymer. The acidic group of the hydrophobic polymer to be added to the organic solvent solution of the polymerizable compound may be neutralized and may be in a salt state or may be in an acid state. This method has an advantage that aggregation of silver halide grains hardly occurs even if the water content of the aqueous silver halide emulsion is relatively small.

[Hydrophobic polymer] The photosensitive composition of the present invention contains a hydrophobic polymer. Further, the hydrophobic polymer used in the present invention has an acidic group which is partially or entirely in a salt state. A polymer having an acidic group in a salt state has hydrophilicity as a whole, but the main chain of the polymer (the portion other than the acidic group) is sufficiently hydrophobic (lipophilic).
, The hydrophobicity of the polymer as a whole is maintained.

The hydrophobic polymer preferably has crosslinkability. For crosslinking, it is preferable to introduce an ethylenically unsaturated bond into the main chain or side chain of the molecule. The crosslinkability may be introduced by copolymerization. Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene,
Mention may be made of natural and synthetic rubbers. Examples of the polymer having an ethylenically unsaturated bond in a side chain of a molecule include a polymer of an ester or amide of acrylic acid or methacrylic acid, wherein a residue of the ester or amide (R of —COOR or —CONHR) is used. A polymer having an ethylenically unsaturated bond can be mentioned.

Examples of the residue having an ethylenically unsaturated bond (the above R) include-(CH ₂ ) _n -CR ¹ = CR ² R ³ ,-(CH ₂ O) _n -C
H ₂ CR ¹ = CR ² R ³ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -NH
-CO-O-CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -O-CO-CR ¹ = CR ² R ³ and-
_{(CH 2 CH 2 O) 2} -X (R 1 ~R 3 , respectively, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, R ¹ And R ² or R ³ may combine with each other to form a ring, and n is 1 to
An integer of 10 and X is a dicyclopentadienyl residue). Specific examples of the ester residue, -CH ₂ CH = CH ₂ (JP-B-7-21633 _{described), - CH 2 CH 2 O} -CH 2 CH = CH 2, -CH 2 C (CH 3) = CH ₂ , -CH ₂ CH = C
HC ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCOO-CH ₂ CH =
CH ₂ and —CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) are included. Specific examples of amide residues include -CH ₂ CH = C
_{H 2, -CH 2 CH 2 -1} -Y (Y is cyclohexene residue) and -C
H ₂ CH ₂ -OCO-CH = CH ₂ is included. In the crosslinkable polymer as described above, a free radical (a polymerization initiation radical or a growing radical in the polymerization process of the polymerizable compound) is added to the unsaturated bonding group, and directly between the polymers or via a polymerization chain of the polymerizable compound. This causes addition polymerization to form crosslinks between the polymer molecules and cure. Alternatively, free radicals abstract atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to unsaturated bond groups) to form polymer radicals, which combine with each other to form crosslinks between polymer molecules. Being cured.

As the non-crosslinkable (non-crosslinkable or weakly crosslinkable) polymer, a saturated aliphatic residue or an aromatic residue may be used instead of the above-mentioned residue (R) having an ethylenically unsaturated bond. , Polymethacrylic esters (eg, polymethyl methacrylate, polybenzyl methacrylate), polyacrylamide, and polymethacrylamide. Examples of other non-crosslinkable polymers include polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethacrylonitrile, polyethylene, polyvinylpyridine, polyvinylimidazole, polyvinylbutyral, polyvinylformal, polyvinylpyrrolidone, chlorinated It includes polyethylene, chlorinated polypropylene, polyester, polyamide, polyurethane, polycarbonate, cellulose ether (eg, ethyl cellulose) and cellulose ester (eg, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate).

In the present invention, an acidic group is introduced into the above-mentioned hydrophobic (and crosslinkable or non-crosslinkable) polymer for use. Examples of the acidic group include a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, and a sulfonimide group.
Carboxyl groups are particularly preferred. Specifically, (meta)
Acrylic acid, styrene sulfonic acid or maleic anhydride monomer is copolymerized during polymer synthesis,
These acidic groups can be incorporated into the polymer of the curable layer. The molar content of the monomer having an acidic group in the copolymer is preferably 1 to 60%,
And more preferably from 50 to 50%.
% Is most preferred. The molecular weight of the hydrophobic polymer having an acidic group is preferably in the range of 1,000 to 500,000. Two or more polymers may be used in combination.

In the present invention, some or all of the acidic groups of the hydrophobic polymer are used in the form of a salt. 1 g of the hydrophobic polymer contains 5 × 10 ^{-5 to} 3 × 10 ^-3 mol of acidic groups in a salt state. The acidic group in a salt state is 1.7 × 10 ^−4.
And preferably from 3 to 10 ³ mol.
More preferably, it is contained in an amount of 0 × 10 ^{−4 to} 3 × 10 ⁻³ mol. The acidic groups preferably form salts with alkali metals, alkaline earth metals, ammonium or organic bases. Alkali metals (eg, potassium, sodium)
Is particularly preferred. As described above, by adding a basic substance to the hydrophobic polymer having an acidic group, the acidic group is neutralized into a salt state. Examples of basic substances include:
Lithium hydroxide, sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium methoxide, potassium methoxide, Mention may be made of sodium acetate, potassium acetate and ammonium hydroxide. For neutralization of the acidic group, it is preferable to use a solution of a basic substance rather than the basic substance itself. There is no particular limitation on the type of the solvent for the basic substance. However, depending on the type of the hydrophobic polymer, the content of the acidic group, or the type of the solvent of the basic substance, the polymer may be precipitated in the preparation of the photosensitive composition. In particular, when the amount of the basic substance or its solvent is large, the polymer is likely to precipitate. In the case of precipitation, the amount of the basic substance solvent added is 20% by weight or less, preferably 10% by weight, based on the organic solvent of the photosensitive composition.
It is preferable to adjust the concentration of the basic substance so as to be not more than% by weight. Further, the precipitation can be prevented by changing the type of the solvent of the basic substance or the type of the organic solvent.

[Polymerizable compound] As the polymerizable compound,
A compound capable of undergoing addition polymerization by a free radical, particularly a compound (monomer or oligomer) having an ethylenically unsaturated group is used. The polymerizable compound is described in JP-A-5-249667. Examples of the compound having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic esters, acrylamides, methacrylic acid and salts thereof, methacrylic esters, methacrylamides, maleic anhydride, maleic esters , Itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers and allyl esters. Acrylic esters or methacrylic esters are particularly preferred. Specific examples of (meth) acrylates include pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester (meth) acrylate and polyurethane (meth) acrylate Can be mentioned. Two or more polymerizable compounds may be used in combination.

[Organic solvent] Examples of the organic solvent include ketones (eg, acetone, methyl ethyl ketone), esters (eg, methyl acetate, ethyl acetate), alcohols (eg, methanol, ethanol, 1-propanol, isopropanol, 1-propanol). Butanol, 2-butanol, tert-butanol, isobutyl alcohol, ethylene glycol,
Propylene glycol monomethyl ether, cyclohexanol), halogenated hydrocarbons (methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride), amides (eg, N-methylformamide, dimethylformamide), sulfoxides (eg, dimethyl sulfoxide) and ethers (Eg, propylene glycol monomethyl ether, tetrahydrofuran, dioxane). The solvent preferably has a boiling point of 30 to 200 ° C., more preferably 40 to 150 ° C., and most preferably 50 to 130 ° C. Two or more solvents may be used as a mixture.

[Aqueous silver halide emulsion] As the silver halide, any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used. Particles can also be used. The shape of the silver halide grains is preferably cubic or tetradecahedral, but is not limited to those having a regular crystal form, and may be those having an irregular crystal form or a complex form thereof. Anomalous crystal forms include potato, spherical, plate and plate crystal forms. In the case of tabular grains, the grain size is generally at least five times the grain thickness. There is no particular limitation on the grain size of the silver halide. Fine particles of 0.01 μm or less can also be used. On the other hand, large particles of about 10 μm can be used. With respect to grain size distribution, monodisperse grains are preferred over polydisperse emulsions. For monodisperse emulsions, see US Pat.
Nos. 628 and 3655394 and British Patent 1413.
No. 748 is described in each specification.

The crystal structure of the silver halide grains may be uniform or may have a different halogen composition between the inside and the outside. It may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining. Further, it may be bonded to a compound other than silver halide. Examples of compounds other than silver halide include silver rhodan and lead oxide. The silver halide grains may contain salts of other elements. Examples of other elements include copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold and Group VIII noble metals (eg, rhodium, iridium, iron, platinum, palladium) Can be mentioned. Salts of these elements can be added during or after the formation of silver halide grains and included in the grains. Specific methods are described in U.S. Patent Nos. 1195432, 1951933, 2448860 and 26281.
Nos. 67, 2950972, 3488709, 3737313, 37372031, 42699
No. 27, and Research Disclosure (RD), Vol. 13452 (June 1975).

By adding an aqueous solution of an iridium compound to the emulsion during the preparation of the aqueous silver halide emulsion, iridium ions can be introduced into the silver halide grains.
Examples of water-soluble iridium compounds include hexachloroiridium (III) and hexachloroiridium (I
V) acid salts. Similarly, rhodium ions may be introduced into silver halide grains by adding an aqueous solution of a rhodium compound to the emulsion. Examples of water-soluble rhodium compounds include rhodium ammonium chloride,
Rhodium trichloride and rhodium chloride can be mentioned. An iridium compound or a rhodium compound may be used by dissolving it in an aqueous solution of a halide for forming silver halide grains. Further, the aqueous solution of the iridium compound or the rhodium compound may be added before the particles are formed, or may be added during the formation of the particles. Further, it may be added during the period from grain formation to chemical sensitization treatment. It is particularly preferred to add while the particles are being formed. The iridium ion or the rhodium ion is preferably used in an amount of 10 ^{-8 to} 10 ^-3 mol, more preferably 10 ^{-7 to} 10 ^-5 mol, per 1 mol of silver halide. When the rhodium compound and the iridium compound are used in combination, the use of the former is preferably at a stage before the use of the latter.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits and grain sizes can be used in combination. Aqueous silver halide emulsions are described in Research Disclosure (RD), no. 17643 (1978)
December 23), pages 22-23, "I. Emulsion Production (Emulsion
preparation and types) "and No. 18716
(November 1979), page 648. The silver halide aqueous emulsion is
Usually, chemical sensitization is performed after physical ripening. It is preferable to use silver halide grains having a relatively low fog value. Additives used in such a process are described in Research Disclosure Magazine, No. No. 17643 and the same No. 18716. Regarding chemical sensitizers, 1764
3 (p. 23) and No. 3 18716 (page 648, right column)
Respectively. Known additives other than those described above are also described in the above two Research Disclosures. For example, for a sensitivity enhancer, N
o. No. 18716 (page 648, right column), No. 1 for the antifoggant and the stabilizer. 17643 (24-25 pages)
And No. 18716 (from page 649, right column).

The aqueous silver halide emulsion is usually used after spectral sensitization. Spectral sensitizing dyes are known in the ordinary photographic art. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Spectral sensitizing dyes can be written on the same photosensitive material with light sources of different wavelengths such as various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and light emitting diodes Therefore, a plurality of sensitizing dyes having different spectral wavelengths can be applied to silver halide in the same or different photosensitive layers. Along with sensitizing dye,
A dye having no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (supersensitizer) may be added to the emulsion. For spectral sensitizing dyes, see Research Disclosure, N
o. 17643 (December 1978), pp. 23-24,
The supersensitizers are described in 18716 (November 1979), page 649.

[Photosensitive Material] The photosensitive material is produced by applying the above-mentioned photosensitive composition on a support and forming a photosensitive curable layer. In addition, any components of the photosensitive curable layer described below can be added to the photosensitive composition of the present invention. An overcoat layer may be provided on the photosensitive curable layer, and an intermediate layer may be provided therebetween. The reducing agent may be added to any of the layers, but is preferably added to the photosensitive curable layer. It is preferable that the components of the photosensitive curable layer are uniformly contained in the layer without using microcapsules. The photosensitive material may be provided with a functional layer other than the above. Other functional layers include an adhesive layer, a release layer and an undercoat layer. The coating amount of the photosensitive composition is preferably 0.01 to 5 g / m ² , more preferably 0.03 to 1 g / m ² , and more preferably 0.05 to 1 g / m ² , in terms of silver halide. Most preferably, it is 0.3 g / m ² . The amount of the hydrophobic polymer is preferably 30 to 95% by weight of the whole photosensitive curable layer, and 50 to 9% by weight.
More preferably, it is 0% by weight. The amount of the polymerizable compound is preferably in the range of 3 to 200% by weight of the amount of the hydrophobic polymer, and more preferably in the range of 10 to 100% by weight.

[Support] As the support, paper, synthetic paper,
Paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg, aluminum, aluminum alloy,
Zinc, iron, copper), and paper or plastic film on which these metals are laminated or deposited can be used. When the photosensitive material is used for producing a lithographic printing plate, preferred supports are an aluminum plate, a polyethylene terephthalate film, a polycarbonate film, paper and synthetic paper. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. Aluminum plates are particularly preferred.

The case where an aluminum plate is used as a support will be further described. The aluminum support is subjected to a surface treatment such as a surface roughening treatment (graining treatment) or a surface hydrophilic treatment as necessary. The surface roughening treatment may be performed by an electrochemical sanding method (for example, a method of sanding an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte) and / or a mechanical sanding method. (For example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is sanded with a polishing ball and an abrasive, a brush grain in which the surface is sanded with a nylon brush and an abrasive) Method).

Next, the grained aluminum plate is chemically etched with an acid or an alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of the alkali treatment is preferably in the range of 20 to 100 ° C. Further, it is preferable to adjust the processing conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² . Usually, after the alkali etching, the aluminum plate is washed with an acid to remove dirt (smut) remaining on the surface.
Preferred acids are nitric, sulfuric, phosphoric, chromic, hydrofluoric and borofluoric acids. The smut removal treatment after the electrochemical graining treatment can be performed by a known method such as a method of contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C.

The aluminum plate subjected to the surface roughening treatment as described above can be subjected to an anodic oxidation treatment or a chemical conversion treatment, if necessary. The anodic oxidation treatment can be performed by a known method. Specifically, in an acid solution,
An anodic oxide film is formed on the aluminum surface by passing a direct current or an alternating current through the aluminum plate. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulphamic acid and benzenesulphonic acid. Anodizing conditions vary depending on the electrolyte used. Generally, the concentration of the electrolyte is 1 to 80% by weight, the temperature of the electrolyte is 5 to 70 ° C., and the current density is 0.5%.
To 60 amps / dm ^2, a voltage of ^from 1 to 100v, and electrolysis time is preferably in the range of 10 to 100 seconds. Particularly preferred anodic oxidation methods are a method of performing anodization at a high current density in sulfuric acid and a method of performing anodization using phosphoric acid as an electrolytic bath. After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in an aqueous solution of sodium silicate). Further, in order to improve the adhesion between the aluminum support and the photosensitive curable layer and the printing characteristics, an undercoat layer may be provided on the support surface.

[Undercoat Layer] The undercoat layer is provided as a hydrophilic layer not only on the aluminum support described above but also on a support whose surface is not sufficiently hydrophilic (eg, a polymer film). As a component constituting the undercoat layer, a polymer (eg,
Gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid); amines (eg, monoethanolamine, diethanolamine, triethanolamine,
Tripropanolamine) and their hydrochlorides, oxalates or phosphates; monoaminomonocarboxylic acids (eg, aminoacetic acid, alanine); oxyamino acids (eg,
Serine, threonine, dihydroxyethylglycine);
Sulfur-containing amino acids (eg, cysteine, cystine); monoaminodicarboxylic acids (eg, aspartic acid, glutamic acid); diaminomonocarboxylic acids (eg, lysine); amino acids having an aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine) Aliphatic aminosulfonic acid (eg, sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (eg, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamine) Acetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). A compound in which some or all of the acid groups of the above compounds have become salts (eg, sodium salt, potassium salt, ammonium salt) can also be used. The above components can be used in combination of two or more. When a polymer film is used as the support, hydrophilic fine particles (eg, silica powder) are preferably added to the hydrophilic undercoat layer instead of the graining treatment of the aluminum support.

[Photosensitive curable layer] The photosensitive curable layer is formed by applying the photosensitive composition of the present invention as described above.

[Overcoat layer] The overcoat layer has a function of protecting the photosensitive material and preventing the intrusion of oxygen in the air to increase the degree of curing of the photosensitive curable layer. Further, the overcoat layer may contain components for promoting image formation (eg, a base, a base precursor, a reducing agent, a silver halide development accelerator, a thermal development accelerator). The overcoat layer is generally formed using a hydrophilic polymer. The coating amount of the overcoat layer is 0.3 to 20 g /
m ² , more preferably 0.5 to 20 g / m ² .

[Intermediate layer] An intermediate layer can be provided on the light-sensitive material. The intermediate layer is an adhesive layer, an antihalation layer,
It can also function as a filter layer or a barrier layer. The intermediate layer has a function of enhancing the adhesive strength between each layer or between the support and the photosensitive curable layer. The antihalation layer and the filter layer are functional layers containing a coloring agent. The barrier layer has a function of preventing components from migrating between layers and diffusing or mixing during storage of the photosensitive material. The material of the intermediate layer is determined according to the application.
The coating amount of the intermediate layer is preferably 10 g / m ² or less.

[Organic metal salt] In addition to the silver halide, an organic metal salt can be added to the light-sensitive material. It is particularly preferable to use an organic silver salt. Examples of the organic compound used to form the organic silver salt include triazoles, tetrazoles, imidazoles, indazoles, thiazoles, thiadiazoles, azaindenes, and aliphatic, aromatic, or aromatic compounds having a mercapto group as a substituent. Heterocyclic compounds can be mentioned. Further, silver salts of carboxylic acids and silver acetylene can also be used as organic silver salts.
Two or more organic silver salts may be used in combination. The organic silver salt is used in an amount of 10 ^{-5 to} 10 mol, preferably 10 ^{-4 to} 1 mol, per 1 mol of silver halide.

[Reducing Agent] The reducing agent has a function of reducing silver halide or a function of promoting polymerization of a polymerizable compound (or crosslinking of a crosslinkable polymer). As the reducing agent, hydrazines, hydroquinones, catechols,
p-aminophenols, p-phenylenediamines,
3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,
5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, o- or p-acylaminophenols,
2-Sulfonamide indanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles and α-sulfonamidoketones are used.

The reducing agent is described in JP-A-61-183640,
Nos. 61-188535, 61-228441, 62-70836, 62-86354 and 62-
No. 86355, No. 62-206540, No. 62-26
No. 4041, No. 62-109437, No. 63-254
442, JP-A-1-267536 and 2-1417
No. 56, No. 2-141775, No. 2-207254
And JP-A-2-262662 and JP-A-2-269352 (including those described as a developing agent or a hydrazine derivative). As for the reducing agent,
"The Theory of the Photographic Proces" by T. James
s "Fourth Edition, pp. 291-334 (1977), Research Disclosure, Vol. 170, No. 17029.
No. 9-15, (June 1978), and the same magazine, Vo
l.176, No.17643, pp.22-31, (1978
December). Further, Japanese Patent Application Laid-Open No. 62-210
As in the light-sensitive material described in Japanese Patent No. 446, a reducing agent precursor that releases the reducing agent under heating conditions or in contact with a base may be used instead of the reducing agent.

The basic reducing agent which forms a salt with an acid can be used in the form of a salt with a suitable acid. Two or more reducing agents may be used in combination. The interaction of two or more reducing agents is, first, to promote the reduction of silver halide (or organic silver salt) by so-called superadditivity, and second, to promote silver halide (or organic silver salt). It is conceivable that the oxidized form of the first reducing agent generated by the reduction of the compound causes polymerization of the polymerizable compound (or suppresses the polymerization) via an oxidation-reduction reaction with another coexisting reducing agent. The reducing agent is preferably used in an amount of 0.1 to 10 mol, more preferably 0.25 to 2.5 mol, per 1 mol of silver halide.

[Anti-fogging agent, silver development accelerator, stabilizer]
In order to improve photographic properties, additives such as an antifogging agent, a silver development accelerator for accelerating silver development, and a stabilizer may be added to any of the layers. Examples thereof include mercapto compounds (described in JP-A-59-111636), azoles and azaindenes (described in Research Disclosure No. 17643, pages 24 to 25 (1978)), and carboxylic acids containing nitrogen. And phosphoric acids (described in JP-A-59-168442), cyclic amides (described in JP-A-61-151841), thioethers (described in JP-A-62-151842), and polyethylene glycol derivatives (described in JP-A-62-151842). No. -151843), thiols (described in JP-A-62-151844), acetylene compounds (described in JP-A-62-87957), and sulfonamides (described in JP-A-62-1782).
No. 32). As the silver development accelerator or the antifoggant, an aromatic ring (carbon ring or heterocyclic) mercapto compound (described in JP-A-6-313967) is particularly preferred. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are more preferred. The mercapto compound may be added to the light-sensitive material as a mercapto silver compound (silver salt). These compounds may be used in an amount of 10 ^-7 mol to 1 mol per mol of silver halide.
Range of moles.

[Hydrophilic polymer] The optional hydrophilic layer (overcoat layer or intermediate layer) contains a hydrophilic polymer as a binder. The hydrophilic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in a molecular structure. Examples of hydrophilic groups include carboxyl, alcoholic hydroxyl, phenolic hydroxyl, sulfo, sulfonamide, sulfonimide and amide. Examples of the hydrophilic bond include a urethane bond, an ether bond and an amide bond. It is preferable to use a water-soluble polymer or a water-swellable polymer as the hydrophilic polymer.
A water-swellable polymer has an affinity for water,
It does not completely dissolve in water due to the crosslinked structure of the polymer. Water-soluble polymers are preferred over water-swellable polymers. As the water-soluble or water-swellable polymer, a natural, synthetic or semi-synthetic polymer compound can be used. For the hydrophilic polymer, see JP-A-5-249.
No. 667 discloses this.

Polyvinyl alcohol is a particularly preferred hydrophilic polymer. Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen permeability, the degree of saponification is preferably 70% or more, and more preferably 80% or more. Copolymerized modified polyvinyl alcohol can also be used. Copolymerization modification is a method of saponifying a copolymer of vinyl acetate and another monomer to synthesize a modified polyvinyl alcohol. Examples of monomers to be copolymerized include ethylene, higher vinyl carboxylate, higher alkyl vinyl ether, methyl methacrylate and acrylamide. Also, post-modified polyvinyl alcohol can be used. The post-modification is a method in which a compound having reactivity with a hydroxyl group of polyvinyl alcohol is used to modify polyvinyl alcohol by a polymer reaction after synthesis. Specifically, the hydroxyl group of polyvinyl alcohol is
Modification by etherification, esterification or acetalization.

Further, a cross-linked polyvinyl alcohol can be used. As the cross-linking agent, an aldehyde, a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid, or an inorganic cross-linking agent (eg, boric acid) can be used. The molecular weight of the hydrophilic polymer is preferably in the range of 3000 to 500,000.

[Base and Base Precursor] The photosensitive material preferably contains a base or a base precursor. As the base, various inorganic and organic bases can be used, and as the base precursor, those precursors (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type or dissociation type) can be used. From the viewpoint of storage stability of photosensitive materials,
Base precursors are preferred over bases. Examples of the decarboxylation type base precursor include salts of organic acids and bases which are decarboxylated by heating (JP-A-63-316760;
4-68746, 59-180537 and 6
No. 1-313431). Examples of the pyrolytic base precursor include a urea compound (described in JP-A-63-96159). Examples of reactive base precursors include:
Transition metal acetylides (described in JP-A-63-25208) can be exemplified. Examples of complex salt-forming base precursors include basic metal compounds that are poorly soluble in water (described in JP-A-1-28282). Examples of dissociative bases include alkali metal salts of organic acids (eg, sodium acetate, sodium salts of polymers having acidic groups). The base precursor preferably generates a base at 50 to 200 ° C, more preferably 80 to 160 ° C. The hydrophobic polymer used in the photosensitive composition of the present invention may function as a base precursor in some cases. The base precursor is preferably used in the range of 0.1 to 20 mol per mol of silver halide,
More preferably, it is in the range of 0.2 to 10 mol.

[Heat Development Accelerator] In order to carry out the heat development at a lower temperature or in a shorter time, a heat development accelerator may be added to any layer of the photosensitive material. As the thermal development accelerator, a compound having a plasticizing effect at room temperature or upon heating with respect to a binder used in any layer of the photosensitive material, or a compound having no plasticizing effect but capable of melting in the layer by heating is used. Can be used. It is considered that the thermal development accelerator promotes thermal development by promoting the diffusion of the reactant in the photosensitive material or by promoting the reaction itself. Examples of the compound having a plasticizing action include “Plastic Additives” Taiseisha, P21-63; “Plastics Additiv 2nd Edition” (Plastics Additiv)
es, 2nd Edition, Hanser Publishers) 5th small, 251
Pp. 296 to 296 can be used. Preferred thermal development accelerators include polyethers (eg, polyethylene glycol, polypropylene glycol), polyhydric alcohols (eg, glycerin, hexanediol), sugars (eg, sorbitol), formate esters, ureas (eg, urea, diethyl) Urea, ethylene urea), amides (eg, acetamide, propionamide, malonamide), sulfamides, sulfonamides, urea resins and phenol resins. Two or more thermal development accelerators can be used in combination. Further, it may be added in two or more layers. The addition amount of the thermal development accelerator is preferably 0.05 to 2 g / m ² , and more preferably 0.1 to 1 g / m ² .

[Colorant] A colorant can be added to a light-sensitive material for the purpose of preventing halation and irradiation, coloring a cured image or adjusting sensitivity (absolute sensitivity or spectral sensitivity). As the colorant, known pigments and dyes can be used as long as they do not significantly hinder the curing reaction or significantly deteriorate the photosensitivity and developability of silver halide. When a colorant is added to prevent halation and irradiation, those capable of absorbing light in the photosensitive wavelength region of silver halide are preferred. Examples of the colorant include JP-A-5-249667, Color Index Handbook, Dye Handbook (edited by The Society of Synthetic Organic Chemistry, 1970).
And the pigments, dyes and colloidal silver described in (1). Dyes for preventing irradiation which have little effect on the sensitivity of silver halide are described in JP-B-41-20389.
JP-A-43-3504, JP-A-43-13168 and JP-A-2-39042, and U.S. Pat.
Nos. 037 and 3423207, British Patent 103039
Nos. 2 and 1100546 are described in each specification. The addition amount of the colorant is preferably in the range of 0.01 to 2 g / m ^2, further preferably in the range of 0.05 to 1 g / m ^2.

[Development Stopping Agent] Various development stopping agents can be used for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during thermal development. A development terminator is a compound that immediately neutralizes a base or reacts with a base to reduce the base concentration in a layer and stop development after proper development, or a compound that interacts with silver and a silver salt to suppress development. is there.
Specifically, an acid precursor that releases an acid upon heating,
An electrophilic compound that undergoes a substitution reaction with a coexisting base upon heating, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof can be used. The thermal development terminator is described in JP-A-62-253159 and JP-A-2-2-159.
Nos. 42447 and 2-262661.

[Surfactant] A known surfactant may be added to any of the layers. Any of a nonionic activator, an anionic activator, a cationic activator and a fluorine activator can be used. For the surfactant, see JP-A-2-195356.
There is a description in the publication. Sorbitans, polyoxyethylenes and fluorinated surfactants are particularly preferred.

[Matting Agent] A matting agent is added to the back layer or overcoat layer of the photosensitive material for the purpose of reducing the tackiness of the front or back surface of the photosensitive material and preventing adhesion when the photosensitive materials are stacked. Can be. As the matting agent, inorganic or organic solid particles that can be dispersed in a hydrophilic polymer are used. Examples of matting materials include:
Oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers can be mentioned. The particle size of the matting agent is 0.
A range of 5 to 50 μm is preferred. The coating amount of the matting agent is preferably in the range of 0.1 to 1 g / m ² .

[Polymerization Inhibitor] In order to prevent the polymerizable compound from being polymerized during storage of the light-sensitive material, a known polymerization inhibitor can be used. Examples of polymerization inhibitors include nitrosamines, ureas, thioureas, thioamides, phenols and amines.

[Exposure Step] The image exposure is performed with light having a wavelength corresponding to the spectral sensitivity of silver halide. The wavelength is visible light,
Near-ultraviolet light and near-infrared light are generally used, but X-rays and electron beams may be used. Examples of light sources include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, and various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, YAG laser), light emitting diode, cathode ray tube and the like. Exposure doses generally range from 0.01 to 10000 ergs / cm ² , preferably from 0.1 to 1000 erg / cm ² .
When the support is transparent, exposure can be performed through the support from the back side of the support.

In the process of forming a latent image of silver halide, the sensitivity is liable to change under the influence of temperature and humidity during exposure. Therefore, it is desirable that the temperature and humidity of the atmosphere of the photosensitive material and the light source be controlled within a certain range. The adjusting means of the image recording apparatus for achieving the above object is disclosed in
These are described in JP-A-63143 and JP-A-3-63637.

[Development Step] The development of the photosensitive material is performed by a dry method (heat development) by heating. The thermal development can be performed by a method in which the photosensitive material is brought into close contact with a heated object (eg, a metal plate or a metal roller), a method in which the photosensitive material is immersed in a heated liquid, or a method in which infrared light is irradiated. The surface of the photosensitive material may be opened to the air and heated from the support side, or the surface may be closely contacted with a heated object and heated while the air is shut off. If you open the surface into the air and heat it,
Since oxygen in the air may proceed into the photosensitive material and inhibit the curing reaction, it is preferable to use the above-described polymer having a low oxygen permeability as a binder for a layer on the surface side such as an overcoat layer. preferable. The heating temperature is in the range of 60 to 200 ° C, more preferably 100 to 160 ° C. The heating time ranges from 1 to 180 seconds, more preferably from 5 to 60 seconds. Before or after the exposure step, the photosensitive material may be preheated at a lower temperature or for a shorter time than the main heating conditions. Post-heating may be performed after the main heating or after the removal step (described later).

[Removing Step] In order to form an image by removing the uncured portion (non-image portion), it is preferable to remove the uncured portion by elution. When a hydrophilic layer such as an overcoat layer is provided on the photosensitive curable layer, the hydrophilic layer may be removed by washing or mechanical peeling before removing the uncured portion. preferable. It is preferable to use an alkaline eluate as the eluate. Examples of the alkaline compound used in the alkaline eluate include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate,
Includes potassium metasilicate, sodium phosphate, potassium phosphate, ammonia and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine). As a solvent for the eluate, water is preferable. If necessary, an organic solvent may be added to water.
As the organic solvent, alcohols or ethers are preferable. Examples of alcohols include lower alcohols (eg, methanol, ethanol, propanol, butanol),
Alcohols having aromatic groups (eg, benzyl alcohol, phenethyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol) and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine) ) Is included. Examples of ethers include cellosolves. The eluate may contain a surfactant, an antifoaming agent, and other various additives as necessary.

[Use of photosensitive material] The photosensitive material can be used for forming a hard copy or a relief image or for producing a printing plate. In particular, it is suitable for producing a printing plate.

[0060]

【Example】

[Example 1] "Preparation of silver halide aqueous emulsion" Gelatin, potassium bromide and water were added, sodium hydroxide was added, and pH at room temperature was added.
Was adjusted to 9.5, the mixture was heated to 55 ° C., and the following thioether compound was added 2.0 × 1 to the added amount of silver nitrate.
0 ^-3 was added in an amount of molar equivalent. While maintaining the pAg value of the reaction vessel at 9.0, the molar ratio of the aqueous solution of silver nitrate and rhodium to the total addition amount of potassium iodide and silver nitrate was 4 ×.
An aqueous potassium bromide solution containing rhodium ammonium chloride in an amount of 10 ^-8 mol was added by a pAg control double jet method to form silver iodobromide particles. Next, sulfuric acid was added to adjust the pH to 6.0,
Subsequently, at 55 ° C. and pAg = 8.6, an aqueous solution of silver nitrate and a potassium bromide solution to which hexachloroiridium (III) acid salt was added at a molar ratio of iridium to silver of 5 × 10 ⁻⁷ mol were added. The mixture was added in two stages by a double jet method to prepare a core / shell type silver iodobromide aqueous emulsion having the following composition.

[0061]

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Core: silver iodobromide (silver iodide content: 8.5 mol%) Shell: pure silver bromide Core / shell: 3/7 (silver molar ratio) Average silver iodide content: 2.55 Mol% average particle size: 0.30 μm

The obtained emulsion grains were monodispersed and contained 98% of all grains within ± 40% of the average grain size. Next, the emulsion was desalted, and the pH was adjusted to 6.5 and p
Ag was adjusted to 9.0. The emulsion was kept at 50 ° C., and while stirring, a methanol solution of the following spectral sensitizing dyes A and B (molar ratio, A: B = 2: 1) was added in a total amount of 8 × 10 5
^-4 mol / mol Ag was added in an equivalent amount, and the mixture was maintained for 20 minutes.
Further, the following thiol sodium salt was added to 6 × 10 ^−4.
An equivalent amount of mol / mol Ag was added, and the mixture was stirred and held for 5 minutes to prepare an aqueous silver halide emulsion.

[0064]

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[0065]

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[0066]

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"Preparation of aqueous phase" Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20)
Wt% polpyrene glycol monomethyl ether solution 1
While stirring 0 g, 3.2 g of a 1N aqueous solution of sodium hydroxide was added thereto to neutralize acidic groups in the polymer. To this solution, 13 g of water and 13 g of the above-mentioned silver halide aqueous emulsion were mixed to prepare an aqueous phase.

"Preparation of pigment dispersion" A pigment dispersion having the following composition was prepared.

────────────────────────────────────Pigment dispersion liquid────────銅 Copper phthalocyanine 15 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio = 80/20) 15 g Methyl ethyl ketone 70 g ────────────────────────────────────

"Preparation of Oil Phase" A mixture having the following composition was stirred to prepare an oil phase.

────────────────────────────────────Oil phase─────────重合 Polymerizable compound (KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.) 1.2 g Allyl methacrylate / Methacrylic acid copolymer (copolymerization molar ratio = 80/20) 3.7 g Propylene glycol monomethyl ether 50.0 g Methyl ethyl ketone 15.0 g 0.4% by weight of the following additive solution in methyl ethyl ketone 4.0 g 10% by weight of the following reducing agent 13.0 g of methyl ethyl ketone solution 12.0 g of the above pigment dispersion liquid 1.8 g of a 10% by weight solution of polyethylene glycol (average molecular weight = 400) in methyl ethyl ketone ─────────── ─────

[0072]

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[0073]

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[Preparation of Photosensitive Composition] A 4% by weight methanol solution of sodium hydroxide 8.3 was stirred while the oil phase was stirred.
g was added to neutralize the acidic groups in the polymer. 10 g of an aqueous phase was added to this solution and stirred to prepare a photosensitive composition. The amount of the salt of the acidic group per 1 g of the hydrophobic polymer is
1.5 × 10 ^-3 mol. Observation of the photosensitive composition with a microscope revealed that the silver halide grains were uniformly dispersed without agglomeration.

Example 2 "Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the aluminum plate according to SA-1050 was grained with a nylon brush and an aqueous suspension of pamistone (400 mesh), and then thoroughly washed with water. Next, the film was immersed in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. It was neutralized and washed with a 20% aqueous nitric acid solution, and then washed with water. The obtained aluminum plate was subjected to a square wave alternating current (condition: anode voltage 12.7 V, ratio of cathode electricity to anode electricity: 0.9, anode electricity 160 coulomb / dm ² ).
Was subjected to electrolytic surface roughening treatment in a 1% by weight aqueous nitric acid solution containing 0.5% by weight of aluminum nitrate. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Subsequent to this treatment, the substrate was immersed in a 1% by weight aqueous solution of sodium hydroxide at 40 ° C. for 30 seconds, and then treated in a 30% by weight aqueous solution of sulfuric acid at 55 ° C. for 1 minute. Next, when the thickness is 2.5 g /
such that dm ^2, 20 wt% under conditions of a current density of 2A / dm ² using a direct current in an aqueous solution sulfuric acid, anodized, washed with water to prepare a dried support.

[Formation of Photosensitive Curable Layer] The photosensitive composition prepared in Example 1 was coated on a support and dried to form a photosensitive curable layer having a dry film thickness of about 2.0 μm. Was.

(Image formation) The above photosensitive material (printing original plate)
First, an original (a halftone image for printing (200 lpi) and a step wedge) and a band-pass filter (about 670 nm)
Then, the resultant was image-exposed using a xenon flash lamp with an exposure time of 10 ⁻⁴ seconds and an energy amount of 2 μJ / cm ³ . Next, the surface of the photosensitive material was brought into close contact with a hot plate heated to 150 ° C., and was thermally developed for 20 seconds. Further, the photosensitive material was immersed in an alkaline eluent (Fuji PS Developer DP-4 manufactured by Fuji Photo Film Co., Ltd.) at 30 ° C. for 20 seconds to elute the uncured portion of the photosensitive curable layer. As a result, a blue image was obtained in the exposed portion.

[Example 3] (Preparation of photosensitive material) In the same manner as in Example 2, a photosensitive curable layer was formed on a support. Next, a coating solution having the following composition is applied on the photosensitive curable layer and dried to a film thickness of about 3.
An overcoat layer of 5 μm was provided.

塗布 Coating solution for overcoat layer────── １０ 10 of acid-modified polyvinyl alcohol (degree of saponification: 98%, manufactured by Kuraray Co., Ltd.) Weight% aqueous solution 100.0 g 5 wt% aqueous solution of the following surfactant 2.0 g ──────

[0080]

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(Image formation) The obtained photosensitive material was used in Example 2.
The photosensitive material was adhered to a hot plate heated to 155 ° C. in the same manner as described above, and heat development was performed for 20 seconds with the surface of the photosensitive material opened to air. Then, Example 1
When treated with the eluate in the same manner as described above, a blue image was obtained in the exposed portion.

Example 4 "Preparation of Base Precursor Dispersion" 250 g of the following base precursor powder was dispersed in 750 g of a 3% by weight aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) using a Dynomill disperser. did. The particle size of the base precursor was about 0.5 μm or less.

[0083]

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(Preparation of photosensitive material) In the same manner as in Example 2, a photosensitive curable layer was formed on a support. Next, a coating solution having the following composition is applied on the photosensitive curable layer and dried,
An overcoat layer having a thickness of about 4.0 μm was provided.

塗布 Coating solution for overcoat layer────── １０ 10 of acid-modified polyvinyl alcohol (degree of saponification: 98%, manufactured by Kuraray Co., Ltd.) Weight% aqueous solution 100.0 g base precursor dispersion liquid 5.0 g 5 wt% aqueous solution of surfactant used in Example 3 2.0 g ───────────────────

(Image formation) The obtained photosensitive material was used in Example 2.
In the same manner as described above, image exposure was performed at an energy of 1 μJ / cm ² , then the support of the photosensitive material was brought into close contact with a hot plate heated to the temperature shown in Table 1 and thermally developed for 20 seconds. afterwards,
When treated with the eluate in the same manner as in Example 1, a blue image was obtained in the exposed portion. At the same heat development temperature (155 ° C.) as in Example 3, an image similar to that of Example 3 was obtained.
When printing was performed using the obtained image (printing plate), a good printed matter was obtained. Table 1 shows the evaluation results of the image quality.

[Example 5] (Preparation of photosensitive material) In the same manner as in Example 2, a photosensitive curable layer was formed on a support. Next, a coating solution having the following composition is applied on the photosensitive curable layer and dried, so that the film thickness becomes about 0.1.
An intermediate layer of 5 μm was provided.

<< Coating Solution for Intermediate Layer >> ３ 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 80%, manufactured by Kuraray Co., Ltd.) Liquid 100.0 g 5% by weight aqueous solution of surfactant used in Example 3 2.0 g ───────

On the intermediate layer, the same overcoat layer as in Example 4 was provided.

(Image formation) The obtained photosensitive material was used in Example 4.
When an image was formed in the same manner as in Example 4, almost the same good results as in Example 4 were obtained.

[Comparative Example 1] [Formation of a curable layer] A coating solution having the following composition was applied onto the support used in Example 1 and dried to obtain a dry film thickness of about 1.8 µm.
m curable layers were provided.

<< Coating Liquid for Curable Layer >> ────────────────────────────── Polymerizable compound (KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.) 1.2 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio = 80/20) 4.2 g Propylene glycol monomethyl ether 55.0 g Methyl ethyl ketone 30.7 g Pigment dispersion used in Example 1 12.0 g ────────────────────────────

"Preparation of Reducing Agent Dispersion" 10 g of the reducing agent powder used in Example 1 was dispersed in 90 g of a 10% by weight aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) using a Dynomill disperser. The particle size of the reducing agent is about 0.5
μm or less.

[Formation of Photosensitive Layer] A coating solution having the following composition was applied on the curable layer and dried to a dry film thickness of about 2.0 μm.
m of photosensitive layers.

{Coating solution for photosensitive layer} ────────────────────────────── Water 14.0g polyvinyl alcohol (Kuraray Co., Ltd., saponification degree: 80%) 25.2 g of a 5% by weight aqueous solution of the surfactant used in Example 1.6 1.6 g of the above-mentioned reducing agent dispersion 5.2 g 0.1% by weight of the additive used in Example 1 in methanol 0.7 g of solution 8.9 g of a mixture of 10 g of the silver halide emulsion used in Example 1 and 43 g of water ──────────

[Formation of Overcoat Layer] A coating solution having the following composition was applied on the photosensitive layer and dried to form an overcoat layer having a dry film thickness of about 4.0 μm.

塗布 Coating solution for overcoat layer────── １０ 10 of acid-modified polyvinyl alcohol (degree of saponification: 98%, manufactured by Kuraray Co., Ltd.) % By weight aqueous solution 100.0 g Base precursor dispersion used in Example 4 7.5 g 5% by weight aqueous solution of surfactant used in Example 3 2.0 g ───────────────────────

(Image formation) The obtained photosensitive material was used in Example 4.
An image was formed and evaluated in the same manner as described above. The results are shown in Table 1 below.

[0099]

[Table 1] Table 1 ──────────────────────────────────── Image quality (dot reproduction range) Photosensitive material Thermal development temperature 145 ° C Thermal development temperature 150 ° C Thermal development temperature 155 ° C ───────────────────────────────── ─── Example 4 4% to 97.5% 3% to 97.0% 2% to 97.0% Comparative Example 1 4% to 97.0% 3% to 96.0% 2% to 95.0 % ────────────────────────────────────

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03F 7/11 501 G03F 7/11 501

Claims (6)

[Claims] 1. A liquid photosensitive composition in which droplets of an aqueous silver halide emulsion are dispersed in an oil phase containing a polymerizable compound, a hydrophobic polymer and an organic solvent, wherein the hydrophobic polymer is A part or all of a salt-containing acidic group, and 1 g of the hydrophobic polymer contains 5 × 10 ^{−5 to} 3 × 10 ⁻³ mol of the acidic group in a salt state. A photosensitive composition comprising: 2. The photosensitive composition according to claim 1, wherein the hydrophobic polymer has an ethylenically unsaturated bond in the molecule. 3. The polymerizable compound is 0.2 to 20 parts by weight, and the hydrophobic polymer is 1 to 3 parts per 100 parts by weight of the organic solvent.
0 parts by weight, and 0.5 to 2 parts of the aqueous silver halide emulsion.
The photosensitive composition according to claim 1, which is contained in an amount of 5 parts by weight. 4. The photosensitive composition according to claim 1, further comprising a reducing agent. 5. A photosensitive material having a photosensitive curable layer formed by applying the photosensitive composition according to claim 4 on a support. 6. A photosensitive curable layer formed by applying the photosensitive composition according to claim 1 on a support, and an overcoat layer containing a hydrophilic polymer on the curable layer. A photosensitive material in which an agent is contained in a photosensitive curable layer or an overcoat layer.