JPH08334902A - Photosensitive material - Google Patents

Abstract

PURPOSE: To provide a photosensitive material preventing the occurrence of a polymer image spottedly polymerized in the non-image area and making the non-image area of printed matter free from a spotted stain. CONSTITUTION: An anodically oxidized coating film of Al, a hardenable layer contg. a polymerizable compd. or a crosslinkable polymer and a photosensitive layer contg. silver halide are successively formed on an Al substrate to obtain the objective photosensitive material. The hardenable layer or the photosensitive layer further contains a reducing agent. and the anodically oxidized coating film has been subjected to sealing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION In the present invention, an aluminum anodic oxide film, a curable layer containing a polymerizable compound or a crosslinkable polymer, and a photosensitive layer containing silver halide are sequentially provided on an aluminum support. , The curable layer or the photosensitive layer further contains a reducing agent.

[0002]

2. Description of the Related Art A method of forming a polymer image by imagewise exposing a light-sensitive material containing a silver halide, a reducing agent and a polymerizable compound to develop the silver halide and thereby polymerizing the polymerizable compound in an image form. However, Japanese Patent Publication No. 45-11149 (US Pat. No. 3,697,275, West German Patent 172).
0665 and British Patent 1131200). In this method, the 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 a radical). on the other hand,
A method in which development of silver halide is performed by heating and a polymer image is formed only by dry processing is disclosed in JP-A-61-6906.
No. 2 and No. 61-73145 (US Patent 46
29676 and European Patent No. 0174634B).

Further, a photosensitive material suitable for producing a printing plate using a dry image forming method is disclosed in JP-A-64-17.
No. 047 (U.S. Pat. No. 4,985,339 and European Patent No. 0298522B), JP-A-5-2496.
67 (U.S. Pat. No. 5,212,443 and European Patent No. 0426692B), JP-A-4-191856.
No. 5,290,659 and Japanese Unexamined Patent Publication No. 7-28248 (US Pat. No. 5,393,651). When the light-sensitive material is used for producing a printing plate, a crosslinkable polymer is used instead of or in addition to the polymerizable compound. Further, it is preferable to provide two or more layers of a curable layer containing a polymerizable compound or a crosslinkable polymer and a photosensitive layer containing silver halide on a support. The reducing agent is added to the curable layer or the photosensitive layer. Furthermore, in the production of printing plates, an aluminum support,
In particular, an aluminum support provided with an anodized film is preferably used. The aluminum support is not limited to the method for producing a printing plate utilizing a curing reaction using silver halide as an optical sensor as described above, but also a photosensitive resin (eg, diazo resin, o-quinonediazide composition, photosensitive azide). The composition is also used in a conventional method for producing a printing plate using an optical sensor. For aluminum supports,
In the conventional method, research has been particularly advanced. The following is a document relating to the improvement of the aluminum support in the conventional method.

Japanese Patent Publication No. 47-5125 and US Pat. Nos. 4,087,341 and 3,834,998 describe that an aluminum support is subjected to surface roughening treatment (graining treatment) or surface hydrophilic treatment. Has been done. Also, US Pat. Nos. 2,098,627 and 3,860.
No. 426, JP-A-60-149491 and JP-A-4-282637, a hydrophilic compound is used as an undercoat layer in order to improve print stains due to contamination of photosensitive layer components in the non-image area. It is described to be provided as. Further, JP-A-58-11759 and JP-A-58-22
No. 1254, No. 62-146694 and No. 62-1
In Japanese Patent Publication No. 48295, the amount of impurities (eg, silicon, copper, iron) contained in aluminum is kept constant in order to prevent so-called ink stains in which ink adheres to non-image areas during printing and stains the printed matter. It is described that a support defined below the value is used. Furthermore, JP-A-59
Japanese Patent Laid-Open No. 114100 describes an aluminum support in which an anodized film is subjected to a sealing treatment.

Most of the improvements of the aluminum support in the conventional method as described above are also effective in the method of producing a printing plate utilizing the curing reaction using silver halide as an optical sensor. However, JP-A-5
Regarding the sealing treatment of the anodic oxide film described in JP-A 9-114100, the effectiveness was not recognized in the method using a silver halide as an optical sensor. JP 59-1
As described in Japanese Patent No. 14100, in the invention described in that publication, a sealing treatment is performed in order to prevent the substance contained in the photosensitive layer from adsorbing to the non-image area and contaminating the non-image area. To do. The substance that actually adsorbs is the photosensitive resin that functions as the above-described optical sensor. Since the photosensitive resin has a photosensitive functional group, it is easily adsorbed on the porous surface of the anodized film.

On the other hand, in a light-sensitive material using silver halide as an optical sensor, generally, a curable layer containing a polymerizable compound or a crosslinkable polymer and a light-sensitive layer containing silver halide are separated from each other to form a support. Provide on top. Polymerizable compounds and crosslinkable polymers are relatively simple compounds and polymers that do not require a photosensitive functional group. Such compounds and polymers are less likely to be adsorbed on the porous surface of the anodized film. Therefore, in the method using silver halide as an optical sensor, the necessity of performing the sealing treatment, that is, the problem of contamination of the non-image area was hardly recognized (see Reference Example 1 of the present specification). For the above reasons, the prior arts relating to the production of printing plates using silver halide as an optical sensor (the above-mentioned Japanese Patent Laid-Open Nos. 64-17047 and 5-24).
No. 9667, No. 4-191856 and No. 7-282.
No. 48), even though there is a description of an aluminum support and an anodized film, there is no mention of sealing treatment.

[0007]

DISCLOSURE OF THE INVENTION The present inventor has further researched a photosensitive material using silver halide as an optical sensor and an aluminum support. In the usual way,
The photosensitive compound was imagewise exposed to heat and developed to cure the polymerizable compound to form a polymer image, and the uncured portion was removed using an alkaline eluent. An image of a polymer polymerized into a small circle (hereinafter referred to as a dot) was observed. Also,
During printing, ink adhered to the non-image area, causing spot-like ink stains.

The above problem is a phenomenon peculiar to using an aluminum support. It is considered that the cause is that the impurity metal (eg, iron, copper) contained in the aluminum support directly acts on the silver halide during the development to catalytically cause the fogging development of the silver halide. Alternatively, a local battery is formed between the impurity metal contained in the support and aluminum, a corrosion reaction occurs due to the intervention of halide ions derived from silver halide, and the corrosion reaction product develops silver halide. It is also presumed that the development was caused by radicals being generated and the polymerizable compound being polymerized and cured. When a printed matter was prepared using a lithographic printing plate made from such a light-sensitive material, spot-like stains were found on the non-image area, and it was found that the printed matter was unsuitable.

The present inventor has already proposed a solution to this problem in Japanese Unexamined Patent Publication No. 7-28248 (US Pat. No. 5,393,651). That is, the above problem can be solved by providing an undercoat layer containing a compound having a specific metal ion or metal oxide ion on the anodized film. However, the provision of the undercoat layer complicates the layer structure of the photosensitive material. Depending on the application of the printing plate, it may be desirable that the layer structure of the light-sensitive material is simple.

An object of the present invention is to provide a light-sensitive material capable of producing a printing plate having almost no polymer image formed by dot-like polymerization in non-image areas. Another object of the present invention is to provide a light-sensitive material suitable for producing a printing plate in which the non-image portion of the obtained print has little spot-like stain. Further, the object of the present invention is also to achieve the above object with a light-sensitive material having a relatively simple layer structure.

[0011]

According to the present invention, an aluminum anodic oxide film, a curable layer containing a polymerizable compound or a crosslinkable polymer, and a photosensitive layer containing silver halide are sequentially provided on an aluminum support. And the curable layer or the photosensitive layer is a photosensitive material further containing a reducing agent,
Provided is a light-sensitive material characterized in that an anodized film is subjected to a sealing treatment. The sealing treatment is preferably carried out by exposing the aluminum support provided with the anodized film to an atmosphere having a steam pressure of 70 to 270 ° C. and a water vapor pressure of 100 Torr.

[0012]

According to the research conducted by the present inventor, it has been found that the sealing of the anodized film can block the connection between the impurity metal or the corrosion reaction product and the silver halide and solve the above-mentioned problems. The fogging of the anodized film can suppress silver fogging. Therefore, when the light-sensitive material of the present invention is used, a polymer image formed by dot-like polymerization in the non-image area can be eliminated, and a printed matter free of dot-like stains and ink stains can be obtained. This effect of the present invention is
The effect of the sealing treatment in the conventional method using a photosensitive resin as an optical sensor is completely different. That is, in the conventional method using the photosensitive resin, the sealing treatment is performed in order to remove the contamination of the non-image portion. Contamination of the non-image area is caused by adsorption of the photosensitive resin on the porous surface of the anodized film, as described above. Specifically, the residual film is formed almost uniformly over the entire non-image area. However, in a photosensitive material using silver halide as an optical sensor, the problem of such a uniform residual film is minor.
On the other hand, in a photosensitive material using silver halide as an optical sensor, a cured residual film is generated in a non-image area due to a battery reaction between an impurity metal or a corrosion reaction product and silver halide. This residual film is generated in a dot shape around the position where the battery reaction occurs. In the present invention, a sealing treatment is carried out in order to eliminate the dot-like residual film.

[0013]

Detailed Description of the Invention

[Aluminum Support] The aluminum plate used as a support in the present invention is made of pure aluminum or an aluminum alloy containing aluminum as a main component and a slight amount of a foreign atom. Heteroatoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign atoms in the aluminum alloy is preferably 10% by weight or less. Although it is ideal to use pure aluminum, completely pure aluminum is difficult to manufacture due to refining technology. On the other hand, any aluminum alloy having a different atom content in the above range can be used in the present invention. As the aluminum support, a conventionally known material can be used. Preferred materials are JIS-A-1050, 1100, 1200, 3003, 3103, 3
005 aluminum plate is included. The thickness of the aluminum support is preferably 0.1 to 0.6 mm.

The aluminum plate is generally used after being roughened. Before the surface-roughening treatment, a degreasing treatment for removing rolling oil on the surface may be carried out. In the degreasing treatment, a surfactant or an alkaline aqueous solution is used. The aluminum support may be treated on only one side or both sides. Since the contents of the process are the same for both sides, the case of one side will be described below. As the roughening treatment method, a method of mechanically roughening the surface,
There are methods of electrochemically dissolving the surface and methods of chemically selectively dissolving the surface. As the method for mechanically roughening the surface, known methods called ball polishing method, brush polishing method, blast polishing method and buff polishing method can be used. Further, as an electrochemical roughening method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution. Also, a combination of both a mechanical surface-roughening method and an electrochemical surface-roughening method (Japanese Patent Laid-Open Publication No. Sho.
No. 4-63902).

[Anodizing Treatment] The anodizing treatment is preferably carried out on the roughened aluminum support as described above. Before the anodizing treatment (after roughening), an alkali etching treatment or a neutralizing treatment may be performed. In the anodizing treatment, an electrolyte that forms a porous oxide film is used. As the electrolyte, sulfuric acid, phosphoric acid,
Oxalic acid, chromic acid, or a mixed acid thereof is used. The treatment conditions for anodization are determined by the type of electrolyte used. Generally, the electrolyte concentration is 1 to 80 wt% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60.
A / dm ² , voltage is 1 to 100 V, and electrolysis time is in the range of 10 seconds to 50 minutes. The amount of anodized film is 1.
It is preferably 0 g / m ² or more, and 2.0 to 6.
It is more preferably in the range of 0 g / m ² . If the anodic oxide film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the lithographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. So-called scratches and stains are likely to occur.

[Sealing treatment] The sealing treatment is a treatment for sealing fine pores of the anodized film to improve the film. The specific treatment methods are roughly classified into (1) hydration method,
It can be classified into (2) metal salt method, (3) organic matter method and (4) coating method. Of these, the hydration method of (1), specifically,
By exposing the anodic oxide film to pressurized steam or boiling water, aluminum hydrate called bayerite or boehmite is generated,
The most general method is to use this crystalline film for sealing. The sealing treatment is performed after forming the anodic oxide film. Before the sealing treatment (after the anodizing treatment), a hydrophilic treatment using an alkali metal silicate may be carried out.

The sealing treatment is described in "Aluminum Surface Technology Handbook" (Light Metal Publishing) and "Aluminum Handbook" (Light Metal Association). A particularly preferable hydration method (pressurized steam method) will be further described. The aluminum support provided with the anodized film is exposed to an atmosphere having a temperature of 70 to 270 ° C. and a water vapor pressure of 100 Torr or more. Temperature is less than 70 ° C or water vapor pressure is 1
If it is less than 00 Torr, the effect of the sealing treatment is hardly obtained. When the temperature is 270 ° C. or higher, the aluminum support becomes blunt and the mechanical strength deteriorates. A more preferable processing temperature is 75 to 170 ° C, and a most preferable processing temperature is 80 to 130 ° C. The processing time is determined according to the temperature and the humidity. Typical processing time is 1 second to 30 minutes. If the processing time is longer than 30 minutes,
In some cases, the abrasion resistance of the anodized film is reduced and the printing durability of the lithographic printing plate is deteriorated. If the treatment time is less than 1 second, the effect of the sealing treatment may not be sufficiently obtained in many cases. The processing temperature is 75 to 170 ° C. (particularly 80 to 130 ° C.).
When set to (° C.), it is possible to easily produce industrially consistent products with a short treatment time.

A hydrophilic treatment may be carried out after the sealing treatment. The hydrophilic treatment is performed by using an aqueous solution of an alkali metal silicate (eg, sodium silicate) (US Pat. No. 2741066).
No. 3,181,461, No. 3,280,734 and No. 3,902,734), potassium fluorozirconate (described in JP-B-36-22063) or polyvinylphosphonic acid (US Pat. No. 3,276,686).
No. 8 specification)). Treatment with an alkali metal silicate is particularly preferred. An undercoat layer may be provided on the anodic oxide coating which has been subjected to the sealing treatment.
An example of a subbing layer is a hydrophilic layer (described in U.S. Pat. No. 3,860,426) containing a water-soluble metal salt (eg, zinc acetate) and hydrophilic cellulose (eg, carboxymethyl cellulose). Further, an undercoat layer containing a compound having a metal ion or a metal oxide ion is formed on the anodized film (JP-A-7-28248 and US Pat. No. 5,393).
No. 651) may be provided.

[Layer Constitution of Photosensitive Material] In the photosensitive material, a curable layer containing a polymerizable compound or a crosslinkable polymer is provided on an anodized film, and a photosensitive layer containing silver halide is provided thereon. The reducing agent is added to the curable layer, the photosensitive layer or both. The reducing agent is preferably added to the photosensitive layer. Further, the photosensitive material may have a constitution of three or more layers including a photosensitive layer, a curable layer and other functional layers. Other functional layers include overcoat layers, adhesive layers, release layers and intermediate layers.

[Curable Layer] The curable layer contains a polymerizable compound or a crosslinkable polymer. The thickness of the curable layer is preferably 0.1 to 20 μm, more preferably 0.3 to 7 μm.

[Photosensitive Layer] The photosensitive layer contains silver halide and generates radicals by imagewise exposure and thermal development. The generated radicals diffuse and enter the curable layer to cure the curable layer. The thickness of the photosensitive layer is 0.1 to 2
The thickness is preferably 0 μm, more preferably 0.5 to 10 μm.

[Overcoat Layer] The overcoat layer has a function of protecting the photosensitive material and preventing oxygen from entering the air to enhance the degree of curing of the curable layer. In addition, a component that accelerates image formation in the overcoat layer (eg,
A base or a base precursor, a heat development accelerator) may be added to function as an image formation promoting layer. The overcoat layer can include a matting agent. The matting agent reduces the tackiness of the surface of the photosensitive material and prevents adhesion when the photosensitive materials are stacked. The thickness of these layers is preferably 0.3 to 20 μm, and 0.5 to 10 μm.
Is more preferable. The overcoat layer is generally formed by using a hydrophilic polymer. However, it is also possible to use a hydrophobic polymer. For example, it can be formed by dissolving a hydrophobic polymer in a solvent and coating it.
It can also be formed by coating a polymer latex. If a hydrophobic polymer is used for the etching process, after thermal development, prior to etching,
It is necessary to remove these layers by peeling.

[Adhesive Layer] When an image is formed using toner, an adhesive layer can be provided on the photosensitive material. The adhesive layer is made of an adhesive polymer to which toner can be attached. As the polymer, natural or synthetic rubber is preferable. Examples of synthetic rubbers include isobutylene rubber, nitrile rubber, butyl rubber, chlorinated rubber, polyvinyl isobutyl ether, silicone elastomer, neoprene and copolymer rubber (eg, styrene-butadiene copolymer, styrene-isobutylene copolymer). When the synthetic rubber is a copolymer, the copolymerization method may be random, block or graft copolymerization. The thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[Release Layer] When an image is formed by transfer, a release layer can be provided on the photosensitive material. The peeling layer is easy to peel from the support and is non-tacky at room temperature, but exhibits tackiness or fusion property when heated. The release layer is
It includes an organic polymer (eg, polyvinyl acetal resin, amide resin) as a matrix. The flow softening point of the polymer used as the matrix is preferably equal to or higher than the heating temperature required for the reduction reaction of the reducing agent. The release layer preferably further contains 1% by weight or more of a fluorine-containing compound. As the fluorine-containing compound, a fluorine-containing surfactant can be preferably used. The thickness of the release layer is preferably 1.0 μm or more, and 1.4 μm
It is more preferable that the above is satisfied.

[Intermediate Layer] An intermediate layer can be provided between the layers. The intermediate layer can also function as an antihalation layer or a barrier layer. The barrier layer has a function of preventing components from moving between layers and diffusing or mixing during storage of the light-sensitive material. The material of the intermediate layer is determined according to the application. You may use the hydrophilic polymer used for a photosensitive layer and an overcoat layer. The thickness of the intermediate layer is preferably 10 μm or less.

[Silver Halide] As the silver halide,
Grains of silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. The shape of the silver halide grains is preferably cubic or tetradecahedral, but not limited to those having a regular crystal form, those having an irregular crystal form, or a composite form thereof. Anomalous crystal forms include potato, spherical, plate and plate crystal forms. In tabular grains, the grain size is generally 5 times or more the grain thickness.

The grain size of silver halide is not particularly limited. Fine particles of 0.01 μm or less can also be used. On the other hand, large particles of about 10 μm can also be used. Regarding the grain size distribution, monodisperse grains are preferable to polydisperse emulsions. For monodisperse emulsions, see US Pat.
628, 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 different halogen compositions inside and 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 rhodanide and lead oxide.

The silver halide grains may contain salts of other elements. Examples of other elements are copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg sulfur, selenium, tellurium), gold and VI.
Group II noble metals (eg, rhodium, iridium, iron, platinum, palladium) can be mentioned. The salts of these elements are
It can be added during or after the formation of silver halide grains to be contained in the grains. The specific method is
US Patents 1195432, 1951933, and 2
448060, 2628167, 295097.
No. 2, No. 3488709, No. 3737313, No. 3
772031, 4269927 and Research Disclosure (RD), Vol. 134,
No. 13452 (June 1975). Iridium ions can be introduced into silver halide grains by adding an aqueous solution of an iridium compound to the emulsion during preparation of the silver halide emulsion. Examples of water-soluble iridium compounds include hexachloroiridium (III) acid salts and hexachloroiridium (IV) acid salts. Similarly, rhodium ions may be introduced into the 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.

The iridium compound or 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 while the particles are formed. Further, it may be added between the grain formation and the chemical sensitization treatment. It is particularly preferred to add it while the particles are being formed. Iridium ion or rhodium ion is preferably used in an amount of 10 ^{−8 to} 10 ⁻³ mol, and more preferably 10 ^{−7 to} 10 ⁻⁵ mol, per mol of silver halide. In addition, when using a rhodium compound and an iridium compound together, it is preferable that the former use is performed before the latter use. Two or more kinds of silver halide grains having different halogen compositions, crystal habits and grain sizes may be used in combination.

Silver halide is preferably used as an emulsion. The silver halide emulsion is described in Research Disclosure (RD) No. 17643 (December 1978)
Mon., pp. 22-23, "I. Emulsion prepa
ration and types) ", and No. 18716 (19)
(November 1979), p.648. The silver halide emulsion is usually subjected to chemical sensitization after physical ripening, but chemical sensitization may not be performed. It is preferred to use silver halide grains having a relatively low fog value. Additives used in such processes are described in Research Disclosure, No. 17643 and No. 17643. 18716. No. for chemical sensitizers. 17643 (page 23) and No. 187
16 (page 648, right column). In addition, other known additives other than those mentioned above are
It is described in Disclosure Magazine. For example, regarding the sensitivity enhancer, No. 18716 (page 648, right column)
No. 1 for antifoggants and stabilizers. 176
43 (pages 24 to 25) and No. 18716 (Page 649, right column).

The silver halide emulsion is usually used after spectral sensitization. The sensitizing dye used in the light-sensitive material may be a silver halide sensitizing dye known in the photographic art and the like. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Along with the sensitizing dye, a dye having no spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (supersensitizer) may be added to the emulsion. Good.

[Organic Metal Salt] An organic metal salt can be added to the photosensitive layer of the light-sensitive material of the present invention together with silver halide. As such an organic metal salt, it is particularly preferable to use an organic silver salt. The organic compound used to form the organic silver salt, triazoles, tetrazoles, imidazoles, indazoles, thiazoles, thiadiazoles, azaindenes, aliphatic having a mercapto group as a substituent, aromatic or Heterocyclic compounds can be mentioned. Further, a silver salt of carboxylic acid or silver acetylene can be used as the organic silver salt.
Two or more kinds of 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 mol of silver halide. Further, instead of the organic silver salt, an organic compound constituting the organic silver salt is added to the photosensitive layer,
It may be converted into an organic silver salt by partially reacting with silver halide in the photosensitive layer.

[Reducing Agent] The reducing agent has a function of reducing silver halide or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include 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, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5 -Pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles,
Included are sulfonamide pyrazolotriazoles, α-sulfonamido ketones and hydrazines.

The above reducing agents are disclosed in JP-A-61-18364.
No. 0, No. 61-188535, No. 61-228441
No. 62-70836, 62-86354, 62-86355, 62-206540, 62.
-264041, ibid. 62-109437, ibid. 63-
254442, JP-A-1-267536, 2-1.
No. 41756, No. 2-141757, No. 2-2072.
No. 54, No. 2-262662, and No. 2-269352 (including those described as a developer or a hydrazine derivative). Regarding the reducing agent, see “The Theory of the Photographic Pro” by T. James.
cess ”4th edition, pages 291-334 (1977), Research Disclosure, Vol. 170, 1702.
No. 9, pp. 9-15 (June 1978), and ibid.
Vol. 176, No. 17643, pages 22-31, (197
(December 8th). Also, JP-A-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, contact with a base, or the like may be used instead of the reducing agent.

Of these reducing agents, those which have a basicity to form a salt with an acid can also be used in the form of a salt with an appropriate acid. These reducing agents may be used alone, or as described in each of the above publications, two or more reducing agents may be used in combination. When two or more reducing agents are used in combination, the reducing agents interact as follows: first, to promote reduction of silver halide (and / or organic silver salt) by so-called superadditivity; Inducing polymerization of a polymerizable compound through a redox reaction with another reducing agent in which an oxidized product of the first reducing agent produced by reduction of silver halide (and / or organic silver salt) coexists. (Or suppressing polymerization) is considered. However,
In actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously. The reducing agent is preferably used in the range of 0.1 to 10 mol, and more preferably in the range of 0.25 to 2.5 mol, per mol of silver halide.

By adjusting the kind and amount of the reducing agent, the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed is selectively polymerized. be able to. The reducing agent develops silver halide and is itself oxidized to an oxidant. When the oxidant of this reducing agent decomposes in the layer to generate radicals,
Polymerization occurs in the area where the latent image of silver halide is formed. Examples of such reducing agents include hydrazines. On the other hand, when the oxidant does not generate (or does not easily generate) radicals and the reducing agent itself or the oxidant has a polymerization suppressing function, it is necessary to include a polymerization initiator (radical generator) with the reducing agent. The part where the latent image of silver halide is not formed (when the oxidation inhibitor has a stronger polymerization inhibiting function than the reducing agent) or the latent image is formed (the reducing agent has a polymerization inhibiting function than the oxidizing agent) When it is strong, polymerization occurs. Examples of the reducing agent having the above functions include 1-phenyl-3-pyrazolidones and hydroquinones. In this case, it is necessary to add a thermal polymerization initiator or a photopolymerization initiator as described below to the photosensitive material.

[Polymerization Initiator] Regarding the thermal polymerization initiator,
It is described in pages 6 to 18 of "Addition Polymerization / Ring-Opening Polymerization" (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science and Editorial Committee of Polymer Experiments, and JP-A-61-243449. Examples of thermal polymerization initiators include azo compounds (eg, azobis (isobutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 2 , 2'-azobis (2-methylbutyronitrile), azobisdimethylvaleronitrile),
Peroxides (eg, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide,
Hydrogen peroxide, potassium persulfate, ammonium persulfate) and sodium p-toluenesulfinate may be mentioned.

For the photopolymerization initiator, see Oster et al., “Ch
Emical Review "Vol. 68 (1968) 125-1
51 pages, "Light-Sensitive System" by Kosar (John W
iley & Sons, 1965) pp. 158-193 and JP-A-61-75342, JP-A-2-207254.
It is described in the official gazette. Examples of the photopolymerization initiator include carbonyl compounds (eg, α-alkoxyphenyl ketones,
Polycyclic quinones, benzophenone derivatives, xanthones, thioxanthones, benzoins, commercially available photopolymerization initiators (eg, “Irgacure 65 manufactured by Ciba Geigy”)
1 "," Irgacure 907 ")), halogen-containing compounds (eg, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones), haloalkanes Kind,
α-halo-α-phenylacetophenones, redox couples of photoreducible dyes and reducing agents, organic sulfur compounds, peroxides, optical semiconductors (eg, titanium dioxide, zinc oxide), metal compounds (eg, iron ( I) salt, metal carbonyl,
Mention may be made of metal complexes, uranyl salts), silver halides, azo and diazo compounds.

Specific examples of the photopolymerization initiator include 2-dimethoxy-2-phenylacetophenone and 2-methyl- {4-.
(Methylthio) phenyl} -2-morpholino-1-propanone, benzoin butyl ether, benzoin isopropyl ether, benzophenone, Michler's ketone,
4,4′-diethylaminobenzophenone, chloromethylbenzophenone, chlorosulfonylbenzophenone,
9,10-anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9,10-phenanthrenequinone, xanthone, chloroxanthone, thioxanthone, chlorothioxanthone, 2,4 -Diethylthioxanthone, chlorosulfonylthioxanthone, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, fluorene and carbon tetrabromide. The polymerization initiator is per 1 g of the polymerizable compound,
It is preferably used in the range of 0.001 to 0.5 g, and more preferably 0.01 to 0.2 g.

[Polymerizable Compound and Crosslinkable Polymer] Examples of the polymerizable compound include compounds having addition polymerizable or ring-opening polymerizable property. The compound having an addition polymerizable property includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable property includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. Examples of the compound having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters. , Itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and derivatives thereof.
Acrylic acid esters or methacrylic acid esters are preferred.

Specific examples of acrylic acid esters include:
n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexane Diol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, tricyclodecane dimethylol diacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A, 2,2-dimethyl-3-
Diacrylate of a condensate of hydroxypropionaldehyde and trimethylolpropane, 2,2-dimethyl-3
A triacrylate of a condensate of hydroxypropionaldehyde and pentaerythritol, a diacrylate of polyoxyethylenated bisphenol F, a polyurethane acrylate, a polyethylene glycol diacrylate,
Polypropylene diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-
5-ethyl-1,3-dioxane diacrylate, 2-
(2-hydroxy-1,1-dimethylethyl) -5,5
Mention may be made of dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

Specific examples of the methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate. And a compound obtained by substituting a part or all of the acryloyl group of the polymerizable monomer compound mentioned as a specific example of the above acrylic acid esters such as dimethacrylate of polyoxyalkylenated bisphenol A with a methacryloyl group.

As the crosslinkable polymer, any known polymer having a group reactive with a radical species can be used. These polymers may be homopolymers or copolymers with monomers that do not have groups reactive with radical species. Such a polymer is a polymer having a double bond group (A) in the main chain or side chain of a molecule to which a radical (a polymerization initiation radical or a growth radical in a polymerization process of a polymerizable monomer) can be added. And (B) main chain or side chain atoms (hydrogen atom, halogen atom such as chlorine) due to radicals
Is a polymer that is easily extracted to generate a polymer radical. Examples of the polymer (A) include polymers having an ethylenically unsaturated double bond in the side chain as described in JP-A No. 64-17047 (eg,
Allyl (meth) acrylate polymers (including copolymers), 1,2-polybutadiene, 1,2-polyisoprene) and polymers having unsaturated double bonds in the main chain (eg, poly-1,4-butadiene, poly) Mention may be made of -1,4-isoprene (including copolymers), natural and synthetic rubbers.

Examples of the above-mentioned polymer (B) include:
The polymers described on pages 147 to 192 of “Polymer Reaction” (Journal of the Polymer Society of Japan / Kyoritsu Shuppan, 1978) can be mentioned. Specifically, poly (meth) acrylate, polyvinyl butyrate, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl acetate, polyvinylidene chloride, vinyl acetate-ethylene copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene, chlorinated polypropylene. , Polycarbonate, diacetyl cellulose, cellulose acetate butyrate, triacetyl cellulose, ethyl cellulose, polyvinyl pyridine, polyvinyl imidazole. As described below, when the etching treatment is performed with an alkaline aqueous solution after the polymerization, the crosslinkable polymer preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups and sulfonimide groups. Specific examples include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. In the case of copolymers, the molar content of monomers with acidic groups is in the range 1 to 50%, more preferably 5 to 30%.

Two or more kinds of the above-mentioned polymerizable compounds may be used in combination. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent or the coloring agent can also be used as the polymerizable compound. As described above, the use of a substance that also serves as a reducing agent and a polymerizable compound or a coloring agent and a polymerizable compound is also included in the aspect of the light-sensitive material. The polymerizable compound is contained in the curable layer in an amount of preferably 3 to 90% by weight based on the total amount of the layer, and 15 to 6
It is more preferable that the content is 0% by weight.

[Binder of the curable layer] The curable layer contains
Further binders can be added to improve the strength. As the binder, natural and synthetic polymer compounds can be used. When a crosslinkable polymer is used as the polymerizable compound, the crosslinkable polymer functions not only as the polymerizable compound but also as the binder. Examples of specific binders include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), polycondensation type synthetic homopolymers and copolymers (eg, polyester, polyamide, polyurethane, Polyester-polyamide). When the etching treatment is carried out with an alkaline aqueous solution after the polymerization, the polymer used as the binder preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups and sulfonimide groups. Specific examples include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. In the case of a copolymer, the molar content of the monomer having an acidic group is preferably 1 to 50%, more preferably 5 to 30%.

As the polymer used for the binder, a crosslinkable polymer having an acidic functional group in its molecule is particularly preferable. An example of such a polymer is a copolymer of allyl (meth) acrylate and (meth) acrylic acid. When a polymer having an ethylenically unsaturated double bond in the side chain is used as the binder or the polymerizable compound, an image can be obtained even if the curable layer does not contain a polymerizable monomer. It is preferable to use a monomer in combination because the hardness can be increased. Further, an image can be obtained even if the curable layer does not contain a binder but contains only a polymerizable monomer, but when the polymerizable monomer is a liquid, the curable layer becomes too soft, which is not preferable. The amount of the binder added to the curable layer is generally 80% by weight or less, preferably 70% by weight or less based on the entire curable layer.

[Hydrophilic polymer] A hydrophilic layer such as a photosensitive layer or an overcoat layer of a photosensitive material contains a hydrophilic polymer as a binder. The hydrophilic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in the molecular structure. Examples of hydrophilic groups include carboxyl, alcoholic hydroxyl group, phenolic hydroxyl group, sulfo, sulfonamide group, sulfonimide and amide. Examples of hydrophilic bonds include urethane bonds, ether bonds and amide bonds. It is preferable to use a water-soluble polymer or a water-swellable polymer as the hydrophilic polymer. What is a water-swellable polymer?
It has an affinity for water but is not completely soluble in water due to the cross-linked structure of the polymer. As the water-soluble or water-swellable polymer, a natural or synthetic polymer compound can be used.

Water-soluble polysaccharides and proteins can be used as the natural polymer. Examples of water-soluble polysaccharides can include starch, starch derivatives, cellulose, cellulose derivatives, alginic acid, pectic acid, acacia, pullulan and dextran. Examples of proteins can include gelatin and casein. If necessary, these natural polymers may be artificially modified before use. Further, in the preparation of a light-sensitive material, a natural polymer can be modified or cross-linked before use. As the synthetic polymer, a polymer of a monomer having a hydrophilic group or a hydrophilic bond as described above or a copolymer of the monomer and another monomer can be used.
In the present invention, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide and derivatives or modified products thereof can be preferably used.
Polyvinyl alcohol is particularly preferred.

Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen transmission rate, the saponification degree is preferably 50% or more, more preferably 80% or more, and 9
It is particularly preferable to be 5% or more. Copolymer modified polyvinyl alcohol can also be used. Copolymerization modification is a method of synthesizing modified polyvinyl alcohol by saponifying a copolymer of vinyl acetate and another monomer. As the monomer to be copolymerized, any monomer can be used as long as it is copolymerized with vinyl acetate. Examples of such monomers include:
Mention may be made of ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, methyl methacrylate and acrylamide. Further, post-modified polyvinyl alcohol can also be used. With post-modification, by using a compound having reactivity with the hydroxyl group of polyvinyl alcohol,
This is a method of denaturing by a polymer reaction after the synthesis of polyvinyl alcohol. Specifically, the hydroxyl group of polyvinyl alcohol is modified by etherification, esterification or acetalization.

Furthermore, it is also possible to use crosslinked polyvinyl alcohol. As the crosslinking agent, an aldehyde, a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid or an inorganic crosslinking agent (eg boric acid, titanium, copper) can be used. The molecular weight of the hydrophilic polymer is preferably in the range of 3000 to 500,000. The amount of hydrophilic polymer used is 0.0
It is preferably 5 to 20 g / m ² , and more preferably 0.1 to 10 g / m ² . When gelatin is used in combination with another hydrophilic polymer in the layer containing silver halide, the pH of the layer containing silver halide is 1.2 or less or 1.2 or more than the isoelectric point of gelatin. It is preferable to adjust

[Base or Base Precursor] The light-sensitive material may contain a base or a base precursor.
In particular, in the case of performing dry development processing by heating, the light-sensitive material preferably contains a base or a base precursor. As the base and the base precursor, inorganic bases and organic bases, or base precursors thereof (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. Examples of inorganic bases are described in JP-A-62-209448. Examples of organic bases include tertiary amine compounds (described in JP-A-62-170954), bis- or tris-, or tetra-amidine compounds (JP-A-6-16065).
3-316760) and bis or tris or tetraguanidine compounds (JP-A-64-68).
746). In the present invention, a base having a pKa of 7 or higher is preferred.

From the viewpoint of storage stability of the light-sensitive material, a base precursor is preferable to a base. Examples of preferable base precursors include salts of organic acids and bases that are decarboxylated by heating (JP-A-63-316760 and 64-68746).
No. 59-180537 and No. 61-31343.
1) and urea compounds that release a base upon heating (described in JP-A-63-96159). Further, as a method of releasing a base by utilizing a reaction, a reaction with a transition metal acetylide or a salt containing an anion having an affinity higher than that of the acetylide anion for the transition metal ion (described in JP-A-63-25208) Or a basic metal compound which is poorly soluble in water and a compound capable of undergoing a complex formation reaction with a metal ion constituting the basic metal compound in water as a medium, and between these two compounds in the presence of water. And a method of releasing a base by the reaction (described in JP-A-1-3282). The base precursor of the present invention preferably releases a base at 50 ° C to 200 ° C, and 80 ° C to 1
More preferably, it releases a base at 60 ° C. The base and the base precursor can be used in combination. The base or base precursor is preferably used in the range of 0.1 to 20 mol, and more preferably 0.2 to 10 mol, per mol of silver halide.

[Heat Development Accelerator] The light-sensitive material used in the present invention may contain a heat development accelerator in any layer in order to accelerate heat development and to carry out heat development processing in a shorter time. .
The thermal development accelerator may be a compound having a plasticizing action at room temperature or upon heating with respect to the binder used in any layer of the light-sensitive material, or a compound having no plasticizing action but capable of being melted in the layer by heating. Any of these can be used. As the compound having a plasticizing effect on the binder used in any layer of the light-sensitive material at room temperature or at the time of heating, all known compounds known as plasticizers for polymer compounds can be used. As such a plasticizer, "Plastic compounding agent" Taiseisha, P21-63;
"Plastics Additives 2nd Edition" (Plastics
Additives, 2nd Edition) Hanser Publishers, Chap.
5 P251-296; "Thermoplastic Additives"
(Thermoplastics Additives) Marcel Dekker Inc. Cha
p.9 P345-379; “Plastics Additives A Industrial Guide” (Plastics Additives A
n Industrial Guide) Noyes Publications, Section-14
P333-485; "The Technology of Solvents.
And Plasticizers "(The Technology of
Solvents and Plasticizers) John Wiley & Sons Inc.
Chap.15 P903-1027); "Industrial Plasticizers, Pergamon"
Press); "Plasticizer Technology No. 1
Volume "(Plasticizer Technology Vol.1, Reinhold Publi
shing Corp.); "Plasticization and Plasticizer Process" (Plusticization a
The plasticizers described in nd Plusticizer Process, American Chemistry) can be used.

Preferred thermal development accelerators are glycols (eg, diethylene glycol, dipolypropylene glycol), polyhydric alcohols (eg, glycerin, butanediol, hexanediol), sugars, formate esters, ureas (eg, urea). , Diethylurea, ethyleneurea,
Propylene urea), urea resin, phenol resin, amide compound (eg, acetamide, propionamide), sulfamides and sulfonamides. Further, two or more of the above thermal development accelerators can be used in combination. It is also possible to add it by dividing it into two or more layers. Addition amount of heat development accelerator is 0.0
It is preferably 5 to 2 g / m ² , and 0.1 to 1
More preferably, it is g / m ² .

[Colorant] A colorant may be added to the light-sensitive material for the purpose of preventing halation and irradiation, or coloring the polymerized image. As the colorant for this purpose, any known colorant regardless of pigment or dye may be used, as long as it does not significantly hinder the polymerization and curing reaction of the curable layer or the light sensitivity and developability of the silver halide. Can be used. When the colorant is used for the purpose of preventing halation or coloring the image, it is preferably added to the curable layer. Further, when it is used for the purpose of preventing irradiation, it is preferably added to the photosensitive layer. When a coloring agent is added to prevent halation and irradiation, it is preferable that the coloring agent can absorb light in the photosensitive wavelength region of silver halide. As a pigment that can be used as a colorant, commercially available pigments and color index (CI) handbooks, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest pigment application technology" (CMC Publishing) , 1986) and "Printing Ink Technology" (CMC Publishing, 1984). Examples thereof include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments. A quinophthalone pigment, a dyed lake pigment, an azine pigment, a nitroso pigment, a nitro pigment, a natural pigment, a fluorescent pigment, and an inorganic pigment can be used.

These pigments may be used without surface treatment or may be subjected to surface treatment before use. Surface treatment methods include resin or wax surface coating, surfactant adhesion, and reactive substances (eg, silane coupling agents, epoxy compounds, polyisocyanates, etc.)
It is possible to consider a method of binding the pigment to the surface of the pigment. The above surface treatment method is "property and application of metal soap" (Koushobo),
"Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in. Particle size of pigment is 0.01 to 10 μm
Is preferably in the range of 0.05 to 1 μm, and more preferably in the range of 0.05 to 1 μm. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dye that can be used as the colorant, commercially available dyes and known dyes described in the literature (for example, "Handbook of Dyes" edited by The Society of Organic Synthetic Chemistry, published in 1970) can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, and methine dyes. Dyes for preventing irradiation, which have little influence on the sensitivity of silver halide, are disclosed in Japanese Examined Patent Publication Nos. 41-20389 and 43-350.
No. 4, 43-13168 and JP-A-2-3904.
No. 2 publications, and US Pat.
No. 23207, No. 2865752, and British Patent 1030.
No. 392 and No. 1100546 are described. The amount of the colorant used is 0.01 to 2 g / m ² , more preferably 0.05 to 1 g / m ² .

[Antifoggant, Development Accelerator, Stabilizer] In order to improve photographic characteristics, an additive such as an antifoggant, a silver development accelerator that promotes silver development, and a stabilizer is contained in any layer. You may let me. Examples of these include azoles and azaindenes (Research Disclosure N.
o. 17643, pages 24 to 25 (1978)), nitrogen-containing carboxylic acids and phosphoric acids (described in JP-A-59-168442), cyclic amides (described in JP-A-61-151841), thioethers (special JP-A-62-151842), polyethylene glycol derivative (JP-A-62-151843), thiol (JP-A-62-151844), acetylene compound (JP-A-62-87957). ) And sulfonamide (JP-A-62-1782).
No. 32 publication). An aromatic ring (carbon ring or heterocycle) mercapto compound is also preferably used as an antifoggant or a development accelerator. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are preferred. The mercapto compound may be added to the photosensitive material as a mercapto silver compound (silver salt). The amount of these compounds used is in the range of 10 ^{-7 to} 1 mol per mol of silver halide.

[Development Stopping Agent] In the present invention, 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 heat development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the layer to stop development after proper development, or inhibits development by interacting with silver and a silver salt. It is a compound that causes. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. Regarding the thermal development stopper, see JP-A-62-2531.
59, JP-A-2-42447 and 2-26.
It is described in each publication of 2661.

[Surfactant] In the present invention, a surfactant can be added to any layer. Known surfactants can be used as the surfactant. Examples include nonionic activators, anionic activators, cationic activators, fluorine activators, and the surfactants described in JP-A-2-195356. In particular, sorbitans, polyoxyethylenes, and nitrogen-containing surfactants are preferable.

[Matting Agent] The matting agent which can be contained in the back layer of the light-sensitive material, or the overcoat layer or the image formation accelerating layer provided on the uppermost layer on the side coated with the light-sensitive layer is a common silver salt photograph. Is a discontinuous solid particle of an inorganic or organic material dispersible in a hydrophilic colloid binder well known in the technical field and. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide), alkaline earth metal salts (eg, barium sulfate, strontium sulfate,
Mention may be made of magnesium sulphate, potassium carbonate), non-image forming silver halide grains and glass.
Further, examples of the organic matting agent include starch, cellulose ester, cellulose ether and synthetic resin. As the synthetic resin, it is preferable to use a water-insoluble or poorly water-soluble synthetic polymer. Examples of such polymers include alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates,
Alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide,
Included are homopolymers or copolymers of methacrylamide, vinyl esters, acrylonitrile, olefins, styrene or benzoguanamine. In the case of the above copolymer, examples of other copolymerized units include acrylic acid,
Methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, sulfoalkyl acrylates, sulfoalkyl methacrylates and styrene sulfonic acids can be mentioned. In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinylcarbazole,
Polyvinylidene chloride can also be used. Further, an alkali-soluble matting agent such as an alkyl methacrylate / methacrylic acid copolymer (JP-A-53-7231 and JP-A-58-66).
937 and 60-8894) and an alkali-soluble polymer having an anionic group (JP-A-58).
No. 166341). The particle size of the matting agent is preferably in the range of 1 to 50 μm. The particle size distribution is
It may be monodisperse or polydisperse. A matting agent whose maximum particle size does not exceed 30 μm.
It is particularly preferable that the content of m or more is 10 vol.% or less. The amount of the above matting agent used is 0.01 to 1 g / m ^2.
Is preferably used in the range of 0.1 to 0.7 g /
More preferably, it is used in the range of m ² .

[Polymerization Inhibitor] A polymerization inhibitor can be added to the curable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. As the polymerization inhibitor for this purpose, any conventionally known polymerization inhibitor can be used. Examples of the polymerization inhibitor include nitrosamine compounds, thiourea compounds, thioamide compounds, urea compounds, phenol derivatives, nitrobenzene derivatives and amine compounds. More specifically,
Cuperon aluminum salt, N-nitrosodiphenylamine, allylthiourea, aryl phosphite, p-toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol. , Pyrogallol, hydroquinone, and alkyl- or aryl-substituted hydroquinones.

Next, each step of image formation will be described. [Image exposure] Image exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity (sensitizing dye) of silver halide. Examples of light sources that can be used include tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, lamps such as carbon arc lamps, various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, (Helim cadmium laser), a light emitting diode, a cathode ray tube and the like. The exposure wavelength is generally visible light, near-ultraviolet light, or near-infrared light, but X-rays or electron beams may be used. The exposure dose is determined by the sensitivity of silver halide,
Generally, it is in the range of 0.01 to 10000 ergs / cm ² , more preferably 0.1 to 1000 ergs / cm ² . When the support is transparent, it is also possible to expose through the support from the back side of the support.

[Development Processing] The development of the light-sensitive material is generally carried out by a dry method (heat development) by heating. However, a wet development process using a developing solution may be adopted. The heat development can be carried out by a method of bringing the heat-sensitive material into close contact with a heated object (for example, a metal plate, a block, a roller), a method of immersing it in a heated liquid, a method of irradiating infrared rays, or the like. The surface of the light-sensitive material may be opened in the air and heated from the side of the support, or the surface may be brought into close contact with a heating object and heated with the air blocked. When the surface is exposed to the air and heated, oxygen in the air may permeate into the light-sensitive material to inhibit the polymerization reaction, so at least part of the layer of the light-sensitive material has the above-mentioned oxygen permeability. It is preferred to use low polymers as binders. The heating temperature is 60 to 200 ° C., more preferably 100 to 150
It is in the range of ° C. The heating time is in the range of 1 to 180 seconds, more preferably 5 to 60 seconds. The exposed photosensitive material may be preheated at a temperature lower than the main heating condition or at a short time, or may be postheated after the main heating. The post-heating may be performed after the image formation post-treatment, for example, after the elution (etching) treatment. When a polymerization image is formed by utilizing the polymerization inhibiting action of the reducing agent or its oxidant, it is necessary to uniformly generate radicals from the polymerization initiator. When a thermal polymerization initiator is used, radicals can be generated by heating at the time of thermal development, so heating is required only once. When a photopolymerization initiator is used, it is necessary to expose the entire surface after thermal development in order to generate radicals. The light at this time must have a wavelength that can be absorbed by the photopolymerization initiator.
The light source can be appropriately selected from those exemplified as the light source used for the image exposure. The exposure dose is in the range of about 10 ^{3 to} 10 ⁷ ergs / cm ² .

After heat development, the resulting image has a chemical or physical property (for example, solubility, surface tackiness, adhesion strength with the support, softening point, etc.) between its cured and uncured areas. Post-treatment is performed by utilizing the difference in refraction, dielectric constant, diffusivity, and colorability. The post-treatment includes elution (etching) treatment, removal treatment (by sheet), transfer treatment, toner development treatment and dyeing treatment. Hereinafter, each process will be described. You may implement combining these processes arbitrarily.

[Elution (Etching) Process] In the elution process, the difference in solubility between the uncured portion and the cured portion is used to elute only the uncured portion to form a polymer image. Generally, after thermal development, the photosensitive material is immersed in a liquid (etching liquid) capable of removing the uncured portion of the curable layer. For the etching solution,
A liquid that dissolves or swells the uncured curable layer, such as an organic solvent, an alkaline aqueous solution or a mixture thereof, is used.
Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium metasilicate, sodium metasilicate, potassium phosphate, sodium phosphate, ammonia and amino alcohols (eg, monoethanolamine, diethanolamine). , Triethanolamine). Various organic solvents may be added to the water-based etching solution, if necessary. As the organic solvent, a lower alcohol (eg, methanol, ethanol, propanol,
Butanol), aromatic ring-containing alcohol (eg, benzyl alcohol, phenethyl alcohol), ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and the amino alcohols described above as the base. Further, a surfactant, a defoaming agent, and other additives can be added to the etching solution as needed. Further, a commercially available developing solution for a printing plate can also be used. The light-sensitive material that has undergone the heat development may be directly immersed in the etching solution, or may be previously immersed in the etching solution after the photosensitive layer other than the curable layer is washed with water or peeled and removed. .

[Removal Treatment (by Sheet)] By utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion, the uncured portion or the cured portion is selectively separated into another sheet (removal sheet).
And remove it. As a result, the portion remaining on the photosensitive material is used as an image. The removal sheet may be laminated with the photosensitive material before image exposure or development.

[Transfer Processing] By utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion, the uncured portion or the cured portion is selectively attached to another sheet (image receiving material). Transcribe. As a result, the portion transferred to the image receiving material is used as an image. The image receiving material may be laminated with the photosensitive material before image exposure or development.

[Toner Development Processing] A coloring substance (toner) is selectively adhered to the uncured portion or the cured portion to visualize the image. Toner can be attached to the uncured portion by utilizing the difference in surface tackiness between the uncured portion and the cured portion. Further, after selectively removing the uncured portion or the cured portion, the toner may be attached to the remaining portion. It is also possible to provide an adhesive layer on the photosensitive material, selectively remove the uncured portion or the cured portion, and then attach the toner to the exposed adhesive layer. Further, the toner developing process can be performed on the image receiving material selectively transferred to the uncured portion or the cured portion.

[Dyeing Process] The uncured part or the cured part is selectively dyed to visualize the image. The dyeing process may be performed on the image receiving material selectively transferred to the uncured portion or the cured portion.

The image obtained as described above can be used for printing plates, color proofs, hard copies, reliefs and the like.

[0073]

【Example】

[Example 1] Preparation of photosensitive material " Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the SA1050 aluminum plate was grained with a nylon brush and an aqueous suspension of pumicetone (400 mesh), and then thoroughly washed with water. Next, it was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, and then washed with running water. It was neutralized and washed with a 20% nitric acid aqueous solution, and then washed with water. The obtained aluminum plate was subjected to a rectangular wave alternating waveform current (condition: voltage at anode 12.
7V, the ratio of the amount of electricity at the cathode to the amount of electricity at the anode is 0.
9. Electricity at anode 160 coulomb / dm ² )
The electroroughening treatment was performed in a 1% aqueous nitric acid solution containing 0.5% aluminum nitrate. The surface roughness of the obtained plate is 0.6.
μm (Ra indication). Following this treatment, it was immersed in a 1% aqueous sodium hydroxide solution at 40 ° C. for 30 minutes, and then treated in a 30% aqueous sulfuric acid solution at 55 ° C. for 1 minute.
Next, so that the thickness becomes 2.5 g / m ² in a 20% aqueous solution of sulfuric acid, using a direct current, a current density of 2A / dm ²
The aluminum support (A) was prepared after anodizing treatment, washing with water and drying under the conditions.

Next, temperature: about 165 ° C., pressure: 7 kg /
A temperature of 95 obtained by ejecting cm ² of water vapor into the air
The support (A) was exposed for 30 seconds in an atmosphere having a water vapor pressure of about 627 Torr at a temperature of ° C to prepare a support (B). Similarly, a support (C) was prepared by exposing it to an atmosphere having a temperature of 75 ° C. and a water vapor pressure of about 700 torr for 25 minutes. further,
1 in an atmosphere with a temperature of 120 ° C and a water vapor pressure of about 110 torr
A support (D) was prepared by exposing for 0 seconds. Furthermore, the support (E) was prepared by exposing it to an atmosphere having a temperature of 95 ° C. and a water vapor pressure of about 40 Torr for 12 minutes.

"Preparation of Pigment Dispersion Liquid" A mixed liquid having the following composition was dispersed in a Dynomill disperser at 300 rpm at 45 ° C. for 1 hour to obtain a pigment dispersion liquid having an average particle size of 0.10 μm.

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Pigment (Chromophtal red A2B) 18g Allylmethacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 12 g Cyclohexanone 30 g Propylene glycol monomethyl ether 40 g ─────────────────────────────────────

[Formation of Curable Layer] The following coating liquid was applied onto the aluminum supports (A) to (E) and dried to form a curable layer having a thickness of 1.8 μm.

──────────────────────────────────── Curable layer coating liquid ────── ────────────────────────────── pentaerythritol tetraacrylate 2.5g allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 20% by weight propylene glycol monomethyl ether solution 37.5 g The above pigment dispersion 13.0 g Methyl ethyl ketone 74.0 g ────────────────────── ───────────────

[Preparation of Silver Halide Emulsion] Gelatin, potassium bromide, and water were added, sodium hydroxide was added, and a solution having a pH of 9.5 at room temperature was heated to 55 ° C. After adding the thioether compound in an amount equivalent to 2.0 × 10 ⁻³ mol based on the total amount of silver nitrate added, the total amount of the aqueous silver nitrate solution, potassium iodide and silver nitrate added while maintaining the pAg of the reaction vessel at 9.0. The aqueous solution of potassium bromide containing rhodium ammonium chloride was added by the pAg control double jet method to form particles on copper iodobromide so that the molar ratio of rhodium to 2 × 10 ⁻⁷ mol was 2 × 10 ⁻⁷ mol. Then add sulfuric acid to set the pH to 6.0,
Subsequently, at 55 ° C. and pAg = 9.3, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridium (III) salt is added so that the molar ratio of iridium to silver is 5 × 10 ⁻⁷ mol. Was added in two stages by the double jet method to prepare core / shell type silver iodobromide emulsion grains having the following composition.

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

These emulsion grains were monodisperse, and 98% of all grains were present within the average grain size ± 40%.
Then, after desalting this emulsion, the following two kinds of spectral sensitizing dyes A and B were mixed in a ratio of 2: 1 while stirring while keeping the temperature at 40 ° C.
Mole ratio mixed methanol solution was 8 × 10 ⁻⁴ mol / mo
1Ag equivalent amount was added and held for 15 minutes, and then a sodium salt of thiol having the following structure was added at 6 × 10 ⁻⁴ mol / m 2.
An equivalent amount of olAg was added, and the mixture was stirred and held for 5 minutes. Then, the emulsion pH was adjusted to 6.5 and pAg to 8.8 to obtain a silver halide emulsion.

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[Chemical 4]

[Formation of Photosensitive Layer] The following coating liquid was prepared, coated on the curable layer and dried to form a photosensitive layer having a dry film pressure of about 1.2 μm.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol with a saponification degree of 79.5% (trade name: PVA-405, Kuraray 10 wt% aqueous solution of Co., Ltd. 10.5 g 0.11 wt% methanol solution of the following additive (SH-1) 0.41 g 0.11 wt% aqueous solution of the following additive (SH-2) 0 .41 g The above silver halide emulsion 0.50 g A 5% by weight aqueous solution of the following surfactant (SA-1) 0.40 g Water 7.80 g The following reducing agent dispersion liquid 1.20 g ───────── ────────────────────────────

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[Chemical 6]

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[Chemical 7]

[Preparation of Reducing Agent Dispersion] 2.2 g of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) was added to 100 g of the following reducing agent powder using a Dynomill disperser.
It was dispersed in 900 g of a weight% aqueous solution. The particle size of the reducing agent was about 0.8 μm or less.

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[Preparation of Base Precursor Dispersion] 250 g of the powder of the following base precursor was added to polyvinyl alcohol (P of Kuraray Co., Ltd.) using a Dynomill disperser.
It was dispersed in 750 g of a 3% by weight aqueous solution of VA-205). The particle size of the base precursor was about 0.5 μm or less.

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[Chemical 9]

[Formation of Overcoat Layer] The following coating solution was prepared, coated on the photosensitive layer and dried to form an overcoat layer having a dry film thickness of about 33 μm.

──────────────────────────────────── Coating solution for the overcoat layer ───── ─────────────────────────────── Polyvinyl alcohol with a saponification degree of 98.5% (trade name: PVA-105, 100.0% by weight aqueous solution of Re Co., Ltd. 200.0 g The above base precursor dispersion 1.25 g 5% by weight aqueous solution of the above surfactant (SA-1) 4.0 g ─────────── ────────────────────────────

"Preparation of alkaline eluent" An alkaline eluent (pH: 13.5) having the following composition was prepared.

──────────────────────────────────── Alkaline eluate ───────── ──────────────────────────── 28% aqueous solution of potassium silicate 125.0 g Potassium hydroxide 15.0 g Water 750.0 g ── ───────────────────────────────────

(Image formation) An original film was brought into close contact with the light-sensitive material obtained as described above, and a 500 W tungsten lamp was used for exposure for 1.5 seconds through a band-pass filter which transmits light of 500 nm. Next, the aluminum support surface of the light-sensitive material was brought into close contact with a hot plate heated to 140 ° C., and heat development was carried out for 50 seconds while the PET film was kept in close contact with the surface of the light-sensitive material. A silver image was observed in the exposed portion. .. Next, this was brush-developed with an automatic etching machine using the above-mentioned alkaline eluent, and then washed well with water to elute and remove the photosensitive layer in the unexposed portion, and the exposed portion was colored red with good contrast. A relief image of the polymer was formed. The maximum density (Dmax) and the minimum density (Dmin) of the printing plate thus obtained, and the degree of generation of the dot-like residual film in the non-image area, the diameter per cm ² was 1
Set the number of spot-like residual films of 0 micron or more to zero, 1 to 2 and 3
It was evaluated in 5 grades of 10 to 11, 11 to 100 and 100 or more. Furthermore, the ink stains on the printed matter were evaluated in the same manner. The results are shown in Table 1.

[0100]

[Table 1] Table 1 ──────────────────────────────────── Aluminum sealing condition Non-image Part Ink support Temperature Steam pressure Time Dmax Dmin Dotted residual film Stain ─────────────────────────────────── ─ A − − − − − − 1.54 0.33 100 or more 100 or more B 95 ° C. 627 Torr 30 seconds 1.56 0.33 Zero Zero C 75 ° C. 700 Torr 25 minutes 1.52 0.33 1 to 2 3 to 10 D 120 ° C. 110 Torr 10 seconds 1.58 0.33 1 2 pieces 1-2 E 95 ° C 42 Torr 12 minutes 1.55 0.33 11-100 pieces 11-100 pieces ────────────────────────────── ──────

Example 2 A photosensitive material was prepared in the same manner as in Example 1 except that the aluminum support (A) used in Example 1 was changed to (F) and (G) shown below. An image was formed and evaluated. The results are shown in Table 2. The support (F) was prepared by keeping the support (A) at 70 ° C. and using a sodium silicate reagent (JIS No. 3, SiO ₂ / Na ₂ O (molar ratio)).
= 3.1 to 3.3) was dipped in a 5% aqueous solution for 30 to 60 seconds and washed with water. Further, the support (F) is exposed for 30 seconds in an atmosphere of a temperature of about 165 ° C., a pressure of 7 kg / cm ² and a temperature of 95 ° C. obtained by jetting water vapor into the air at a steam pressure of about 627 Torr. A support (G) was prepared.

[0102]

[Table 2] Table 2 ──────────────────────────────────── Aluminum sealing condition Non-image Part Ink support Temperature Steam pressure Time Dmax Dmin Dotted residual film Stain ─────────────────────────────────── ─ F − − − − − − 1.56 0.33 100 or more 100 or more G 95 ° C. 627 Torr 30 seconds 1.52 0.33 Zero Zero ───────────────────────── ───────────

Example 3 A light-sensitive material was prepared in the same manner as in Example 1 except that the aluminum support (A) used in Example 1 was changed to (H) and (I) shown below. An image was formed and evaluated. The results are shown in Table 3. An aqueous solution containing 1% of carboxymethyl cellulose and 1% of nickel acetate (tetrahydrate) was applied onto the support (A) by a roll coater and dried to prepare a support (H). Also the temperature:
The support (H) is exposed for 30 seconds in an atmosphere having a temperature of 95 ° C. and a steam pressure of about 627 torr obtained by ejecting steam having a pressure of about 165 ° C. and a pressure of 7 kg / cm ² into the air. I) was prepared.

[0104]

[Table 3] Table 3 ──────────────────────────────────── Aluminum sealing condition Non-image Part Ink support Temperature Steam pressure Time Dmax Dmin Dotted residual film Stain ─────────────────────────────────── ─ H − − − − − − 1.52 0.33 100 or more 100 or more I 95 ° C. 627 Torr 30 seconds 1.56 0.33 Zero Zero ───────────────────────── ───────────

As can be seen from the above results, the light-sensitive material prepared according to the present invention has no point-like residual film in the non-image area, a clear image with good discrimination can be obtained, and also in printed matter. It gives good prints without spots.

Reference Example 1 In the production of the aluminum support A of Example 1, the amount of the anodic oxide film was 2.5 g / m 2.
Supports J and K were prepared in the same manner except that the amount was changed from ² to 5.0 g / m ² or 10.0 g / m ² .
Each layer was provided on Supports A, J and K in the same manner as in Example 1 to prepare a light-sensitive material. An image was formed in the same manner as in Example 1 using each light-sensitive material. The degree of contamination of the non-image area of the obtained image was examined. Then supports A, J and K
The following photosensitive solution was applied onto the above so that the coating weight was 2.5 g / m ² to form a photosensitive layer. The obtained light-sensitive material corresponds to the light-sensitive material using the substrate A in the example of JP-A-59-114100 (comparative example).

──────────────────────────────────── Photosensitive liquid (optical sensor: o-quinonediazide compound) ──────────────────────────────────── Naphthoquinone-1,2-diazide-5-sulfonyl chloride (o -Quinone diazide compound) and an esterification product of pyrogallol-acetone resin 0.90 g cresol novolac resin 2.00 g phthalic anhydride 0.20 g 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -S- Tolazine 0.02 g Oil-soluble dye (CI: 42595) 0.03 g Ethylene chloride 15 g Methyl cellosolve 12 g ───────────────────────────── ────────

A light-sensitive material using an o-quinonediazide compound as a photosensor was exposed through a transparent positive film in a vacuum baking frame from a distance of 1 m with a metal halide lamp of 3 Kw for 50 seconds, and then exposed to SiO ₂ / NaO.
Was developed with a 5.26% aqueous solution of sodium silicate (pH = 12.7) having a molar ratio of 1.74 (JP-A-59-11).
4100). The degree of contamination of the non-image area of the obtained image was examined. Fourth result
Shown in the table.

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Table 4 of Table 4 ──────────────────────────────────── aluminum anodic oxide non-image portion Contamination (light sensor of photosensitive material) Support Amount of film (silver halide) (o-quinonediazide compound) ─────────────────────────── ────────── A 2.5 g / m ² 0.02 0.09 J 5.0 g / m ² 0.05 0.17 K 10.0 g / m ² 0.09 0.35 ─ ───────────────────────────────────

As is clear from the results shown in Table 4, the problem of contamination of the non-image area is not serious in the light-sensitive material using silver halide as an optical sensor, even if the sealing treatment is not carried out.

Claims (2)

[Claims] 1. An aluminum anodic oxide film, a curable layer containing a polymerizable compound or a crosslinkable polymer, and a photosensitive layer containing silver halide are sequentially provided on an aluminum support. A photosensitive material, wherein the functional layer further contains a reducing agent, and the anodic oxide film is subjected to a sealing treatment. 2. The anodic oxide coating is subjected to a sealing treatment by exposing the aluminum support provided with the anodic oxide coating to a temperature of 70 to 270 ° C. and an atmosphere having a water vapor pressure of 100 Torr or more. The light-sensitive material described in 1.