JPH09281707A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress aggregation or precipitation in a water-base eluting liquid and to enable stable treatment for a long time by controlling the amt. of gelatin in a photosensitive layer to a specified weight ratio to the amt. of water-soluble synthetic polymers and treating a photosensitive material in a water-based eluting liquid containing a protein decomposing enzyme in a specified range. SOLUTION: This method includes a process to expose a photosensitive material 1 containing a reducing agent for an image, a process to heat the photosensitive material to form a hardened part and nonhardened part corresponding to the exposed part and the nonexposed part in a hardened layer, a process to remove the photosensitive layer with a water-based eluting liquid 8, and a process to remove the nonhardened part in the hardened layer with an alkali eluting liquid 18 to form the remaining image comprising the hardened part on a base body. In this method, the amt. of gelatin in the photosensitive layer is 0.01 to 10wt.% of water-soluble synthetic polymers and the photosensitive material 1 is treated with a water-based eluting liquid 8 containing a protein decomposing enzyme in 1 to 30m<2> /l range. The gelatin is decomposed by adding a protein decomposing enzyme to the water-based eluting liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention utilizes the photosensitivity of silver halide to cure a polymerizable compound or a crosslinkable polymer into an image and then removes the uncured portion to form a residual image consisting of a cured portion. The present invention relates to an image forming method for forming an image on a support.

[0002]

2. Description of the Related Art A light-sensitive material containing a silver halide, a reducing agent and a polymerizable compound is imagewise exposed, and the silver halide is thermally developed, whereby the polymerizable compound is polymerized imagewise to form a polymer image. The method is disclosed in Japanese Patent Publication Nos. 3-12307 and 3-12308 (US Pat. No. 4629).
676 and European Patent No. 0174634). 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 an oxidant radical). .

Further, a light-sensitive material suitable for producing a printing plate using this image forming method is disclosed in JP-A-64-17047 (US Pat. No. 4,985,339 and European Patent Publication No. 0298522A), JP-A No. 5-2496
67 (U.S. Pat. No. 5,122,443 and European Patent Publication No. 0426192A) and JP-A-4
No. 191856. Furthermore, an image forming method suitable for producing a color proof is disclosed in JP-A-4-3.
It is described in Japanese Patent No. 38955. Crosslinkable polymers may be used in addition to or in place of the polymerizable compounds in the production of printing plates or color proofs. In addition, a light-sensitive material used for such image formation is often provided with a photosensitive layer containing silver halide and a curable layer containing a polymerizable compound or a crosslinkable polymer separately.

In an image forming method using a photosensitive material in which a photosensitive layer and a curable layer are separated from each other, the photosensitive layer is removed with an aqueous eluent after thermal development, and then the curable layer is removed with an alkaline eluent. The uncured part is removed and a residual image consisting of the cured part is formed on the support. Conventionally, simple water (preferably warm water) has been used as the aqueous eluent. It is possible to elute the photosensitive layer and the uncured part at the same time,
If the two types of layers are removed at the same time, the eluate will deteriorate rapidly. Although it is possible to remove the photosensitive layer by peeling, it is difficult to actually peel the photosensitive layer completely. The photosensitive layer is generally a layer containing a hydrophilic polymer as a binder and containing silver halide grains dispersed in the binder. On the other hand, the silver halide grains are
Prepared as a silver halide emulsion using gelatin as a protective colloid. Therefore, a photosensitive layer (silver halide emulsion layer) containing gelatin as a binder can be formed only by coating the silver halide emulsion. However, in the photosensitive layer using gelatin as a binder,
A good image could not be obtained.

Therefore, in the above-mentioned image forming method, a water-soluble synthetic polymer such as polyvinyl alcohol is used as a binder instead of gelatin. Unlike a natural polymer such as gelatin, a synthetic polymer can be arbitrarily designed in its molecular structure and can introduce a strong or large number of hydrophilic groups. The photosensitive layer containing a water-soluble synthetic polymer as a binder can be easily dissolved in water and easily removed. A good image can be formed with the photosensitive layer using the water-soluble synthetic polymer. The use of gelatin is essentially indispensable for the formation of silver halide grains (preparation of silver halide emulsion). That is, it is difficult to form uniform silver halide grains without gelatin. The gelatin used for the preparation of silver halide emulsion is contained in the photosensitive layer in a state of being attached to the surface of silver halide grains. In the conventional image forming method, the amount of gelatin attached to the surface of silver halide grains did not hinder the removal of the photosensitive layer.

[0006]

The present inventor has conducted research on an image forming method using a photosensitive material in which a photosensitive layer and a curable layer are separated, and a large amount of the photosensitive material is produced by an aqueous eluent using an apparatus. After treatment (treatment in the range of 1 to 30 m ² / liter), we encountered problems that could not have been predicted in the conventional experimental stage. That is, when a large amount of a light-sensitive material is processed for a long time using an apparatus, the components of the photosensitive layer are dissolved in an aqueous eluent (warm water) for removing the photosensitive layer, and the eluate gradually becomes a thick solution. . Then, coagulation of the components of the photosensitive layer and precipitation of insoluble components occurred at a concentration much lower than the concentration at the limit of use of the eluate estimated from the solubility of the components of the photosensitive layer. The resulting precipitate was a sludge-like precipitate that was not redispersible. The binder (matrix) of the photosensitive layer is a water-soluble synthetic polymer such as polyvinyl alcohol. Gelatin, which is contained in the photosensitive layer in a small amount (generally 0.01 to 10% by weight of the amount of the water-soluble synthetic polymer), is also a highly hydrophilic protein. The photosensitive layer also contains a water-insoluble component such as silver halide, but the amount of the layer as a whole is small and can be dispersed or emulsified in an aqueous eluate. The water-soluble synthetic polymer also has a function of promoting dispersion or emulsification of water-insoluble components. It was quite unexpected that the above problems would occur in the treatment of removing the photosensitive layer having high hydrophilicity as a whole with water.

Upon investigation by the inventor, the resulting precipitate was a mixture of silver halide emulsion components, water-soluble synthetic polymers and water-insoluble components of the photosensitive layer. When the present inventors further investigated the cause of precipitation, it was found that gelatin contained in a small amount in the photosensitive layer was involved in the formation of precipitate. Gelatin has poor compatibility with water-soluble synthetic polymers, and the mixture of gelatin and water-soluble synthetic polymers is
Each of them can be dissolved in water only at a lower concentration than when used alone. Further, the presence of gelatin reduces the function of promoting the dispersion or emulsification of the water-insoluble component of the water-soluble synthetic polymer. It is considered that due to mixing of the precipitates caused by these causes, a sludge-like precipitate having no redispersibility was generated. When a large amount of a light-sensitive material is processed using the apparatus, even if the amount of the precipitate is small, the circulation system of the elution removal tank is clogged and the precipitate is fixed around the elution bath. For this reason, the aqueous eluate had to be replaced with a slight treatment of the light-sensitive material so that no precipitate was formed. An object of the present invention is to provide an image forming method capable of suppressing coagulation or precipitation in an aqueous eluate for removing a photosensitive layer and performing stable processing for a long time.

[0008]

The above-mentioned object was achieved by the image forming method (1) or (2) below. (1) A curable layer containing a polymerizable compound or a crosslinkable polymer and a photosensitive layer in which silver halide grains to which gelatin is attached are dispersed in a binder made of a water-soluble synthetic polymer on a support. Step of imagewise exposing a photosensitive material which is provided sequentially and further contains a reducing agent; heating the photosensitive material to form a cured portion and an uncured portion corresponding to an exposed portion or an unexposed portion in a curable layer. Removing the photosensitive layer with an aqueous eluent; and removing the uncured portion of the curable layer with an alkaline eluent,
An image forming method comprising a step of forming a residual image comprising a cured part on a support, wherein the amount of gelatin in the photosensitive layer is 0.01 to 10% by weight of the amount of the water-soluble synthetic polymer, 1 to 30 m of light-sensitive material with the above aqueous eluent
An image forming method characterized in that the treatment is carried out within a range of ² / liter, and the aqueous eluate contains a proteolytic enzyme. (2) A curable layer containing a polymerizable compound or a crosslinkable polymer and a photosensitive layer in which silver halide grains to which gelatin is attached are dispersed in a binder made of a water-soluble synthetic polymer on a support. Step of imagewise exposing a photosensitive material which is provided sequentially and further contains a reducing agent; heating the photosensitive material to form a cured portion and an uncured portion corresponding to an exposed portion or an unexposed portion in a curable layer. Removing the photosensitive layer with an aqueous eluent; and removing the uncured portion of the curable layer with an alkaline eluent,
An image forming method comprising the step of forming a residual image comprising a cured part on a support, wherein the amount of gelatin in the photosensitive layer is 0.01 to 10 of the amount of the water-soluble synthetic polymer.
1% to 30% by weight of the photosensitive material with the above aqueous eluent.
An image forming method, wherein the treatment is carried out in a range of m ² / liter, and the aqueous eluate contains a surfactant.

[0009]

As described above, according to the research conducted by the present inventors, it was found that the first cause of the above-mentioned problem of the precipitation is gelatin contained in a small amount in the photosensitive layer.
Since gelatin was present in such a small amount that it was attached to the surface of silver halide grains, it was completely unexpected that such a serious problem would occur. In order to solve this problem, in the first embodiment of the present invention, a protease is added to the aqueous eluate to decompose gelatin. When gelatin is decomposed, the generation of precipitates is suppressed, and the aqueous eluate is kept for a long time.
Specifically, it can be used up to the solubility limit of each component of the photosensitive layer. Further, the problem can be similarly solved by adding a surfactant to the aqueous eluate. As described above, the action of gelatin reduces the function of dispersing or emulsifying the water-insoluble component of the water-soluble synthetic polymer,
A precipitate has formed. In the second aspect of the present invention, a surfactant may be added to compensate for the reduced dispersing or emulsifying function. As described above, in the image forming method of the present invention, coagulation or precipitation in the aqueous eluate for removing the photosensitive layer is suppressed, and the treatment can be stably performed for a long time.

The above two types of solutions themselves are known in another technical field. For example,
55567 discloses a non-silver photosensitive layer capable of forming a water-insoluble lipophilic image on a support having a hydrophilic surface,
Further, in a plate making method using a photosensitive lithographic printing plate having a gelatin silver halide light-sensitive emulsion layer thereon, a method in which a fixing solution and / or a wash-out solution for the gelatin silver halide light-sensitive emulsion layer contains a protease. Is disclosed. It is already known that the use of a proteolytic enzyme is effective in removing a layer containing gelatin as a binder (matrix), such as this gelatin silver halide photosensitive emulsion layer. However, it was a totally unexpected result that the use of proteolytic enzyme was effective even though the amount was small enough to be attached to the surface of silver halide grains.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

[Proteolytic enzyme] In the first embodiment of the present invention, a proteolytic enzyme is added to the aqueous eluate. The proteolytic enzyme used in the present invention needs to have a function of degrading gelatin. However, gelatin is a protein that is easily decomposed, and ordinary proteolytic enzymes can decompose gelatin. Any of animal enzymes, plant enzymes and microbial enzymes can be used. Examples of animal enzymes include pepsin,
Includes trypsin and chymotrypsin. Examples of plant enzymes include ficin and papain. Many microbial enzymes are used as commercially available proteolytic enzymes. As a commercially available protease, Takamine H
T ^TM (manufactured by Miles Laboratory), bioprase PN-4
^TM (manufactured by Nagase Seikagaku Corporation) and Pronase ^TM (Calb
iochem-Novabiochem) is used. For the proteolytic enzyme used for the decomposition of gelatin, see Japanese Patent Publication No. 45-
No. 36205, JP-A No. 52-97738, Research Disclosure No. 15025, British Patents 1179769, 1354186, US Pat. Nos. 3,515,551, 3,565,618, and 3,620.
It is described in each specification of 737 and 382178. You may use together two or more types of proteolytic enzymes.
The concentration of proteolytic enzyme in the aqueous eluate was 0.001
To 10% by weight, preferably 0.01 to 5
More preferably, it is% by weight. PH of aqueous eluate
Is preferably adjusted to the optimum pH of the protease used.

[Surfactant] In the second embodiment of the present invention,
Add surfactant to the aqueous eluate. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants and fluorine-based surfactants can be used. Nonionic surfactants and amphoteric surfactants are preferred, and amphoteric surfactants are particularly preferred. The nonionic surfactant is constituted by chemically linking a nonionic hydrophilic atomic group and a hydrophobic atomic group. As the nonionic hydrophilic atomic group, polyoxyalkylene, polyhydric alcohol (including sugar and sugar alcohol) and polyethylene polyamine are generally used. Polyoxyalkylenes, especially polyoxyethylene, are preferred. The hydrophobic atomic group is generally a hydrocarbon group. Aliphatic hydrocarbon groups are preferred over aromatic hydrocarbon groups. Saturated aliphatic (alkyl) groups are preferred over unsaturated aliphatic groups.

Examples of nonionic surfactants are polyoxyethylene alkyl ethers, polyooxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid moieties. Ester, pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene Castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide, , N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters and trialkylamine oxides. The polyoxyethylene moieties in the above examples are other polyoxyalkylenes (eg, polyoxymethylene, polyoxypropylene, polyoxybutylene).
May be replaced with

The anionic surfactant is formed by chemically linking an anionic hydrophilic atomic group and a hydrophobic atomic group. As the anionic hydrophilic atomic group, carboxylic acid, sulfuric acid ester, sulfonic acid, alkylaryl sulfonate, phosphoric acid ester and alkylphosphonic acid are used. Carboxylic acids are particularly preferred. The hydrophobic atomic group is
Similar to the nonionic surfactant, it is generally a hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic (alkyl) group.

The cationic surfactant is constituted by chemically linking a cationic hydrophilic atomic group and a hydrophobic atomic group. Various amines (including quaternary ammonium and imines, amidines and guanidines) are used as the cationic hydrophilic atomic group. Like the nonionic surfactant, the hydrophobic atomic group is generally a hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic (alkyl) group.

Amphoteric surfactants are anionic (hydrophilic)
It is composed of chemical linkages of atomic groups, cationic (hydrophilic) atomic groups, and hydrophobic atomic groups. About each atomic group, it is the same as that of the anionic surfactant and the cationic surfactant. A particularly preferred amphoteric surfactant is represented by the following formula (I).

[0017]

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In the formula (I), R ¹ has 5 carbon atoms.
To 22 hydrocarbon groups. R ¹ constitutes a hydrophobic atomic group. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups and aralkyl groups. Alkyl groups and alkenyl groups are preferred, with alkyl groups being particularly preferred. The alkyl portion of the alkyl group, alkenyl group, alkynyl group and aralkyl group may be linear, branched or cyclic. The aryl group may be substituted with an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. R ¹ preferably has 8 to 20 carbon atoms. l is 1 or 2. p is 0, 1, 2 or 3. p may be 0.
That linking groups corresponding to [NH- (CH _{2) l]} may be omitted. R ² is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. The definition of the hydrocarbon group is the above R ¹
Is the same as m is 1 or 2. q is 0, 1, 2
Or 3. q may be 0. That is, [NH-
There may be no linking group corresponding to (CH ₂ ) _m ]. R ³
Is a hydrogen atom or methyl. n is 1 or 2. Specific examples of the amphoteric surfactant represented by the formula (I) are shown below. Are used).

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

[Chemical 6]

[0024]

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[0025]

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The fluorinated surfactant is a compound in which a hydrogen atom bonded to a carbon atom of the hydrophobic atomic group of the usual surfactant as described above is substituted with a fluorine atom. A compound in which all hydrogen atoms of an alkyl group which is a hydrophobic atomic group are substituted with fluorine atoms (having a perfluoroalkyl group) is preferable. You may use together 2 or more types of surfactant. It may be used in combination with the first aspect of the invention, ie a proteolytic enzyme. The concentration of the surfactant in the aqueous eluate is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. Hereinafter, each step of the image forming method of the present invention,
The elution device, the layer structure of the photosensitive material, and the components of the photosensitive material that can be used in the present invention will be sequentially described.

[Exposure Step] Image exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity of silver halide (sensitizing dye) which is a photosensor. Examples of light sources include tungsten lamps, halogen lamps, xenon lamps,
Lamps such as xenon flash lamps, mercury lamps, carbon arc lamps, various lasers (eg semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser),
A light emitting diode, a cathode ray tube, etc. can be mentioned.
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 generally in the range of 0.01 to 10000 erg / cm ² , more preferably 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 general, the process of exposing silver halide, that is, the process of forming a latent image, is affected by temperature and humidity during exposure,
It is known that the sensitivity of photosensitive materials changes. Therefore, it is desirable that the temperature and humidity of the atmosphere of the light-sensitive material and the light source at the time of exposure are controlled within a constant range as much as possible. Specific adjusting means of the image recording apparatus for achieving the above object is disclosed in JP-A-3-63143 and JP-A-3-63143.
-63637. In the image exposure, it is preferable to set one point in the range of 5 to 40 ° C. (preferably 10 to 35 ° C.) as a set temperature and control the temperature within ± 5 ° C. from the set temperature. It is preferable to similarly control the atmospheric humidity in the apparatus including the photosensitive material and the optical system. The humidity is preferably in the range of 10 to 80% (relative humidity), more preferably in the range of 15 to 75%, most preferably in the range of 25 to 70%.

[Heat development step] The heat development is carried out by a method of bringing the light-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. be able to. The heating temperature is 80 ° C. or higher, preferably 80 to 200 ° C., more preferably 100 to 150 ° C. The heating time is in the range of 1 to 180 seconds, more preferably 5 to 60 seconds. The light-sensitive material, before or after the exposure step,
Preheat at a temperature higher than the main heating temperature for a short time, or
Alternatively, post-heating may be performed after main heating. Pre-heating or post-heating can improve the sensitivity and the curing degree of the image. The post-heating may be performed after the post-treatment of image formation, for example, after the elution step. When a cured image is formed by utilizing the polymerization inhibiting action of the reducing agent or its oxidized product, it is necessary to uniformly generate radicals from the polymerization initiator. When a thermal polymerization initiator is used, heating can be performed once, since radicals can be generated by heating during thermal development. When a photopolymerization initiator is used, the entire surface must be exposed after thermal development in order to generate radicals. The light at this time must have a wavelength that the photopolymerization initiator absorbs. 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 10 ^{3 to} 10 ⁷ erg / cm ² .

[Removing Step of Photosensitive Layer] The photosensitive layer is removed using the aqueous eluent containing the above-mentioned proteolytic enzyme or surfactant. The photosensitive material is (described later)
When there is a hydrophilic layer other than the photosensitive layer such as the overcoat layer, those hydrophilic layers are also removed at the same time as the photosensitive layer. In addition to the proteolytic enzyme and the surfactant, a protein denaturing agent, a chelating agent or an antifoaming agent may be added to the aqueous eluate. The protein denaturing agent is particularly effective when used in combination with a proteolytic enzyme. The chelating agent and the defoaming agent are particularly effective when used in combination with the surfactant. A protein denaturing agent generally breaks a hydrogen bond of a polypeptide and denatures a protein. Examples of protein denaturants include inorganic salts (eg, calcium chloride, zinc chloride, sodium sulfite), organic acid salts (eg, sodium citrate, sodium acetate), urea and its derivatives, and potassium thiocyanide. According to the present invention, the aqueous eluate can be used stably for a long time. The aqueous eluent of the present invention processes a photosensitive material (having a photosensitive layer thickness of 6 μm) in the range of 1 to 30 m ² / liter on average. 1 to 15
It is more preferable to process the light-sensitive material in the range of m ² / liter.

[Unhardened part removing step] The alkaline eluent (etching liquid) for removing the uncured part is an aqueous solution of an alkaline compound, an organic solvent containing an alkaline compound, or an aqueous solution containing an alkaline compound and an organic compound. It is a mixture with a solvent. As the alkaline compound,
Various organic and inorganic compounds can be used.
Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, ammonia and amino alcohols (eg, Monoethanolamine, diethanolamine, triethanolamine).

As the solvent of the alkaline eluate, water or various organic solvents can be used as described above. The solvent of the eluate is preferably mainly composed of water. An organic solvent can be added to the eluate mainly composed of water, if necessary. Alcohols or ethers are preferred as the organic solvent. Examples of alcohols include lower alcohols (eg, methanol, ethanol, propanol, butanol), alcohols having an aromatic group (eg, benzyl alcohol, phenethyl alcohol),
Examples thereof include polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol) and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine). Examples of ethers include
Cellosolves can be mentioned. The alkaline eluent may contain a surfactant, a defoaming agent, and other various additives as required. An amphoteric surfactant is preferably used as the surfactant. P of alkaline eluate
H is preferably 9.0 to 14.0, and 1
More preferably, it is 0.0 to 13.7.

[Transfer Processing] A transfer processing may be carried out in which the cured image formed on the photosensitive material is attached to another sheet (image receiving material) and transferred. As a result, the portion transferred to the image receiving material is used as an image. The toner image obtained may be transferred by first performing the following toner development processing.

[Toner Development Processing] A colored substance (toner) may be attached to the cured image to visualize the image. It is also possible to provide an adhesive layer on the photosensitive material, selectively remove the uncured portion, and then attach the toner to the exposed adhesive layer. Further, the toner developing process can be performed on the image receiving material to which the cured portion is selectively transferred.

[Staining Treatment] The cured image can be dyed to visualize the image. You may perform dyeing processing with respect to the image receiving material which transferred the cured image. The image obtained as described above can be used for printing plates, color proofs, hard copies, reliefs and the like.

[Elution Device] The image forming method of the present invention has a two-step elution process. These steps are preferably processed automatically by using an apparatus. FIG. 1 is a schematic sectional view of an elution device preferably used in the present invention. FIG.
As shown in, the photosensitive material (1) includes a guide roller (2a to 2f, 12a to 12f, 22), a transport roller (3a to 3d, 13a to 13d) and a guide plate (6,
It is transported and guided by 16) and passes through two types of elution tanks. The aqueous eluent (8) is placed in the first elution tank, and the photosensitive material (1) moves in the first elution tank while being immersed in the aqueous eluent (8). A circulation pump (7) is attached to the first elution tank, and the circulated aqueous eluate becomes a water flow by the jetting devices (4a and 4b) to wash the surface of the photosensitive material (1). Also, in the first elution tank,
A roller brush (5) is also attached, and the surface of the photosensitive material (1) is rubbed by the brush. In this way, the photosensitive layer and other hydrophilic layers are removed from the photosensitive material. As shown in FIG. 1, the photosensitive material (1)
If the treatment is carried out while being immersed in the aqueous eluent (8), generation of bubbles is prevented.

An alkaline eluent (1
8) is put therein, and the photosensitive material (1) moves in the second elution tank while being immersed in the alkaline eluent (18). A circulation pump (17) is also attached to the second elution tank, and the circulated aqueous eluate becomes a water flow by the ejection devices (14a and 14b) to wash the surface of the photosensitive material (1). In addition, the roller brush (15) is also used in the second elution tank.
Is attached, and the surface of the photosensitive material (1) is rubbed with a brush. In this way, the uncured portion of the curable layer is removed from the photosensitive material. As shown in FIG. 1, when the photosensitive material (1) is processed in a state of being immersed in the alkaline eluate (18), deterioration of the eluate and generation of bubbles are prevented. As shown in FIG. 1, the first elution tank and the second elution tank have basically the same structure. Therefore, a commercially available automatic elution device (for example, processor PS850NX / PX / PX manufactured by Fuji Photo Film Co., Ltd.) is used.
The elution device shown in FIG. 1 can be easily designed or manufactured by connecting two B).

The elution device shown in FIG. 1 may be additionally provided with a device for washing treatment (washing with running water or circulating water) and desensitizing treatment. Furthermore, the following mechanisms may be provided in each elution tank. Mechanism for automatically replenishing the elution tank with the required amount of replenisher Mechanism for discharging more than a certain amount of the eluent solution Mechanism for automatically replenishing the elution tank with the required amount of water Mechanism for detecting passage of photosensitive material Mechanism for calculating the treated area of the material The calculated treated area is a mechanism for controlling the amount of replenisher, the amount of water replenished and the timing of replenishment. A mechanism for controlling the temperature of the eluate. A mechanism for detecting the pH or concentration of the eluate. For detecting the amount of replenisher, the amount of replenishment of water, and the timing of replenishment depending on the pH or concentration of the eluate

[Layer Structure of Photosensitive Material] In the photosensitive material of the present invention, a curable layer and a photosensitive layer are sequentially provided on a support. The curable layer contains a polymerizable compound or a crosslinkable polymer. The photosensitive layer is. Includes silver halide grains, gelatin and water soluble synthetic polymers. Further, a reducing agent is contained in the curable layer or 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 image formation promoting layers, overcoat layers, tacky layers and release layers.

[Photosensitive Layer] The photosensitive layer 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 preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm. The gelatin contained in the photosensitive layer was used as a protective colloid in the preparation of the silver halide emulsion (described later) and is attached to the silver halide grains. The amount of gelatin in the photosensitive layer is 0.01 to 10% by weight of the amount of the water-soluble synthetic polymer which is the binder of the photosensitive layer,
It is preferably 0.1 to 3% by weight.

[Curable Layer] The curable layer is cured by polymerizing or crosslinking 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.

[Overcoat Layer] The overcoat layer has a function of protecting the light-sensitive material and preventing the ingress of oxygen in the air to enhance the degree of curing of the curable layer. Ingredients that accelerate image formation (eg, basic adjuster, reducing agent, heat development accelerator) are added to the overcoat layer to provide a protective function as an overcoat layer and a function to accelerate image formation. You may. 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, more preferably 0.5 to 10 μm. The overcoat layer is generally formed 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 treatment, these layers must be removed by peeling after thermal development and prior to etching.

[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.

[Peeling Layer] When an image is formed by transfer, a peeling 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
More preferably, it is the above.

[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.

[Support] As the material of the support, paper, synthetic paper, synthetic resin (eg, polyethylene, polypropylene,
Polystyrene laminated paper, plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg aluminum, aluminum alloy,
Zinc, iron, copper), paper or plastic film in which these metals are laminated or vapor-deposited can be used. When the light-sensitive material is used for producing a lithographic printing plate, preferable support materials are aluminum plate, polyethylene terephthalate film, polycarbonate film, paper and synthetic paper. A composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable.

The case where an aluminum plate is used as a support will be described below. The aluminum support is subjected to surface treatment such as surface roughening treatment (graining treatment) or surface hydrophilization treatment, if necessary. The surface roughening treatment is performed by an electrochemical graining method (for example, a method in which a current is applied to an aluminum plate in a hydrochloric acid or nitric acid electrolytic solution to grain the grain) and / or a mechanical graining method. (For example, a wire brush grain method of scratching an aluminum surface with a metal wire, a ball grain method of sanding the aluminum surface with a polishing ball and an abrasive, and a brush grain method of sanding the surface with a nylon brush and an abrasive. Law).

Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of alkaline agents 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 alkali treatment is preferably in the range of 20 to 100 ° C. Furthermore, it is preferable to adjust the treatment conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² . Usually, after alkaline etching, the aluminum plate is washed with acid to remove stains (smuts) left on the surface.
Preferred acids are nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid. The smut removal treatment after the electrochemical graining treatment can be carried out by a known method such as a method of contacting with sulfuric acid having a concentration of 15 to 65% by weight at 50 to 90 ° C.

The aluminum plate surface-roughened as described above can be subjected to anodizing treatment or chemical conversion treatment, if necessary. The anodizing treatment can be performed by a known method. Specifically, in an acid solution,
A direct current or an alternating current is applied to the aluminum plate to form an anodized film on the aluminum surface. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzene sulfonic acid. Anodizing conditions vary depending on the electrolyte solution used. Generally, the concentration of the electrolytic solution is 1 to 80% by weight, the temperature of the electrolytic solution is 5 to 70 ° C., and the current density is 0.5.
It is preferable that the range is from 60 to 60 amps / dm ² , the voltage is from 1 to 100 v, and the electrolysis time is from 10 to 100 seconds. Particularly preferred anodizing methods are a method of anodizing in sulfuric acid at a high current density and a method of anodizing 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 sodium silicate solution). An undercoat layer may be provided on the surface of the support in order to improve the adhesion between the aluminum support and the curable layer and the printing characteristics.

[Undercoat layer] As a component of the undercoat layer, a polymer (eg, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid); amine (eg, monoethanolamine, Diethanolamine, triethanolamine, tripropanolamine) and their hydrochlorides; monoaminomonocarboxylic acids (eg oxalates,
Phosphate, aminoacetic acid, alanine); Oxyamino acid (eg, serine, threonine, dihydroxyethylglycine); Sulfur-containing amino acid (eg, cysteine, cystine); Monoaminodicarboxylic acid (eg, aspartic acid, glutamic acid); Diaminomono Carboxylic acid (eg, lysine); Amino acid having aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine, anthranil); Aliphatic aminosulfonic acid (eg, sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (Eg,
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). It is also possible to use a compound in which some or all of the acid groups of the above compounds are salts (eg, sodium salt, potassium salt, ammonium salt). The above components may be used in combination of two or more.

[Silver Halide Grain] The silver halide is any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Particles can also 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 the grain thickness.
More than double the value. There is no particular limitation on the grain size of 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 also be used. Regarding the grain size distribution, monodisperse grains are preferable to polydisperse emulsions. For monodisperse emulsions, US Pat.
74628, 3655394 and British Patent 14
No. 13748 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. Salts of these elements
The silver halide can be added during or after grain formation to be contained in the grains. The specific method is
U.S. Pat. Nos. 1195432, 1951933, 2
No. 448060, No. 2628167, No. 295097
No. 2, 3488709, 3737313, 3
Nos. 772031 and 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. 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 may be used in combination. It is preferable to use silver halide as an emulsion. The silver halide emulsion is described in Research Disclosure (RD) No. 17643
(December, 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 2, p.
18716 (November 1979), p.648, using gelatin as a protective colloid.

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 N
o. 18716. No. for chemical sensitizers. 17643 (page 23) and No. 18716
(P. 648, right column). Also,
Other known additives are also described in the above two Research Disclosures. For example, regarding the sensitivity enhancer, No. No. 18716 (page 648, right column), No. 1 for the antifoggant and the stabilizer. 17643
(Pages 24 to 25) and No. 18716 (from page 649, right column).

The silver halide emulsion is usually used after spectral sensitization. As the sensitizing dye used in the light-sensitive material, a silver halide sensitizing dye known in photographic technology or the like can be used. 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] In the photosensitive layer of the photosensitive material,
An organic metal salt can be added together with the silver halide. It is particularly preferable to use an organic silver salt as such an organic metal salt. Organic compounds used to form the organic silver salt include triazoles, tetrazoles, imidazoles, indazoles, thiazoles,
Examples thereof include thiadiazoles, azaindenes, and aliphatic, aromatic, or heterocyclic compounds having a mercapto group as a substituent. Further, a silver salt of carboxylic acid or silver acetylene can be used as the organic silver salt. 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, and preferably 10 ⁻⁵ mol, per mol of silver halide.
^{-4 to} 1 mol are used. Also, instead of organic silver salts,
The organic compound constituting the compound may be added to the photosensitive layer and partially reacted with silver halide in the photosensitive layer to be converted to an organic silver salt.

[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. The reducing agent includes 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, sulfonamidopyrazolobenzimidazoles,
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, No. 62-86354, No. 62-86355, No. 62-206540, No. 62
-264404, 62-10937, 63-
254442, JP-A-1-267536 and 2-1
41756, 2-141775, 2-2072
No. 54, No. 2-262662 and No. 2-269352 (including those described as developing agents or hydrazine derivatives). For the reducing agent, see “The Theory of the Photographic Pro” by T. James.
cess "4th edition, pp. 291-334 (1977), Research Disclosure, Vol. 170, No. 1702
No. 9, pp. 9-15 (June 1978), and ibid.
Vol.176, No.17643, pp.22-31, (197
(December 2008). 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.

Among these reducing agents, those having a basicity to form a salt with an acid can be used in the form of a salt with a suitable acid. These reducing agents may be used alone, or as described in 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 firstly by promoting the reduction of silver halide (and / or organic silver salt) by so-called super-additivity. Causing polymerization of a polymerizable compound through an oxidation-reduction reaction with another reducing agent in which an oxidized form of a first reducing agent formed by reduction of silver halide (and / or an organic silver salt) coexists. (Or to inhibit polymerization). However,
In actual use, since the above-mentioned reactions can occur simultaneously, it is difficult to specify which action it is. The reducing agent is preferably used in the range of 0.1 to 10 mol, more preferably 0.25 to 2.5 mol, per 1 mol of silver halide.

By adjusting the type 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 the silver halide and oxidizes itself to an oxidized form. When the oxidized form of this reducing agent is decomposed in the layer to generate radicals,
Polymerization occurs in the portion where the silver halide latent image is formed. Examples of such reducing agents include hydrazines. On the other hand, when the oxidant does not generate (or hardly generates) a radical and the reducing agent itself or the oxidant has a polymerization suppressing function, the polymerization initiator (radical generating agent) is included together with the reducing agent to form a halogen. The part where the latent image of silver halide is not formed (when the oxidized product has a stronger polymerization suppressing function than the reducing agent) or the portion where the latent image is formed (the reducing agent has a more polymerization suppressing function than the oxidized product) If 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] The thermal polymerization initiator is a compound capable of decomposing upon heating to generate free radicals that can be added to the polymerizable compound or the crosslinkable polymer. The thermal polymerization initiator is described in “Addition Polymerization / Ring-Opening Polymerization” (edited by the Society of Polymer Science, Editing Committee for Polymer Experiments) (1983,
Kyoritsu Shuppan), pages 6-18 and JP-A-61-2344.
No. 9 describes this. Examples of the thermal polymerization initiator include azo compounds (eg, azobis (isobutyronitrile), 1,
1'-azobis (1-cyclohexanecarbonitrile)
And peroxides. Photopolymerization initiators are compounds that can generate free radicals that can be added to a polymerizable compound or a crosslinkable polymer upon exposure. Regarding the photopolymerization initiator, Oster et al. “Chem
ical Review, Vol. 68 (1968), 125-15
Page 1, Kosar, "Light-Sensitive System" (John Wil
ey & Sons, 1965), pp. 158-193, JP-A-6
These are described in JP-A-1-75342 and JP-A-2-207254. Examples of the photopolymerization initiator include a carbonyl compound, a halogen-containing compound, a redox couple of a photoreducing dye and a reducing agent, an organic sulfur compound, a peroxide, an optical semiconductor, and a metal compound.
The polymerization initiator is preferably used in the range of 0.001 to 0.5 g, and more preferably 0.01 to 0.2 g, per 1 g of the polymerizable compound.

[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, allyl esters and derivatives thereof. Acrylic esters or methacrylic esters are preferred. Specific examples of the acrylates include pentaerythritol tetraacrylate, trimethylolpropane triacrylate,
Mention may be made of dipentaerythritol hexaacrylate, polyester acrylates and polyurethane acrylates. The polymerizable compound is contained in the curable layer in an amount of preferably 3 to 90% by weight, more preferably 15 to 60% by weight, based on the total amount of the layer. Two or more polymerizable compounds may be used in combination.

[Polymer contained in the curable layer] It is preferable to add a polymer as a binder to the curable layer. The polymer may or may not have crosslinkability. As the crosslinkable polymer, a polymer having an ethylenically unsaturated group in the main chain or side chain of the molecule is preferably used. The crosslinkable polymer may be a copolymer. Examples of polymers having an ethylenically unsaturated group in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene, natural and synthetic rubbers. Examples of polymers having an ethylenically unsaturated group in the side chain of the molecule include poly-1,2-butadiene and poly-1,2-isoprene.

Further, a polymer of an ester or amide of acrylic acid or methacrylic acid, to which a specific residue (R group of --COOR or --CONHR) is bonded, can be used as the crosslinkable polymer. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ² = CR ³ R
⁴ ,-(CH ₂ O) _n -CH ₂ CR ² = CR ³ R ⁴ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ² = CR ³
R ⁴ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ² = CR ³ R ⁴ ,-(CH ₂ ) _n -O-CO-CR ²
= CR ³ R ⁴ and-(CH ₂ CH ₂ O) ₂ -X (R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or aryl. Is an oxy group, R ² and R ³ or R ⁴ may combine with each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue). Can be mentioned. Specific examples of the ester residue, -CH ₂ CH = CH ₂ (JP 64-17
047 JP allyl (meth) corresponding to the polymer of the _{acrylate), - CH 2 CH 2 O} -CH 2 CH = CH 2, -CH 2 C (CH 3) = CH 2,
-CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCO
O-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) are included. Specific examples of amide residues include -C
H ₂ CH = CH ₂ , -CH ₂ CH ₂ -1-Y (Y is a cyclohexene residue) and -CH ₂ CH ₂ -OCO-CH = CH ₂ are included.

In the crosslinkable polymer as described above, free radicals (polymerization initiation radicals or growing radicals during the polymerization process of the polymerizable compound) are added to the unsaturated bond group, and the polymer is polymerized directly or between the polymers. Addition polymerization is carried out through chains, and crosslinks are formed between polymer molecules to cure. Alternatively, atoms in the polymer (eg, hydrogen atoms on the carbon atom adjacent to the unsaturated bond group) are abstracted by free radicals to form polymer radicals, which bond to each other to form crosslinks between polymer molecules. Is cured.

Examples of non-crosslinkable polymers (polymers that are not crosslinkable or weakly crosslinkable) are polyacrylic acid ester, polymethacrylic acid ester, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, Polymethacrylonitrile, polyethylene,
Polyvinyl pyridine, polyvinyl imidazole, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, chlorinated polyethylene, chlorine polypropylene,
Polyester, polyamide, polyurethane, polycarbonate, ethyl cellulose, triacetyl cellulose,
Mention may be made of diacetyl cellulose and cellulose acetate butyrate. Of these repeating units of the polymer, those which can be copolymerized can be arbitrarily combined and used as a copolymer. 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 uncured curable layer is removed by elution with an alkaline aqueous solution after curing, the (crosslinkable or non-crosslinkable) polymer used for the curable layer may have an acidic functional group in its molecule. preferable. Examples of the acidic functional group include a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group and a sulfonimide group. Specifically, monomers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride can be copolymerized at the time of synthesizing the above-mentioned polymer to incorporate these acidic groups 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%, more preferably 5 to 40%. The polymer of the curable layer is most preferably a copolymer obtained by copolymerizing the above-mentioned monomer having a crosslinkable group and a monomer having an acidic functional group. The molecular weight of the polymer of the curable layer is preferably in the range of 1,000 to 500,000.
You may use together 2 or more types of polymers. The content of the polymer in the curable layer is 10 to 90% by weight based on the whole curable layer.
Is preferable, and more preferably 30 to 80% by weight.

[Water-soluble synthetic polymer] A hydrophilic layer such as a photosensitive layer or an overcoat layer of a light-sensitive material contains a water-soluble synthetic polymer as a binder. The water-soluble synthetic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in the molecular structure. Examples of the hydrophilic group include carboxyl, alcoholic hydroxyl group, phenolic hydroxyl group, sulfo, sulfonamide group, sulfonimide and amide. Examples of the hydrophilic bond include a urethane bond, an ether bond, and an amide bond. A particularly preferred water-soluble synthetic polymer is polyvinyl alcohol. Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen permeability, the saponification degree is preferably 50% or more, more preferably 80% 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. Examples of copolymerizable monomers include ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, 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 and then modified 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, crosslinked polyvinyl alcohol can also be used. 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 water-soluble synthetic polymer is 3000
The range of up to 500,000 is preferable. The amount of the water-soluble synthetic polymer used is preferably 0.05 to 20 g / m ² , and more preferably 0.1 to 10 g / m ² .

[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. .
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. Any of them can be used. As the compound having a plasticizing action at room temperature or under heating with respect to a binder used in any layer of the photosensitive material, all known compounds known as a plasticizer of a high molecular compound can be used. As such a plasticizer, "Plastic compounding agent" Taiseisha, P21-63;
"Plastics Additives Second 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
(Plasticizer Technology Vol.1, Reinhold Publi
shing Corp.); "Plasticization and Plasticizer Process" (Plusticization a
nd Plusticizer Process, American Chemistry).

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 resins, phenolic resins, amide compounds (eg, acetamide, propionamide), sulfamides and sulfonamides. Further, two or more of the above thermal development accelerators can be used in combination. Further, it can be added separately in two or more layers. The addition amount of the thermal development accelerator is 0.0
5 to 2 g / m ² , preferably 0.1 to 1 g / m ^2.
g / m ² is more preferable.

[Colorant] A colorant can be added to the light-sensitive material for the purpose of preventing halation and irradiation or coloring the cured image. As the colorant, known pigments and dyes can be used as long as they do not significantly impede the curing reaction of the curable layer or significantly impair the photosensitivity and developability of silver halide. When using a colorant 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 the colorant, the pigments or dyes described in JP-A-5-249667, "Color Index Handbook", and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, 1975) can be used. Dyes for preventing irradiation which have little influence on sensitivity are disclosed in Japanese Examined Patent Publication No. 41-20389 and 4
No. 3-3504, No. 43-13168, and Japanese Patent Laid-Open No. Hei 2
-39042 and U.S. Pat. No. 3697037.
No. 3,423,207, British Patent Nos. 1030392 and 1100546. The content of the colorant is preferably 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 thereof include azoles and azaindenes (Research Disclosure Magazine N
o. 17643, pages 24-25 (1978)), carboxylic acids and phosphoric acids containing nitrogen (described in JP-A-59-168442), cyclic amides (described in JP-A-61-151841), thioethers (described in JP-A-62-151842), polyethylene glycol derivatives (described in JP-A-62-151844), thiols (described in JP-A-62-151844), acetylene compounds (described in JP-A-62-87957). ) And sulfonamides (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 mol 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. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the layer and to inhibit development by interacting with a compound or silver and silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Thermal development terminators are disclosed in JP-A-62-2531.
No. 59, JP-A-2-42447 and 2-26
No. 2661, each of which is described.

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

[Matting Agent] A matting agent may be added to the back layer or the uppermost layer of the light-sensitive material for the purpose of lowering the tackiness of the front surface or the back surface of the light-sensitive material and preventing adhesion when the light-sensitive materials are stacked. it can. As the matting agent, inorganic or organic solid particles that can be dispersed in a hydrophilic polymer are used. Such grains are known in the art of ordinary silver halide photography. Examples of materials for the matting agent include oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers. The particle size of the matting agent is 1 to 50 μm
Is preferred. Matting agent is 0.01 to 1 g / m
² , preferably 0.1 to 0.7 g
/ M ² is more preferably used.

[Polymerization Inhibitor] A polymerization inhibitor may be added to the curable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. Conventionally known polymerization inhibitors can be used. Examples of polymerization inhibitors include nitrosamine compounds, urea compounds, thiourea compounds, thioamide compounds, phenol derivatives and amine compounds.

[0078]

【Example】

 [Example 1] Preparation of photosensitive material "Creation of aluminum support" 0.30 mm thick aluminum
Nylon brush and pumice stone (4
(00 mesh) with a water suspension and then sand it with water.
Washed well. Next, add 10% sodium hydroxide solution
After dipping at 70 ° C for 60 seconds to etch it, run it under running water.
Washed Neutralize and wash with 20% nitric acid solution,
I washed it with water. Alternating the obtained aluminum plate with a rectangular wave
Waveform current (condition: voltage at anode 12.7v, electricity at anode
Ratio of electricity at cathode to 0.8, electricity at anode 16
0 coulomb / dm^Two ) In a 1% nitric acid aqueous solution.
A surface roughening treatment was performed. The surface roughness of the obtained plate was 0.
It was 6 μm (Ra indication). Following this process, 30
% Desulfuric acid aqueous solution at 55 ° C. for 2 minutes. Next
And has a thickness of 2.7 g / dm^Two 20% sulfur
Anodizing treatment was performed in an aqueous acid solution (current density: 2 A / d
m^Two ). The obtained aluminum plate was treated with 3% by weight of silicic acid.
Immerse in sodium aqueous solution at 70 ℃ for 20 seconds, wash with water and dry
Dried.

[Preparation of Pigment Dispersion] A mixture having the following composition was mixed with a Dynomill disperser at 3000 rpm at 45 ° C. for 1 hour.
After time-dispersion, a pigment dispersion having an average particle size of 0.10 μm was obtained.

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Pigment (chromophthal red A2B) 18g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 83 / 17) 12g Cyclohexanone 30g Propylene glycol monomethyl ether 40g ─────────────────────────────────────

[Formation of Curable Layer] The following coating liquid was applied onto the undercoat layer and dried to form a curable layer having a dry film thickness of 1.3 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 placed in a container heated at 55 ° C, and the following thioether compound was added to the total amount of silver nitrate added in an amount of 2.0.
It was added in an amount corresponding to × 10 ^-3 mol. While maintaining the pAg value of the reaction vessel at 9.2, the molar ratio of rhodium to the total amount of the aqueous solution of silver nitrate and 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 the pAg control double jet method to form silver iodobromide grains. Further subsequently, at the same temperature, pAg =
At 8.9, an aqueous solution of silver nitrate and a potassium bromide solution to which hexachloroiridium (III) acid salt was added so that the molar ratio of iridium to silver was 10 ⁻⁷ mol were added in two stages by the double jet method. A core / shell type silver iodobromide emulsion having the following composition was prepared.

[0084]

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Core: Silver iodobromide (silver iodide content: 7.5 mol%) Shell: Pure silver bromide Core / shell: 3/7 (silver mol ratio) Average silver iodide content: 2.3 Mol% Average particle size: 0.28 μm

The emulsion grains thus obtained were monodisperse, and 98% of all grains were present within ± 40% of the average grain size. The weight ratio of gelatin to silver in the silver halide emulsion was 0.2. Then, this emulsion was desalted, and the following methanol solutions of spectral sensitizing dyes (I) and (II) (each 0.5 × 10 ^-2 M / liter) were added to silver nitrate 1
Add 100 ml for each mole equivalent emulsion, p
The H was adjusted to 6.2 and the pAg was adjusted to 8.7. Further, gold / sulfur sensitization was carried out using sodium thiosulfate and chloroauric acid to prepare a silver halide emulsion.

[0087]

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[0088]

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[Preparation of mercapto silver compound] Polyvinyl alcohol (PVA-420, manufactured by Kuraray Co., Ltd.) 2.8
g was dissolved in 60 g of water, 10.3 g of 0.1N potassium hydroxide aqueous solution was added, and the mixture was heated to 50 ° C. While stirring
An aqueous solution containing 0.93 millimoles of silver nitrate in this solution,
A methanol solution containing 0.93 mmol of the following mercapto compound was simultaneously added dropwise over 20 minutes, and after the completion of the addition, the mixture was stirred for 20 minutes. Then, after cooling to room temperature, the pH was adjusted to 6.3. In this way, a mercapto silver compound in which -SH of the following mercapto compound was converted to -SAg was prepared. The yield was 113.68g. The pAg of the solution of this compound was 6.31.

[0090]

[Chemical 12]

[Formation of Photosensitive Layer] The following coating solution was prepared, coated on the curable layer and dried to form a photosensitive layer having a dry film thickness of about 1.2 μm. The amount of gelatin in the photosensitive layer was 0.6% by weight of the amount of polyvinyl alcohol.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol (Product name: PVA-405, Kuraray Co., Ltd.) 5.23 g 5% by weight aqueous solution of nonionic surfactant of 1.68 g 10% by weight aqueous dispersion of the following reducing agent 10.08 g Phosphate buffer (KH ₂ PO ₄ : 0.025 mol / liter + Na ₂ HPO ₄ : 0. 025 mol / liter) 1.68 g 0.11% by weight aqueous solution of the above mercapto silver compound 3.20 g The above silver halide emulsion (4.3-fold diluted with water) 18.48 g water 47.69 g ──── ────────────────────────────────

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[0094]

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

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[Formation of Image Formation Accelerating Layer] The following coating solution was prepared, coated on the above-mentioned photosensitive layer and dried to form an image formation promoting layer having a dry film thickness of about 3.3 μm.

──────────────────────────────────── Coating solution for the image formation promoting layer ──── ──────────────────────────────── Polyvinyl alcohol with a saponification degree of 98.5% (PVA-105, Kuraray Co., Ltd. )) 10 wt% aqueous solution 200.0 g The above base precursor dispersion 1.25 g 5 wt% aqueous solution of the above nonionic surfactant 4.0 g ────────────────── ────────────────────

[Preparation of Aqueous Eluate] An aqueous eluate having the following composition was prepared. This was placed in the first elution tank of the elution device shown in FIG.

──────────────────────────────────── Aqueous eluate ──────── ──────────────────────────── Water 10 liters Pronase ^™ (Calbiochem-Novabiochem) 50 g ───────── ────────────────────────────

[Preparation of Alkaline Eluate] An alkaline eluate having the following composition was prepared. This was placed in the second elution tank of the elution device shown in FIG. ──────────────────────────────────── Alkaline eluent ─────────── ───────────────────────── 28 wt% aqueous solution of potassium silicate 125.0 g potassium hydroxide 15.0 g Amphoteric surfactant (I-1 ) 10.0g water 750.0g ────────────────────────────────────

(Image formation) The resulting photosensitive material was imagewise scanned and exposed with an argon laser. The aluminum support surface of the light-sensitive material is brought into close contact with a hot plate heated to 155 ° C.
When heat-developed for a second, a silver image was seen in the exposed portion. The light-sensitive material was processed by the elution device shown in FIG. The replenishing amounts of the aqueous eluate and the alkaline eluate were 150 cc / m ^{2 of the} light-sensitive material, respectively. Processing temperature is 3
5 ° C. In this way, when continuous treatment was carried out for 1 week at a treatment of 30 m ² / day, occurrence of sludge and
No clogging of the ejection device (4a, 4b, 14a, 14b) shown in Fig. 4 was observed, and stable processing could be continued.

Example 2 In the preparation of the aqueous eluate of Example 1, bionase PN-4 was used instead of Pronase ^™.
Except that ^TM (manufactured by Nagase Seikagaku Co., Ltd.) was used in the same amount.
The light-sensitive material was processed in the same manner as in Example 1. After continuous treatment for one week, generation of sludge and clogging of the ejection device were not observed, and stable treatment could be continued.

Comparative Example 1 A light-sensitive material was processed in the same manner as in Example 1 except that the same amount of water was used instead of the aqueous eluent of Example 1. After continuous treatment for 1 week, precipitation on sludge was observed in the first elution tank. Also, the ejection device was clogged and stopped functioning.

Example 3 A light-sensitive material was processed in the same manner as in Example 1 except that the composition of the aqueous eluent of Example 1 was changed to the following. After continuous treatment for one week, generation of sludge and clogging of the ejection device were not observed, and stable treatment could be continued.

──────────────────────────────────── Aqueous eluate ──────── ──────────────────────────── Water 10 liters Amphoteric surfactant (I-1) 200 g ───────── ────────────────────────────

Example 4 A light-sensitive material was processed in the same manner as in Example 1 except that the composition of the aqueous eluent of Example 1 was changed to the following. After continuous treatment for one week, generation of sludge and clogging of the ejection device were not observed, and stable treatment could be continued.

──────────────────────────────────── Aqueous eluate ──────── ──────────────────────────── Water 10 liters The above nonionic surfactant 200 g ───────────── ────────────────────────

Example 5 A light-sensitive material was processed in the same manner as in Example 1 except that the composition of the aqueous eluent of Example 1 was changed to the following. After continuous treatment for one week, generation of sludge and clogging of the ejection device were not observed, and stable treatment could be continued.

──────────────────────────────────── Aqueous eluent ──────── ──────────────────────────── Water 10 liter Amphoteric surfactant (I-1) 200 g Pronase ^™ (Calbiochem-Novabiochem) 50 g ────────────────────────────────────

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an elution device preferably used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photosensitive material 2a-2f, 12a-12f, 22 Guide roller 3a-3d, 13a-13d Conveying roller 4a, 4b, 14a, 14b Spouting device 5,15 Roller brush 6,16 Guide plate 7,17 Circulation pump 8 Aqueous elution Liquid 18 Alkaline eluate

Claims (3)

[Claims] 1. A photosensitive material comprising a support, a curable layer containing a polymerizable compound or a crosslinkable polymer, and silver halide grains to which gelatin is attached, dispersed in a binder composed of a water-soluble synthetic polymer. Imagewise exposing a light-sensitive material, which is sequentially provided with layers and further contains a reducing agent;
A step of heating a photosensitive material to form a cured portion and an uncured portion corresponding to an exposed portion or an unexposed portion on a curable layer; a step of removing the photosensitive layer using an aqueous eluent;
An image forming method comprising the step of removing the uncured portion of the curable layer using an alkaline eluent and forming a residual image of the cured portion on the support, wherein the amount of gelatin in the photosensitive layer is Is 0.01 in the amount of the above water-soluble synthetic polymer.
1 to 10% by weight, and the light-sensitive material is mixed with the above aqueous eluent.
To 30 m ² / liter, and the aqueous eluate contains a proteolytic enzyme. 2. A photosensitive material comprising a support, a curable layer containing a polymerizable compound or a crosslinkable polymer, and silver halide grains to which gelatin is attached, dispersed in a binder made of a water-soluble synthetic polymer. Imagewise exposing a light-sensitive material, which is sequentially provided with layers and further contains a reducing agent;
A step of heating a photosensitive material to form a cured portion and an uncured portion corresponding to an exposed portion or an unexposed portion on a curable layer; a step of removing the photosensitive layer using an aqueous eluent;
And, an image forming method having a step of removing an uncured portion of the curable layer with an alkaline eluent to form a residual image consisting of the cured portion on a support, wherein the gelatin in the photosensitive layer is The amount of the water-soluble synthetic polymer is 0.0
1 to 10% by weight, a light-sensitive material is treated with the aqueous eluate in the range of 1 to 30 m ² / liter, and the aqueous eluate contains a surfactant. 3. The image forming method according to claim 2, wherein the surfactant is an amphoteric surfactant.