JPH09311453A - Photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure a wide temp. latitude of heat development and to enable stable heat development over a wide temp. region with high reproducibility by forming a photosensitive curable layer contg. a basicity regulating agent whose decomposition temp. or m.p. is a specified value or above. SOLUTION: A photosensitive curable layer contg. silver halide, a reducing agent, a polymerizable compd. or a crosslinkable polymer and a basicity regulating agent made of salt of a di-, tri- or tetravalent org. base and di-, tri- or tetracarboxylic acid and having >=80 deg.C decomposition temp. or m.p. is formed on a substrate. Since the salt is used as the basicity regulating agent, it is made possible to increase basicity in the photosensitive layer by heating and to reduce it by cooling. The salt can function as a reversible basicity regulating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material in which a photosensitive hardenable layer containing a silver halide, a reducing agent and a polymerizable compound or a crosslinkable polymer is provided on a support.

[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 Nos. 3-12307 and 3-12308 (US Pat. No. 46296)
76 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). . A base or a base precursor is generally added to this photosensitive material as a development accelerator.

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, the photosensitive material used for such image formation is often provided with a photosensitive layer containing a silver halide and a curable layer containing a polymerizable compound separately. Further, the photosensitive material may be provided with an image formation promoting layer containing a base or a base precursor.

In the above-mentioned image forming method, instead of using the alkaline developer, the photosensitive material is heated at a high temperature (80 ° C. above) to perform the developing treatment. In this thermal development, the development reaction of silver halide and the curing reaction of the polymerizable compound or the crosslinkable polymer proceed. The development reaction of silver halide proceeds rapidly under basic conditions. Therefore, a base or a base precursor is added to the photosensitive layer containing silver halide or a layer adjacent thereto (image formation promoting layer). 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.) are used. Examples of inorganic bases are described in JP-A-62-209448. The publication also describes the use of a salt of a weak acid and a strong base (inorganic base) as the basic substance. Examples of organic bases include tertiary amine compounds (JP-A-62-17095).
4), bis, tris or tetraamidine compounds (described in JP-A-63-316760) and bis, tris or tetraguanidine compounds (described in JP-A-64-68746).

As an example of the base precursor, a salt of an organic acid and a base which is decarboxylated by heating (Japanese Patent Laid-Open No. 63-31676).
No. 0, No. 64-68746, No. 59-180537 and No. 61-313431) and a urea compound that releases a base upon heating (JP-A-63-961).
No. 59 publication). 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 with respect to the transition metal ion (Japanese Patent Laid-Open No. SHO 6-96).
3-25208), or a basic metal compound which is poorly soluble in water and a compound capable of performing a complex formation reaction with water as a medium for a metal ion constituting the basic metal compound, and in the presence of water. A method of releasing a base by a reaction between these two compounds (described in JP-A-1-3282) is known.

[0006]

The present inventor has conducted research on a photosensitive material for heat development, and as a result, the heat development temperature at which an image of a constant image quality can be obtained is limited to an extremely narrow temperature range (heat development). The temperature latitude is narrow). That is, if the heating temperature is low, the thermal development is not sufficiently performed and the development becomes insufficient. On the contrary, if the heating temperature is high, the fogging development proceeds to the non-image area. The temperature range of heat development that can actually be used is very narrow, only a few degrees Celsius (2 to 3 degrees Celsius)
Is limited to the range. Therefore, a heating device capable of extremely precise temperature control is required. However, although such a control device is possible in the experimental stage, it is difficult or very expensive to implement in the practical stage. The expansion of the temperature latitude of heat development is an important problem to be solved in order to put the above light-sensitive material into practical use.

Many of the above-mentioned base precursors utilize a chemical reaction such as a decomposition reaction by heating,
It becomes strongly basic when heated. However, even if the temperature is lowered thereafter, the basicity is maintained and the pH change is irreversible. Therefore, the base generated at a high temperature remains in the system even after the temperature is lowered, and therefore the system is in a strongly basic state even if the thermal development is completed and the base is no longer needed. This is
In the past, there was no problem as to what kind of influence it has on the thermal development conditions such as temperature latitude. Further, a base precursor that produces a base by a conventional decomposition reaction produces a gas such as carbon dioxide by a decomposition reaction, and therefore, depending on the conditions of heat development,
There is a problem that spot-shaped image defects are generated due to the generation of gas. Furthermore, conventional base precursors include those lacking practical convenience, such as the need to add a certain amount of water from the outside during heat development.

An object of the present invention is to provide a light-sensitive material having a wide temperature latitude of heat development and capable of carrying out heat development stably and with good reproducibility over a wide temperature range. Also,
An object of the present invention is also to provide a light-sensitive material which does not cause image defects due to generation of gas during heat development. Another object of the present invention is to provide a light-sensitive material capable of forming a clear image by a simple method.

[0009]

The above objects have been achieved by the following light-sensitive materials (1) to (3). (1) Silver halide, a reducing agent, a polymerizable compound or a crosslinkable polymer, and a salt of a divalent, trivalent or tetravalent organic base with a divalent, trivalent or tetravalent carboxylic acid on a support. And a photosensitive material provided with a photosensitive curable layer containing a basic adjusting agent having a decomposition temperature or a melting point of 80 ° C. or higher. (2) A curable layer containing a polymerizable compound or a crosslinkable polymer on a support, and a silver halide and a divalent, trivalent or tetravalent organic base, and a divalent, trivalent or tetravalent carboxylic acid. Of salt of 80 ℃ and decomposition temperature or melting point
A photosensitive material having a photosensitive layer containing the basic adjusting agent described above and containing a reducing agent in the photosensitive layer or the curable layer.

(3) On the support, a curable layer containing a polymerizable compound or a crosslinkable polymer, a photosensitive layer containing silver halide, a divalent, trivalent or tetravalent organic base and a divalent,
It has an image formation accelerating layer which is composed of a salt with a trivalent or tetravalent carboxylic acid and which contains a basic adjusting agent having a decomposition temperature or a melting point of 80 ° C. or higher. Photosensitive material included. The carboxylic acid is two,
It is preferably composed of three or four carbonyl groups and an aliphatic group connecting them, and a triple bond, a sulfonyl group and an aromatic group are preferably not present in the aliphatic linking group.

[0011]

According to the study of the present inventors, a salt of a divalent, trivalent or tetravalent organic base having a decomposition temperature or a melting point of 80 ° C. or higher with a divalent, trivalent or tetravalent carboxylic acid is used as a base. It has been found that when used as a sex adjusting agent, it is possible to increase the basicity in the photosensitive layer by heating and then weaken the basicity in the photosensitive layer by cooling.
That is, the above-mentioned salt can function as a reversible basicity adjusting agent. Salts of divalent, trivalent or tetravalent organic bases with divalent, trivalent or tetravalent carboxylic acids are described in JP-A-63-316760 and 64-68746 mentioned above as base precursors. Has been suggested. However, since these salts are base precursors, carboxylic acids are compounds that decompose when heated (for example, 80 ° C.).

In the light-sensitive material of the present invention, when the light-sensitive material is cooled after heat development, the above salt functions as a reversible basicity adjusting agent. As a result, the light-sensitive material of the present invention can rapidly stop the heat development reaction. As described above, the heat development reaction of silver halide rapidly proceeds under high temperature and basic conditions. On the contrary, by lowering both the heat development temperature and the basicity in the photosensitive layer, it became possible to rapidly stop the heat development reaction. The above-mentioned fog development in the non-image area has a slower reaction progress than the development in the image area.
Therefore, by cooling the photosensitive material and abruptly stopping the thermal development reaction, it is possible to suppress only the fog development in the non-image area without suppressing the development in the image area. As a result, the light-sensitive material of the present invention has a wide temperature latitude of heat development and can be stably heat-reproduced over a wide temperature range with good reproducibility. That is, even if the temperature is slightly higher or lower than the optimum heat development temperature, the light-sensitive material of the present invention can suppress only fog development in the non-image area, so that a sufficiently clear image can be formed. it can.

Further, the reversible basicity adjusting agent used in the present invention does not cause a decomposition reaction unlike conventional base precursors. Therefore, the light-sensitive material of the present invention does not cause image defects due to generation of gas during thermal development. Only by cooling the light-sensitive material of the present invention, the reversible basicity modifier functions and the basicity of the photosensitive layer is lowered. Therefore, the heat development reaction can be stopped very easily. That is, when the light-sensitive material of the present invention is used, a clear image can be formed by a simple method. Further, since the basic adjusting agent is a salt, it has high water solubility, and there is also an effect that it can be easily removed after the image forming process. Conventional thermal decomposition type base precursors generally have a hydrophobic group for accelerating the decomposition reaction. For this reason,
There is a problem that the hydrophobic compound remains in the photosensitive material after the decomposition, which makes it difficult to remove and the cleaning liquid for removal immediately deteriorates. In addition, the generated hydrophobic compound also causes a problem of clogging of piping and pump in the elution device.
In the light-sensitive material of the present invention, the basic adjusting agent can be easily removed as needed without such a problem. Furthermore,
The basicity adjusting agent used in the present invention has a stable salt structure with a polyvalent organic base and a polyvalent carboxylic acid, and therefore is excellent in stability as a compound.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

[Basic Adjusting Agent] The light-sensitive material of the present invention uses a salt of a divalent, trivalent or tetravalent organic base and a divalent, trivalent or tetravalent carboxylic acid as a basic adjusting agent. The carboxylic acid is preferably divalent or trivalent, and more preferably divalent. Carboxylic acids consist of two, three or four carboxylic groups and a divalent, trivalent or tetravalent group connecting them. The linking group is preferably an aliphatic group. In the aliphatic linking group, a bond or group that promotes the decarboxylation reaction of a carboxylic acid, that is, a triple bond (-C≡C
-), sulfonyl group (-SO ₂ -) or an aromatic group (aryl, it is preferred that the arylene) is not present. In the aliphatic linking group, in addition to a carbon-carbon single bond and a carbon-hydrogen bond, other bonds and groups such as a carbon-carbon double bond (>
C = C <), an ether bond (-O-), a thioether bond (-S-) or an alcoholic hydroxyl group (-OH) may be present. The aliphatic linking group may have a cyclic structure. The cyclic structure also includes a condensed ring (eg, bicyclo ring). The number of carbon atoms in the aliphatic linking group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 12 and 1 to 1
Most preferably, it is 0. Specific examples of the carboxylic acid will be given below.

(A-1) Malonic acid (A-2) Succinic acid (A-3) Glutaric acid (A-4) Adipic acid (A-5) Suberic acid (A-6) 2-Methylmalonic acid (A -7) 2-Cyclohexyl succinic acid (A-8) 3,3-Dimethylglutaric acid (A-9) 2,2-Dimethylglutaric acid (A-10) Diglycolic acid

(A-11) thiodiglycolic acid (A-12) tartaric acid (A-13) camphoric acid (A-14) 1,1-cyclopropanedicarboxylic acid (A-15) 1,2-cyclopropanedicarboxylic acid Acid (A-16) 1,1-Cyclobutanedicarboxylic acid (A-17) 1,1-Cyclopentanedicarboxylic acid (A-18) 1,2-Cyclopentanedicarboxylic acid (A-19) 1,1-Cyclohexanedicarboxylic acid Acid (A-20) 1,2-cyclohexanedicarboxylic acid

(A-21) 1,4-Cyclohexanedicarboxylic Acid (A-22) 1,1-Cyclopentanediacetic Acid (A-23) 1,1-Cyclohexanediacetic Acid (A-24) Maleic Acid (A- 25) Fumaric acid (A-26) Itaconic acid (A-27) Bicyclo [2,2,2] octane-2,3
-Dicarboxylic acid (A-28) propanetricarboxylic acid (A-29) citric acid (A-30) butanetetracarboxylic acid

The organic base is preferably divalent or trivalent, and more preferably divalent. The organic base comprises two, three or four basic groups and a divalent, trivalent or tetravalent group connecting them. The basic group may be any of an amino group (primary, secondary or tertiary), a quaternary ammonium group, an imino group, an amidino group and a guanidino group. The strongly basic amidino group or guanidino group is preferable, and the guanidino group is more preferable. The linking group is preferably an aliphatic group. Like the carboxylic acid, in the aliphatic linking group, in addition to the carbon-carbon single bond and the carbon-hydrogen bond, other bonds and groups such as a carbon-carbon double bond (> C = C <) and an ether bond are included. (-O-), a thioether bond (-S-) and an alcoholic hydroxyl group (-OH) may be present. The aliphatic linking group may have a cyclic structure. The cyclic structure also includes a condensed ring (eg, bicyclo ring). The number of carbon atoms in the aliphatic linking group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 12, and most preferably 1 to 10. Specific examples of the organic base are shown below.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

[Chemical 12]

[0031]

Embedded image

[0032]

Embedded image

The basic modifier used in the present invention is a salt obtained by combining the above-mentioned carboxylic acid and organic base. There is no particular limitation on the combination of acid and base. However, the salt to be formed needs to have a decomposition temperature or a melting point of 80 ° C. or higher. Decomposition point or melting point is 100
C. or higher is preferable, 120.degree. C. or higher is more preferable, 140.degree. C. or higher is further preferable, and 160.degree. C. or higher is most preferable. Table 1 below shows examples of the basic modifier used in the present invention, that is, examples of the combination of the carboxylic acid and the organic base. In Table 1, the numbers of the above-mentioned carboxylic acid (A) are arranged vertically and the numbers of the above organic base (B) are arranged horizontally. The numbers of the specific examples of the basic modifier of the present invention are shown at the intersections of the carboxylic acid rows and the organic base columns. For example, specific example number (1
1) is a salt composed of a combination of a carboxylic acid (A-3) and an organic base (B-2). Similarly, the specific example number (21) is a carboxylic acid (A-5) and an organic base (B-
It is a salt consisting of a combination with 6).

[0034]

[Table 1] Table 1 ──────────────────────────────────── Acid \ Base 1 2 35 6 7 8 9 10 11 12 13 14 15 16 ───────────────────────────────────── 1 1 17 33 40 2 2 14 18 36 42 46 3 3 11 19 38 48 4 4 4 15 20 34 43 5 16 21 6 5 12 12 7 22 37 50 8 6 23 44 9 49 11 24 13 7 13 25 39 14 8 26 35 45 15 27 16 28 21 9 29 41 22 10 30 47 23 31 26 32 ──────────────────────────────────── ─

The basic modifier used in the present invention can be synthesized by mixing a carboxylic acid and an organic base in an organic solvent and separating the resulting salt. When the salt formed is soluble in the solvent, the solvent can be distilled off to obtain the salt. Below, the synthetic example of the basic adjusting agent used for this invention is shown. Other basic modifiers can be synthesized by the same method.

[Synthesis Example 1] Synthesis of basic modifier (23) 4.0 g of 3,3-dimethylglutaric acid was added to 10 parts of methanol.
It was dissolved in 0 ml and heated to 60 ° C. To this solution, 5.5 g of a carbonate of a bisguanidine compound having the following structure was added little by little. After completion of the addition, the mixture was stirred for 2 hours while heating under reflux, and cooled to room temperature. The produced crystals were collected by filtration, repeatedly washed with methanol, and dried under reduced pressure for 8 hours. Yield 6.23
g, the yield was 78%. Elemental analysis value (C12H26
N6O4) is as follows. Calculated value: C 45.27% Actual value: C 45.31% H 8.23% H 8.06% N 26.40% N 26.37%

[0037]

Embedded image

[Synthesis Example 2] Synthesis of basic modifier (26) 3.25 g of 1,1-cyclopropanedicarboxylic acid was dissolved in 100 ml of methanol and heated to 60 ° C. To this solution, a carbonate of the bisguanidine compound of the above structure 5.5
g was added in small portions. After completion of the addition, the mixture was stirred for 2 hours while heating under reflux, and cooled to room temperature. The produced crystals were collected by filtration, repeatedly washed with methanol, and dried under reduced pressure for 8 hours. The yield was 5.73 g, and the yield was 80%. Elemental analysis value (C1
0H20N6O4) is as follows. Calculated value: C 41.66% Actual value: C 41.46% H 6.99% H 6.88% N 29.15% N 29.14%

Whether or not the above compound functions as a reversible basicity adjusting agent can be confirmed by the method described in the preliminary experiment described later. That is, an aqueous solution of each compound is added
It can be easily confirmed by impregnating H test paper (for example, Universal Stick manufactured by Merck & Co., Inc.), drying it, and observing the color reaction when heated and cooled. According to this method, the reversible basicity adjusting agent exhibits strong basicity only when heated at a high temperature, the pH is lowered by cooling, and again exhibits strong basicity when heated again. Further, even if the pH test paper itself is similarly heated as a blank test, the indicator color does not change at all.
This is because the desorption and addition of the proton of the dye of the pH indicator carried on the pH test paper is not affected by the temperature change itself, but the change of the basic modifier caused by the temperature change is reversible with temperature. Is shown. That is, it can be said that the basic modifier reversibly changes the pH depending on the temperature and gives strong basicity only at a high temperature.

The basic modifier used in the present invention may not be completely reversible depending on the heating temperature, the heating time, and the boiling point of the acid or base constituting the salt. That is, when heated for a long time at a temperature equal to or higher than the boiling point of the acid, the acid evaporates and decreases, and even when cooled, the initial pH may not be lowered and the pH may be slightly shifted to the basic side. However, there is no substitute for showing strong basicity when it is heated, and basically, reversibility remains. In the case of applying to a reversible chemical reaction system, it is necessary to select a salt having reversibility as a basic modifier in consideration of the above. On the other hand, when applied to an irreversible chemical reaction system, not so strict reversibility is required.

In the present invention, the acid or base constituting the basic modifier changes its initial chemical structure as an acid or base due to a decomposition reaction (eg decarboxylation reaction) under the heating temperature conditions used. Don't As described above, the reaction involving the change in the chemical structure is irreversible, and the reversible pH change required by the present invention is completely lost. The basic modifier used in the present invention does not need to supply water during heating.
Therefore, the heat development step can be carried out at a temperature above the boiling point of water (for example, 150 ° C.) under the condition that water is substantially absent and the surface of the light-sensitive material is opened to the air. As mentioned above,
It is speculated that the basicity adjusting agent used in the present invention expresses basicity not by a reaction such as hydrolysis but by a reversible process such as thermal dissociation. The reversibility of pH change also supports such a thermal dissociation mechanism. However, the details of the mechanism are still unclear.

Since acid-basicity is a phenomenon determined by a dissociation reaction, when the polarity of the medium changes, the equilibrium changes greatly and the expression of basicity also changes. In the present invention, the light-sensitive material is processed under the condition that it contains substantially no water.
By "substantially free of water" is meant free of enough water to change this dissociation equilibrium. Therefore, systems that include steps that intentionally provide water are not within the scope of the invention. On the other hand, a small amount of water naturally contained in the coating layer of the light-sensitive material does not significantly change the dissociation equilibrium, and is therefore acceptable in the present invention. The hydrolysis reaction or the like under basicity is a reaction in which addition of water to a substrate activated by a base is essential, but at a level at which water itself does not significantly participate in dissociation equilibrium itself of basic expression, the present invention It is included in the range of. Also in this case, water is limited to the water contained naturally in the light-sensitive material. The amount of water allowed in the present invention is 5% or less of the total weight of the coating layer of the light-sensitive material. The present invention is 8
Since the heat development treatment is carried out at a temperature of 0 ° C. or higher, most of the water existing under these natural conditions evaporates out of the reaction system,
It is thought to be removed. The basic modifier is
It is preferably used in the range of 1 to 20 mol, and more preferably 1 to 5 mol, per mol of the reducing agent.

The layer structure of the photosensitive material, the components of each layer and the image forming method using the photosensitive material will be described below. [Layer Structure of Photosensitive Material] The layer structure of the photosensitive material can be determined according to the application. However, the photosensitive curable layer containing a silver halide, a reducing agent and a polymerizable compound or a crosslinkable polymer is a two-layer structure including a photosensitive layer containing a silver halide and a curable layer containing a polymerizable compound or a crosslinkable polymer. It is preferably composed of 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. The basic modifier is added to the photosensitive curable layer, the photosensitive layer or the image formation promoting layer. Even if a basic adjusting agent is added to a layer other than the photosensitive layer such as the image formation promoting layer, the basic adjusting agent diffuses into the photosensitive layer during thermal development.

[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.

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

[Overcoat Layer and Image Formation Accelerating Layer] The overcoat layer has a function of protecting the light-sensitive material and preventing oxygen from entering the air to enhance the degree of curing of the curable layer. Components that accelerate image formation in the overcoat layer (eg, basic modifiers, reducing agents, heat development accelerators)
May be added to have a function of promoting image formation in addition to a protective function as an overcoat 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 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. When performing an etching treatment, if a hydrophobic polymer is used, after thermal development, prior to etching,
It is necessary to remove these layers by peeling.

[Adhesive Layer] When an image is formed using a 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
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 aluminum plate subjected to the graining treatment 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 constituting 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] 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. 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.

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 also be used in the form of a salt with an appropriate 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 which 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 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 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 its unsaturated bond group to directly polymerize the polymer or polymerize the polymerizable compound. 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.

[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 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. 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 does not completely dissolve in water due to the crosslinked structure of the polymer. As the water-soluble or water-swellable polymer, natural, synthetic or semi-synthetic polymer compounds can be used. The hydrophilic polymer is described in JP-A-5-249667. Polyvinyl alcohol is a particularly preferred hydrophilic polymer. Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen transmittance, it is preferable that the saponification degree is 50% or more,
It is more preferable to set it to 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 hydrophilic polymer is 3000-5
The range of 0,000 is preferable. The amount of the hydrophilic polymer used is
It is preferably 0.05 to 20 g / m ² ,
More preferably, it is 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 than the isoelectric point of gelatin or 1.
It is preferable to adjust the value to 2 or more.

[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 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. 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 or 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.

[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) that 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 photopolymerization initiator is a photosensor, it is generally 1
0 ² to 10 ⁷ erg / cm ² , more preferably 10 ³ to
It is in the range of 10 ⁵ 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.
It is described in each publication of No. -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. In the heat development step, the above-mentioned basicity adjusting agent acts to strengthen the basicity in the photosensitive layer. As a result, the development reaction of silver halide in the photosensitive layer proceeds rapidly. Heating temperature is 80
C. or higher, preferably 80 to 200.degree. C., more preferably 100 to 150.degree. Heating time is 1 to 1
It is 80 seconds, more preferably 5 to 60 seconds. The photosensitive material may be preheated at a temperature higher than the main heating temperature for a short time before the exposure step or after the exposure step, or may be postheated after the 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 .

[Cooling Step] In the image forming method using the photosensitive material of the present invention, it is preferable to carry out the cooling step subsequent to the heat development step. In the cooling step, the reversible basicity adjusting agent described above acts to weaken the basicity in the photosensitive layer. As a result, the silver halide development reaction in the photosensitive layer is suddenly stopped. Cooling is 3 after heating is completed.
Within 0 seconds, the temperature is cooled to 40 ° C. or more lower than the heating temperature. Preferably, within 20 seconds, the temperature is higher than the heating temperature by 4
Cool to a temperature below 0 ° C. Cooling can be performed using a known cooling device. For example, an indirect method by blowing air or a direct method by contact with a cooled medium can be implemented. The direct method is preferable because the cooling efficiency is high. As a cooling medium by the direct method,
A variety of solid or liquid materials are available. As the solid, metal, rubber, or other polymer compound is used. The cooling solid is used in a shape such as a plate shape or a roller shape. If a substance such as metal having high thermal conductivity is used as the cooling medium, the cooling efficiency can be increased.

As a result of the processing in each of the above steps, the curable layer is selectively image-wise cured. In summary, the image forming method using the light-sensitive material of the present invention comprises the step of image-exposing the light-sensitive material; heating the light-sensitive material to 80 ° C. or higher to increase the basicity in the photosensitive curable layer, and thereby, Developing the silver halide and curing the polymerizable compound or the crosslinkable polymer; and cooling the photosensitive material to a temperature lower than the heating temperature by 40 ° C. or more within 30 seconds after the completion of heating to cool the photosensitive material. It consists of weakening the basicity and thereby stopping the development of silver halide. Further, the following processing may be performed.

[Removing Step] In the removing step, the uncured portion of the curable layer is removed. The hydrophilic layer is preferably removed before removing the curable layer. Removal of the hydrophilic layer can be easily carried out using water (preferably warm water). The removal process includes a method using an eluate and a method using a removal sheet. First, the method using the eluate will be described. As the eluent (or etching solution) for removing the uncured portion, any solvent can be used as long as it can remove the uncured portion of the curable layer. Preferably, an alkaline solvent is used. The alkaline solvent is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic 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 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), and polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene). Glycol, polyethylene glycol) and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine). Examples of ethers include cellosolves. The eluate may contain a surfactant, an antifoaming agent, and other various additives as required.

Next, the method of using the removal sheet will be described. When the removal sheet is brought into close contact with the surface of the curable layer, the adhesive force between the interface between the curable layer and the removal sheet becomes different between the uncured portion and the cured portion. When the curable layer and the removal sheet are peeled off, the adhesive force at the interface between the uncured portion and the adhesive layer is greater than the adhesive force at the removal sheet side, and the adhesive force at the interface between the cured portion and the adhesive layer is at the removal sheet side. When the adhesion is smaller than that, only the cured portion is transferred to the removal sheet. Conversely, when the adhesive force at the interface between the uncured portion and the adhesive layer is smaller than the adhesive force at the removal sheet side, and the adhesive force at the interface between the cured portion and the adhesive layer is greater than the adhesive force at the removal sheet side, Only the uncured portion is transferred to the removal sheet. Whether the cured part is transferred or the uncured part is transferred depends on the property of the polymerizable compound in the curable layer, the amount of the polymerizable compound added, the property of the binder in the curable layer, and the property of the curable layer. The adhesive strength may vary depending on the properties of other components and the addition amount thereof, as well as various conditions of the removing step (heating temperature, time, pressurizing temperature, etc.).

[Transfer Processing] In the transfer processing, the cured image is transferred by being attached to another sheet (image receiving material). 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. Further, the toner image obtained may be transferred by first performing the following toner development processing.

[Toner Development Processing] A coloring substance (toner) is 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 process] The cured image is 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.

[0093]

【Example】

[Preliminary Experiment 1] A 5% by weight aqueous solution of the basic modifier (23) was added to a pH test paper (Universal Stick, manufactured by Merck).
And was dried. At room temperature, pH 7 showed pH 7 as a color reaction of the test paper. When this was brought into contact with a hot plate heated to 150 ° C, the indicator color of the pH test paper changed,
The color reaction showed a pH of 11. When it was returned to room temperature, the pH returned to 7. Further, by repeating heating and cooling, the indicator color of the pH test paper repeatedly changed according to the temperature change. Further, even if the pH test paper itself was heated in the same manner as a blank test, the indicated color did not change at all. The above results show that the desorption and addition of protons from the dye of the pH indicator carried on the pH test paper are not affected by the temperature change itself, but are affected by the change of the compound (23) due to the temperature change, and this change is It is shown to be reversible with temperature. That is, it is shown that the compound (23) changes the pH reversibly with temperature and gives strong basicity only at high temperature.

[Preliminary Experiment 2] The pH test paper was heated and cooled in exactly the same manner as in Preliminary Experiment 1 except that the compound (23) used in Preliminary Experiment 1 was replaced with barium acetate. As a result, the coloration of the test paper remained to indicate pH 9.
Therefore, barium acetate does not have the ability to impart strong basicity at high temperatures.

[Preliminary Experiment 3] The color reaction with pH test paper was observed in the same manner as in Preliminary Experiment 1 except that the compound (23) used in Preliminary Experiment 1 was changed to guanidine trichloroacetate. Guanidine trichloroacetate functions as a base precursor because trichloroacetic acid is decarboxylated by heating to form chloroform and carbon dioxide, and only guanidine which is a base remains (US Patent 3220).
846 specification). At room temperature, pH was 9 due to the color reaction of the pH test paper. When this was brought into contact with a hot plate heated to 150 ° C. and heated, the indicator color of the pH test paper changed, and the pH showed 14 from the color reaction. When it was returned to room temperature, the pH remained at 14. That is, it can be seen that guanidine trichloroacetate gives a strong base at high temperature, but retains strong basicity even when cooled, and does not show a reversible change with temperature.

[Example 1] Preparation of photosensitive material " Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the aluminum plate according to S-A-1050 was grained with a nylon brush and an aqueous suspension of pumicetone (400 mesh), and then thoroughly washed with water. Next, 10%
It was immersed in the aqueous solution of sodium hydroxide for 30 minutes at 70 ° C. 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 alternating current (conditions: voltage at anode 12.7 v, ratio of electricity at cathode to electricity at anode was 0.9, electricity at anode was 160 coulomb / dm ² ). Then, electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution containing 0.5% aluminum nitrate. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Following this treatment, it was immersed in a 1% aqueous sodium hydroxide solution at 40 ° C. for 30 seconds 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 / dm ² ,
Current density 2A using direct current in 20% sulfuric acid aqueous solution
Anodizing treatment was performed under the condition of / dm ² . The obtained aluminum plate was washed with water and dried to prepare a support.

"Formation of Undercoat Layer" A 0.02 wt% silver nitrate aqueous solution was applied on the above support by a whiler (200 rp).
m) and dried at 100 ° C. for 1 minute to form an undercoat layer.

[Formation of Curable Layer] The following coating liquid was applied on the undercoat layer and dried to form a curable layer having a dry film thickness of about 1.3 μm.

──────────────────────────────────── Curable Layer Coating Liquid ────── ────────────────────────────── Pentaerythritol tetraacrylate 0.23 g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 0.50 g Pigment dispersion liquid below 4.47 g 0.56 wt% methanol solution of the following additives 0.56 g Surfactant (Megafuck F176PF, manufactured by Dainippon Ink and Chemicals, Inc.) 3% by weight aqueous solution 1.00 g methyl ethyl ketone 0.62 g propylene glycol monomethyl ether 2.50 g ──────────────────────────────── ────

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Pigment (chromophthal red A2B) 6.90g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 5.73 g Cyclohexanone 12.90 g Propylene glycol monomethyl ether 74.47 g ──────────────────────────────── ─────

[0101]

Embedded image

[Preparation of Silver Halide Emulsion] The following thioether compound was added to a container containing gelatin, potassium bromide and water and heated at 55 ° C. to 2.0% of the total amount of silver nitrate added.
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.

[0103]

Embedded image

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 grain size: 0.28 μm

The resulting emulsion grains were monodisperse, and 98% of all grains were present within ± 40% of the average grain size. Then, this emulsion was desalted, and then the following spectral sensitizing dye A in methanol (5 × 10 ⁻³ M / liter) and the following spectral sensitizing dye B in methanol (5 × 10 ⁻³ ) were added.
M / l) was added to 100 ml of each emulsion corresponding to 1 mol of silver nitrate, and the pH was 6.2 and pAg was 8.
Adjusted to 7. Further, gold / sulfur sensitization was carried out using sodium thiosulfate and chloroauric acid to prepare a silver halide emulsion.

[0106]

Embedded image

[0107]

Embedded image

"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.

[0109]

Embedded image

[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 thickness of about 1.2 μm.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol (trade name: PVA-405, Kuraray Co., Ltd.) 5.23 g 5% by weight aqueous solution of the surfactant of 1.68 g, 10% by weight aqueous dispersion of the following reducing agent 10.08 g Phosphate buffer solution (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 ───── ───────────────────────────────

[0112]

[Chemical 21]

[0113]

Embedded image

[Formation of Image Formation Accelerating Layer] The following coating liquid 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 3.7 μm.

──────────────────────────────────── Coating solution for the image formation promoting layer ──── ──────────────────────────────── Polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd.) 10.0 g Basic Conditioner (19) 1.3 g Water 90 g 5% by weight aqueous solution of the above-mentioned surfactant 1.2 g ──────────────────────────── ─────────

(Image formation) The obtained photosensitive material was 488n
Image exposure of 3 μJ / cm ² was performed with m monochromatic light. Next, a hot plate heated to a predetermined temperature was pressed against the back surface (the surface on the side of the aluminum support) of the photosensitive material, and heated for 30 seconds for thermal development. A metallic cooling roller was installed adjacent to the hot plate, and the heat-developable photosensitive material was heated by the hot plate and immediately cooled while being conveyed by the cooling roller. After removing the photosensitive layer and the image formation promoting layer, the curable layer was placed in an automatic developing machine using an alkaline aqueous solution (DP-4 manufactured by Fuji Photo Film Co., Ltd. diluted with water to 1/8). After brush development, it was washed thoroughly with water to elute and remove the curable layer in the unexposed area. As a result, a relief image of the same polymer without fog was obtained in a wide temperature range of the thermal temperature (heat development temperature) of 145 ° C to 165 ° C. That is, the range of the appropriate heat development temperature is 15
It was found that the thermal development can be stably performed against the fluctuation of the thermal development temperature. Next, this photosensitive material is heated to 45 ° C.
After left in an environment of relative humidity of 75% for 3 days, the image forming process was performed in the same manner as above. As a result, a good polymer relief image without fogging could be obtained as in the above. Further, in order to examine the image strength, a PET adhesive tape was attached on the obtained image and then peeled off. PE
No transfer of the polymer image onto the T-tape was observed.

[Examples 2 to 15, Comparative Examples 1 to 3] In place of 1.3 g of the basic modifier (19) used in Example 1, the basic substances shown in Table 2 were added in the amounts shown in the table. Except that it was used in
A light-sensitive material was prepared in the same manner as in Example 1, and an image was formed and evaluated. The results are shown in Table 2.

[0118]

[Table 2] Table 2 ──────────────────────────────────── Image development heat development temperature Width image Sensitive material Basic substance Usage amount Immediately after production Strength after storage ──────────────────────────────────── Example 1 (19) 1.30 g 145 to 160 ° C. 145 to 160 ° C. A Example 2 (3) 0.62 g 145 to 160 ° C. 145 to 160 ° C. A Example 3 (4) 0.65 g 145 to 160 ° C. 145 to 160 ° C A Example 4 (7) 0.77g 140 to 160 ° C 140 to 160 ° C A Example 5 (11) 0.75g 145 to 160 ° C 145 to 160 ° C A Example 6 (15) 0.90g 145-160 ° C. 145-160 ° C. A Example 7 (18) 0.62 g 145-160 ° C. 145-1 60 ° C A Example 8 (21) 0.68g 145-160 ° C 145-160 ° C A Example 9 (23) 0.71g 140-160 ° C 140-160 ° C A Example 10 (26) 0.64g 140- 160 ° C. 140 to 160 ° C. A Example 11 (29) 0.74 g 150 to 160 ° C. 150 to 160 ° C. A Example 12 (36) 1.32 g 145 to 160 ° C. 145 to 160 ° C. A Example 13 (40) 0 .71 g 145 to 160 ° C. 145 to 160 ° C. A Example 14 (43) 0.68 g 145 to 160 ° C. 145 to 160 ° C. A Example 15 (46) 0.37 g 145 to 160 ° C. 145 to 160 ° C. A ─── ───────────────────────────────── Comparative Example 1 Sodium acetate 0.58 g 145-160 ° C. 145-155 B Comparative Example 2 (X) 0.58 g 145 to 160 ° C. 145 to 150 ° C. B Comparative Example 3 (Y) 0.12 g 150 to 160 ° C. 150 to 160 ° C. B ───────────── ─────────────────────── Note: The image strength is A, although no transfer of the polymer image onto the PET tape is observed. The item was evaluated as B. In Comparative Example 2, when the photosensitive material was heat-developed at 160 ° C. after storage, fogging occurred in the image. In Comparative Example 3, the image was fogged when the light-sensitive material was thermally developed at 155 ° C. after storage.

[0119]

Embedded image

[0120]

Embedded image Furthermore, in order to investigate the image intensity, PE was added on the obtained image.
Attach T adhesive tape

Example 16 A curable layer was formed on a support in the same manner as in Example 1.

[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 thickness of 3.5 μm.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) 5.23g 5% by weight aqueous solution of the surfactant used in Example 1. 1.68 g 10% by weight aqueous dispersion of the reducing agent used in Example 1 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 mercapto silver compound used in Example 1. 3.20 g The silver halide emulsion used in Example 1 (4.3 with water). Double dilution) 18.48 g Basic conditioner (19) 1.65 g Water 47.69 g ──────────── ────────────────────────

(Image formation) The obtained photosensitive material was 488n
Image exposure of 3 μJ / cm ² was performed with m monochromatic light. Next, a hot plate heated to a predetermined temperature is pressed against the back surface of the photosensitive material (surface on the aluminum support side), and a polyethylene terephthalate film having a thickness of 100 μm is pressed on the surface of the photosensitive material (surface on the photosensitive layer side). It was applied and heated for 30 seconds for thermal development. A metallic cooling roller was installed adjacent to the hot plate, and the heat-developable photosensitive material was heated by the hot plate and immediately cooled while being conveyed by the cooling roller. After removing the photosensitive layer, the curable layer was brush-developed with an automatic developing machine using an alkaline aqueous solution (DP-4 manufactured by Fuji Photo Film Co., Ltd. diluted with water to 1/8). After thorough washing with water, the curable layer in the unexposed area was eluted and removed. As a result, the heat temperature (heat development temperature) is 140
In the wide temperature range from 0 ° C to 155 ° C, relief images of the same polymer without fogging were obtained. That is, it was found that the appropriate range of the heat development temperature was 15 degrees, and the heat development could be stably performed against the fluctuation of the heat development temperature.
Next, this photosensitive material was allowed to stand in an environment of a temperature of 45 ° C. and a relative humidity of 75% for 3 days, and then image forming processing was performed in the same manner as described above. As a result, a good polymer relief image without fogging could be obtained as in the above. Further, in order to examine the image strength, a PET adhesive tape was attached on the obtained image and then peeled off. No transfer of the polymer image onto the PET tape was observed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area // C08F 2/46 MDY C08F 2/46 MDY

Claims (4)

[Claims] 1. A silver halide, a reducing agent, a polymerizable compound or a crosslinkable polymer, and a divalent, trivalent or tetravalent organic base and a divalent, trivalent or tetravalent carboxylic acid on a support. And a photosensitive curable layer containing a basic adjusting agent having a decomposition temperature or a melting point of 80 ° C. or higher. 2. A curable layer containing a polymerizable compound or a crosslinkable polymer, a silver halide and a divalent, trivalent or tetravalent organic base and a divalent, trivalent or tetravalent carvone on a support. A photosensitive material comprising a salt with an acid, having a photosensitive layer containing a basic adjusting agent having a decomposition temperature or a melting point of 80 ° C. or higher, and containing a reducing agent in the photosensitive layer or the curable layer. 3. A support, a curable layer containing a polymerizable compound or a crosslinkable polymer, a photosensitive layer containing silver halide, and a divalent, trivalent or tetravalent organic base, and a divalent or trivalent organic base. Alternatively, it has an image formation promoting layer which is composed of a salt with a tetravalent carboxylic acid and which contains a basic adjusting agent having a decomposition temperature or a melting point of 80 ° C. or higher, and a reducing agent is contained in the photosensitive layer or the curable layer. Sensitive material. 4. The carboxylic acid comprises two, three or four carboxyl groups and an aliphatic group connecting them, and a triple bond, a sulfonyl group and an aromatic group are not present in the aliphatic linking group. Item 4. The photosensitive material according to any one of items 1 to 3.