JPH10111572A - Photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the bonding strength of a hardenable layer to a photosensitive layer in a photosensitive material without adversely affecting the material and image formation and to prevent peeling between the two layers by forming an adhesive layer contg. a water-soluble synthetic polymer having a specified mol% of specified repeating units. SOLUTION: This photosensitive material has an adhesive layer contg. a water-soluble synthetic polymer having >=50mol% repeating units represented by formula I or II. In the formulae I, II, each of R<1> and R<2> is H or methyl, each of R<11> and R<12> is H, an aliphatic or arom. group, R<11> and R<12> may bond to each other to form a 5- or 6-membered N-contg. hetero ring, each of R<21> and R<22> is H, an aliphatic or arom. group, R<21> and R<22> may bond to each other to form a 5- or 6-membered N-contg. hetero ring and R<23> is alkylene or arylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material in which a curable layer and a photosensitive layer are provided on a support, and the adhesiveness between the curable layer and the photosensitive layer is improved.

[0002]

2. Description of the Related Art A method for forming a polymer image by imagewise exposing a photosensitive 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-like manner. Are disclosed in Japanese Patent Publication Nos. 3-12307 and 3-12308 (U.S. Pat.
No. 6 and European Patent 0174634). In this method, polymerization is initiated by an oxidant radical of a reducing agent that has reduced silver halide (which may be a radical generated by decomposition of an oxidant of the reducing agent; hereinafter, simply referred to as an oxidant radical). . Specifically, the photosensitive material is heated to develop the silver halide,
Thermal development for forming a cured image of the polymerizable compound is performed.

[0003] The image forming method described above can also be applied to the production of a printing plate. A photosensitive material suitable for producing a printing plate is disclosed in JP-A-5-249667 (US Pat.
No. 22443 and European Patent No. 0426192) and JP-A-4-191856 (U.S. Pat.
No. 29,659). In a photosensitive material used for producing a printing plate, generally, a curable layer containing a polymerizable compound and a hydrophobic polymer, and a photosensitive layer containing silver halide and a hydrophilic polymer are provided on a support. A reducing agent is included in any of the layers. In the method of manufacturing a printing plate using silver halide, after curing the polymerizable compound by thermal development, the photosensitive layer is removed from the photosensitive material,
The uncured portion of the curable layer is removed using an eluent, and the remaining cured image is used as an image of a printing plate.

A curable layer containing a polymerizable compound and a hydrophobic polymer is a hydrophobic layer, and a photosensitive layer containing silver halide and a hydrophilic polymer is a hydrophilic layer. For this reason, the adhesion between these two layers is weak, and peeling occurs at the interface between the two layers in handling the photosensitive material, causing a problem that the photosensitive material is destroyed. For example, when cutting the photosensitive material with a cutter, when strongly rubbing the surface of the photosensitive material, or after winding or stacking the photosensitive material in a roll,
When removing photosensitive material from rolls or laminates,
A considerable force is applied, causing delamination between the two layers. As means for solving the above problems, Japanese Patent Application Laid-Open No.
No. 5, No. 8-146600, No. 8-184968,
JP-A-8-194314 discloses an invention for enhancing the adhesive strength between a curable layer and a photosensitive layer.

Japanese Patent Application Laid-Open No. Hei 8-123035 discloses a photosensitive material containing a hydrophobic polymer having an acidic group in a salt state as a binder for a curable layer. JP-A-8-146600 discloses a coating comprising a mixture of a good solvent and a poor solvent of a hydrophobic polymer, wherein the boiling point of the poor solvent is higher than the boiling point of the good solvent by 3 ° C. or more. A method for producing a photosensitive material in which a curable layer is formed by applying a liquid is described. JP-A-8-184968 describes a photosensitive material containing a hydrophobic polymer having an acidic group as a binder for a curable layer, and a photosensitive layer containing a hydrophilic polymer and an amino alcohol.

Japanese Patent Application Laid-Open No. 8-194314 discloses a binder or an additive which is proposed in each of the above publications for enhancing the adhesive strength. The light-sensitive material added to the layer is described.
These are inventions in which the polymer used as a binder for the photosensitive layer or the curable layer is improved to enhance the adhesive strength between the two layers. Therefore, in these inventions, it is possible to use a binder which has been conventionally recognized as not causing a problem in the photosensitive material and the image formation, with a slight improvement.

[0007]

SUMMARY OF THE INVENTION The inventors of the present invention have studied the inventions described in each of the above publications relating to the enhancement of the adhesive strength between the curable layer and the photosensitive layer. There was found. A hydrophobic polymer having an acidic group in a salt state described in JP-A-8-123535 releases a counter ion of an acidic group under a high temperature and high humidity condition to make the inside of a photosensitive material basic. I do. For this reason, the sensitivity of the photosensitive material is reduced, and a problem occurs in storage stability. As described in JP-A-8-146600, when a mixture of a good solvent and a poor solvent for a hydrophobic polymer is used, a slight phase separation occurs in the formation of the curable layer, and the components of the curable layer are uniform. There is a problem that is not distributed to. The amino alcohol used in the invention described in JP-A-8-184968 is a basic component and has an effect of reducing the storage stability of the light-sensitive material. JP 8
In the case of the photosensitive material provided with the adhesive layer described in JP-A-194314, the same problem as described above was observed.

To solve the above problems, the present inventor has
Instead of improving the conventional polymer used as a binder for the curable layer or the photosensitive layer, the development of a new binder having a function of enhancing the adhesion between the two layers was started. Numerous polymers have already been proposed as binders for enhancing adhesive strength in applications such as adhesives. However, a photosensitive material for forming a cured image using the sensitivity of silver halide has a very complicated structure. Further, the image forming system also includes a very complicated combination of reactions. Therefore, most of the polymers known as a binder or an adhesive could not be used due to some problems in the photosensitive material and image formation. Specifically, there have been various problems such as insufficient adhesive strength, difficulty in producing the photosensitive material, deterioration in storage stability of the photosensitive material, and failure of image formation. SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material in which the adhesion between the curable layer and the light-sensitive layer is enhanced without adversely affecting the light-sensitive material and image formation, and peeling between the two layers hardly occurs.

[0009]

The above object has been attained by the following photosensitive materials (1) to (8). (1) On a support, a curable layer containing an ethylenically unsaturated polymerizable compound and a hydrophobic polymer having an acidic group, a photosensitive layer containing silver halide and a hydrophilic polymer, and a curable layer and a photosensitive layer Wherein any one of the layers is a photosensitive material containing a reducing agent, and the adhesive layer contains 50 mol of a repeating unit represented by the following formula (I) or (II). % Of a water-soluble synthetic polymer having at least 1% by weight.

[0010]

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Wherein R ¹ and R ² are each hydrogen or methyl; R ¹¹ and R ¹² are each hydrogen, aliphatic or aromatic, or R ¹¹ and R 2 ¹² are bonded to each other to form a nitrogen-containing heterocyclic 5- or 6-membered; R ²¹ and R ^22, respectively,
Is a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²² combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring; and R ²³ is an alkylene group or an arylene group. is there. A photosensitive material, wherein the adhesive layer contains a water-soluble synthetic polymer having a repeating unit represented by the following formula (I) in an amount of 50 mol% or more.

(2) The water-soluble synthetic polymer is a copolymer having a repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II), each having 5 mol% or more. Photosensitive material. (3) The photosensitive material according to (1), wherein the adhesive layer further contains a water-soluble polysaccharide. (4) The photosensitive material according to (1), further comprising an image formation accelerating layer containing a base or a base precursor on the photosensitive layer.

(5) A curable layer containing an ethylenically unsaturated polymerizable compound and a hydrophobic polymer having an acidic group, and a photosensitive layer containing silver halide are provided on a support. A photosensitive material containing a reducing agent, wherein the photosensitive layer further contains a water-soluble synthetic polymer having a repeating unit represented by the formula (I) or (II) in an amount of 50 mol% or more. material. (6) The photosensitive material according to (5), wherein the water-soluble synthetic polymer is a copolymer having a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II) in an amount of 5 mol% or more. (7) The photosensitive material according to (5), wherein the photosensitive layer further contains a water-soluble polysaccharide. (8) The photosensitive material according to (5), further comprising an image formation promoting layer containing a base or a base precursor on the photosensitive layer.

[0014]

The light-sensitive material of the present invention is characterized in that the adhesive strength between the curable layer and the photosensitive layer is enhanced by using the above-mentioned water-soluble polyacrylamide-based or amino-substituted polyacrylate-based synthetic polymer. . The water-soluble synthetic polymer is
It is added to the adhesive layer or the photosensitive layer provided between the curable layer and the photosensitive layer. In the embodiment in which the water-soluble synthetic polymer is added to the adhesive layer, the adhesiveness between the adhesive layer and the photosensitive layer (hydrophilic layer) is very good because the polymer is water-soluble. The acidic group of the hydrophobic polymer contained in the curable layer and the amide bond or amino group contained in the water-soluble synthetic polymer have an electrostatic affinity due to acid-base interaction. Therefore, it is considered that the adhesiveness between the curable layer and the adhesive layer containing the water-soluble synthetic polymer or the photosensitive layer is also improved. As described above, the adhesive force between the curable layer and the photosensitive layer was enhanced, and as a result, in the photosensitive material of the present invention,
During handling of the photosensitive material, the number of failures in which the photosensitive material is destroyed due to peeling of the interface between the two layers is greatly reduced. Further, as a result of investigations by the present inventors, the water-soluble synthetic polymer used in the present invention hardly recognized any adverse effects on photosensitive materials and image formation.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION

[Water-soluble synthetic polymer] The water-soluble synthetic polymer has a repeating unit represented by the following formula (I) or (II) in an amount of 50 mol% or more.

[0016]

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In the formula (I), R ¹ is a hydrogen atom or methyl. In the formula (I), R ¹¹ and R ¹² are
Each is a hydrogen atom, an aliphatic group or an aromatic group, or R ¹¹ and R ¹² are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. It is preferred that at least one of R ¹¹ and R ¹² are either an aliphatic group or an aromatic group, or to form the nitrogen-containing heterocyclic, and R ¹¹ and R
More preferably at least one of ¹² to form a is either or above nitrogen-containing heterocyclic aliphatic group, more preferably at least one of R ¹¹ and R ¹² is an aliphatic group, R ¹¹ and R Most preferably, one of ¹² is an aliphatic group and the other is a hydrogen atom.

The aliphatic group includes an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
It means a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. Alkyl, substituted alkyl, alkenyl, substituted alkenyl, aralkyl and substituted aralkyl are preferred, alkyl, substituted alkyl, alkenyl and substituted alkenyl are more preferred, alkyl and substituted alkyl are more preferred, Substituted alkyl groups are most preferred. The total number of carbon atoms including the substituent of the aliphatic group is preferably from 1 to 40, more preferably from 1 to 20, still more preferably from 1 to 15, and preferably from 1 to 10. Most preferred. The number of carbon atoms of the aliphatic group excluding the substituent is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10,
Most preferably, it is 1 to 6. As the aliphatic group, a chain aliphatic group is more preferable than a cyclic aliphatic group. The chain aliphatic group may have a branch.

The aromatic group means an aryl group and a substituted aryl group. The total number of carbon atoms including the substituent of the aromatic group is preferably from 6 to 60, more preferably from 6 to 40, further preferably from 6 to 30, and further preferably from 6 to 20. Preferably 6 to 1
Most preferably, it is 2. Examples of the substituent for the aliphatic group and the aromatic group include a hydroxyl, a halogen atom (eg,
Chlorine), amino, substituted amino groups, heterocyclic groups (eg, morpholino) and cyano. The substituent of the substituted amino group is the above-mentioned aliphatic group or aromatic group. Examples of the substituent of the aromatic group further include the above-mentioned aliphatic group. The heterocyclic ring formed by R ¹¹ and R ¹² bonded to each other is 6
It is preferably a membered ring. The heterocycle is preferably a saturated heterocycle. Examples of the repeating unit represented by the formula (I) are shown below. In the following examples, the names of the compounds of the monomers used as the raw materials of the repeating units are also described.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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In the formula (II), R ² is a hydrogen atom or methyl. In the formula (II), R ²¹ and R ^21
22 is a hydrogen atom, an aliphatic group or an aromatic group, respectively, or R ²¹ and R ²² are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. It is preferred that at least one of R ²¹ and R ²² are either an aliphatic group or an aromatic group, or to form the nitrogen-containing heterocyclic, R ²¹
Whether at least one of R ²² is an aliphatic group, or it is more preferable to form the above-mentioned nitrogen-containing heterocyclic ring, R
Even more preferably at least one of ²¹ and R ²² is an aliphatic group, and most preferably both R ²¹ and R ²² is an aliphatic group. Aliphatic group, aromatic group and 5 or 6 members
The definition of the membered nitrogen-containing heterocycle and the substituents thereof are the same as those in formula (I).

In the formula (II), R ²³ is an alkylene group or an arylene group. The alkylene group and the arylene group may have a substituent. The total number of carbon atoms (including the substituent) of the alkylene group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and still more preferably 1 to 6. Is most preferred. The alkylene group may have a branch. The number of carbon atoms (total including substituents) of the arylene group is preferably from 6 to 60, preferably from 6 to 40, more preferably from 6 to 30, and preferably from 6 to 20. More preferably, 6 to 1
Most preferably, it is 0. Examples of the substituent of the alkylene group and the arylene group include a hydroxyl, a halogen atom (eg, chlorine), an amino, a substituted amino group, a heterocyclic group (eg, morpholino) and cyano. The substituent of the substituted amino group is the above-mentioned aliphatic group or aromatic group. Examples of the substituent of the arylene group further include the above-mentioned aliphatic group. Examples of the repeating unit represented by the formula (II) are shown below. In the following examples, the names of the compounds of the monomers used as the raw materials of the repeating units are also described.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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As the water-soluble synthetic polymer, a homopolymer comprising only the repeating unit represented by the formula (I) or (II) may be used. Further, as a copolymer combined with another repeating unit, the properties (for example, water solubility) of the polymer can be adjusted. When the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) are used together in a copolymer, the total of both is 5
If it is 0 mol% or more, the definition of the present invention is satisfied. The proportion of the repeating unit represented by the formula (I) or (II) in the copolymer is preferably at least 70 mol%,
More preferably 80 mol% or more, and 90 mol%.
More preferably, it is at least 95 mol%, most preferably at least 95 mol%.

Copolymers having a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II) in an amount of 5 mol% or more (50 mol% or more in total) are particularly preferred. The following are examples of copolymers.

──────────────────────────────────── Copolymer (Repeating unit I) _mol% (Repeating unit II) _mol% {CP-1 (I-1) ₉₀ ( II-16) ₁₀ CP-2 (I-2) ₉₀ (II-16) ₁₀ CP-3 (I-11) ₉₀ (II-16) ₁₀ CP-4 (I-3) ₉₀ (II-16) ₁₀ CP-5 (I-28) ₉₀ (II-16) ₁₀ CP-6 (I-8) ₉₀ (II-16) ₁₀ CP-7 (I-10) ₅₀ (II-16) ₅₀ CP-8 (I -29) ₂₀ (II-16) ₈₀ CP-9 (I-16) ₉₀ (II-16) ₁₀ CP-10 (I-16) ₅₀ (II-2) ₅₀ CP-11 (I-30) ₁₀ ( II-2) ₉₀ CP-12 (I-19) ₈₀ (II-16) ₂₀ CP-13 (I-1) ₉₀ (II-3) ₁₀ CP-14 (I-1) ₉₀ (II-18) ₁₀ CP-15 (I-1) ₉₀ (II-19) ₁₀ CP-16 (I-1) ₉₀ (II-20) ₁₀ mm

The polymer used in the present invention can be synthesized by radical polymerization of an ethylenically unsaturated group using a monomer exemplified as a repeating unit as a catalyst and a polymerization initiator as a catalyst. The polymer used in the present invention may be synthesized by synthesizing polyacrylamide, polymethacrylamide, polyacrylate, polymethacrylate, or a copolymer thereof, and then modifying the side chain. When forming a copolymer containing a repeating unit other than the repeating unit represented by the formula (I) or (II), the other repeating units can be derived from various ethylenically unsaturated polymerizable compounds. As the ethylenically unsaturated polymerizable compound, the same compounds as the examples of the ethylenically unsaturated polymerizable compound which is a component of the curable layer described later can be used. The molecular weight of the water-soluble synthetic polymer used in the present invention is preferably in the range of 2,000 to 500,000,
More preferably in the range of 3000 to 300,000,
The range is more preferably from 4,000 to 200,000, and most preferably from 5,000 to 150,000.

When the water-soluble synthetic polymer is added to the adhesive layer, its amount is preferably adjusted so that the weight of the adhesive layer is 0.01 to 2 g / m ² . The film weight of the adhesive layer is more preferably from 0.02 to 1.5 g / m ² , and most preferably from 0.025 to 1.0 g / m ² . When a water-soluble synthetic polymer is added to the photosensitive layer, the amount used is preferably 1 to 80% by weight, more preferably 3 to 60% by weight, and more preferably 5 to 60% by weight of the film weight of the photosensitive layer. Most preferably, it is 50% by weight.

[Water-soluble polysaccharide] The water-soluble polysaccharide is a polymer in which a monosaccharide is bonded to a glycoside. Depending on the type of monosaccharide and the mode of glycosidic linkage, various types of polysaccharides occur naturally. Water-soluble polysaccharides used industrially include cellulose, starch, pullulan, xanthan gum and dextran. Natural polysaccharides may be modified or chemically modified before use. Cellulose and dextran are easily chemically modified and their hydrophilicity / hydrophobicity is easily adjusted. A cellulose derivative obtained by chemically modifying cellulose is particularly preferably used. As the cellulose derivative, a cellulose ester and a cellulose ether are preferable, and a cellulose ether is particularly preferable. Water-soluble polysaccharides have very high water-solubility because they have many hydroxyl groups. When a water-soluble polysaccharide is used in combination with the above-mentioned water-soluble synthetic polymer, a layer (adhesive layer or photosensitive layer) containing these polymers can be very easily removed using an aqueous liquid.

Cellulose ethers have all or part of the hydrogen atoms of the three hydroxyl groups of the monosaccharide unit (glucose having a β1 → 4 glycosidic bond) constituting cellulose.
A compound substituted with an alkyl group (including a substituted alkyl group). Examples of cellulose ethers include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, diethylaminoethyl cellulose,
1,3-dihydroxypropylcellulose is included.
The carboxyl group may be in the form of a salt such as an alkali metal (eg, sodium) salt. A mixed ether of cellulose substituted by two or more kinds of alkyl groups may be used. Examples of the mixed ether include carboxymethyl hydroxyethyl cellulose (the carboxyl group may be in a salt state), hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, ethyl hydroxyethyl cellulose, and 2-hydroxyethyl-1-hydroxyethyl cellulose. Is included. The water-soluble polysaccharide is added to a layer containing a water-soluble synthetic polymer (adhesive layer or photosensitive layer). When the layer containing the water-soluble synthetic polymer is an adhesive layer, the water-soluble polysaccharide is particularly effective (effect of facilitating elution of the layer). The amount of the water-soluble polysaccharide used is preferably in the range of 5 to 150% by weight, more preferably in the range of 10 to 120% by weight, and more preferably in the range of 15 to 100% by weight of the amount of the water-soluble synthetic polymer. Is more preferable, and most preferably in the range of 20 to 80% by weight.

[Layer Structure of Photosensitive Material] The photosensitive material is preferably provided on a support in the order of a curable layer and a photosensitive layer. However, when a photosensitive material is used for producing a color proof, a photosensitive layer and a curable layer can be provided on a support in this order. In either case, the adhesive layer is provided between the curable layer and the photosensitive layer. The photosensitive material may have a structure of four or more layers including a curable layer, an adhesive layer, a photosensitive layer, and an overcoat layer. The reducing agent can be added to the curable layer or the photosensitive layer. It is preferable that the components of each layer described above are uniformly contained in the layer without using microcapsules. The photosensitive material may be provided with a functional layer other than the above. Other functional layers include an adhesive layer, a release layer, an undercoat layer and an intermediate layer. Less than,
A typical layer configuration will be described with reference to the drawings.

FIG. 1 is a schematic sectional view showing a typical layer structure of the light-sensitive material of the present invention. In the photosensitive material shown in FIG. 1, a curable layer (2), an aluminum support (1),
An adhesive layer (3), a photosensitive layer (4) and an image formation accelerating layer (5) are sequentially provided. The curable layer (2) contains an ethylenically unsaturated polymerizable compound (6) and a hydrophobic polymer (7) having an acidic group. The adhesive layer (3) contains a water-soluble synthetic polymer (8) and has a function of enhancing the adhesion between the curable layer (2) and the photosensitive layer (4). The photosensitive layer (4) contains a silver halide (9), a reducing agent (10) and a hydrophilic polymer (11). Image formation accelerating layer (5)
Comprises a base precursor (12) and a hydrophilic polymer (13). FIG. 2 is a schematic sectional view showing another typical layer constitution of the photosensitive material of the present invention. In the photosensitive material shown in FIG. 2, a curable layer (22), a photosensitive layer (23) and an image formation accelerating layer (24) are sequentially provided on an aluminum support (21). The curable layer (22)
It includes an ethylenically unsaturated polymerizable compound (25) and a hydrophobic polymer having an acidic group (26). Photosensitive layer (2
3) silver halide (27), reducing agent (28), water-soluble synthetic polymer (29) and hydrophilic polymer (30)
including. The image formation promoting layer (24) includes a base precursor (31) and a hydrophilic polymer (32).

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

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

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

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

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

[Curable Layer] The curable layer is a layer containing an ethylenically unsaturated polymerizable compound or an ethylenically unsaturated crosslinkable polymer (preferably both). The amount of the ethylenically unsaturated polymerizable compound is preferably in the range of 3 to 200% by weight of the amount of the hydrophobic polymer having an acidic group,
More preferably, it is in the range of 10 to 100% by weight. The amount of the ethylenically unsaturated crosslinkable polymer is preferably 30 to 95% by weight of the whole curable layer,
More preferably, it is from 90 to 90% by weight. The thickness of the curable layer is preferably 0.1 to 20 μm,
More preferably, it is 0.3 to 7 μm.

[Adhesive Layer] The adhesive layer is a layer containing the water-soluble synthetic polymer described above.

[Photosensitive Layer] The photosensitive layer is a layer containing silver halide and a hydrophilic polymer. The coating amount of silver halide is preferably 0.01 to 5 g / m ² , more preferably 0.03 to 1 g / m ² , and more preferably 0.05 to 0.3 g / m ^{2 in} terms of silver. Is most preferred. The thickness of the photosensitive layer is 0.07 to 13 μm
Is preferably, and more preferably, 0.2 to 5 μm.

[Overcoat Layer and Image Forming Acceleration Layer] The overcoat layer has a function of protecting the photosensitive material, preventing penetration of oxygen in the air, and increasing the degree of curing of the curable layer. Components that promote image formation (eg, a base, a base precursor, a thermal development accelerator) can be added to the overcoat layer to function as an image formation accelerator. The thicknesses of the overcoat layer and the image formation promoting layer are preferably 0.3 to 20 μm.
More preferably, it is 5 to 7 μm.

[Intermediate Layer] An intermediate layer can be provided on the light-sensitive material. The intermediate layer can also function as an antihalation layer, a filter layer, or a barrier layer. The antihalation layer and the filter layer are functional layers containing a coloring agent. The barrier layer has a function of preventing components from migrating between layers and diffusing or mixing during storage of the photosensitive material. The material of the intermediate layer is determined according to the application. The thickness of the intermediate layer is preferably 10 μm or less.

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

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

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

Two or more kinds of silver halide grains having different halogen compositions, crystal habits and grain sizes can be used in combination. Silver halide is preferably used as an emulsion. Silver halide emulsions are described in Research Disclosure (RD) Magazine, No. 17643 (December 1978
Mon., pp. 22-23, "I. Emulsion Production (Emulsion prepa
ration and types) "and No. 18716 (19
Nov. 1979), p. 648. The silver halide emulsion is usually subjected to chemical sensitization after physical ripening. It is preferable to use silver halide grains having a relatively low fog value. Additives used in such a process are described in Research Disclosure Magazine, No. No. 17643 and the same No. 18716. Regarding chemical sensitizers, 17643 (23
Page) and No. 18716 (page 648, right column). Known additives other than those described above are also described in the above two Research Disclosures. For example, as for the sensitivity enhancer, 1871
No. 6 (right column on page 648), No. 6 No. 17643 (pages 24 to 25) and no. 1
8716 (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 the photographic art can be used. Examples of sensitizing dyes include cyanine dyes,
Examples include merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Spectral sensitizing dyes are used to adjust the spectral sensitivity of photosensitive materials to different light source wavelengths such as various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and light emitting diodes. Can also be used. For example, applying a plurality of spectral sensitizing dyes having different spectral wavelengths to silver halide in the same or different photosensitive layers to enable writing on the same photosensitive material using light sources having different wavelengths. Can also. In addition to the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (supersensitizer) can be added to the emulsion. Good. Spectral sensitizing dyes are described in Research Disclosure Magazine, No. 17643 (197
December, 8), pp. 23-24, for supersensitizers
No. 18716 (November 1979), p. 649,
Each is listed.

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

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

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

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

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

[Hydrophilic polymer] The photosensitive layer and the optional hydrophilic layer (overcoat layer or intermediate layer) contain a hydrophilic polymer as a binder. The hydrophilic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in a molecular structure. Examples of hydrophilic groups include carboxyl,
Alcoholic hydroxyl group, phenolic hydroxyl group, sulfone,
Includes sulfonamide groups, sulfonimides and amides. Examples of the hydrophilic bond include a urethane bond, an ether bond and an amide bond. It is preferable to use a water-soluble polymer or a water-swellable polymer as the hydrophilic polymer. A water-swellable polymer is one that has an affinity for water but is not completely soluble in water due to the crosslinked structure of the polymer. Water-soluble polymers are preferred over water-swellable polymers. As the water-soluble or water-swellable polymer, a natural, synthetic or semi-synthetic polymer compound can be used. The hydrophilic polymer is described in JP-A-5-249667.

[0077] Polyvinyl alcohol is a particularly preferred hydrophilic polymer. Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen permeability, the degree of saponification is preferably 70% or more, and more preferably 80% or more. Copolymerized modified polyvinyl alcohol can also be used. Copolymerization modification is a method of saponifying a copolymer of vinyl acetate and another monomer to synthesize a modified polyvinyl alcohol. Examples of monomers to be copolymerized include ethylene, higher vinyl carboxylate, higher alkyl vinyl ether, methyl methacrylate and acrylamide.

Further, post-modified polyvinyl alcohol can also be used. The post-modification is a method in which a compound having reactivity with a hydroxyl group of polyvinyl alcohol is used to modify polyvinyl alcohol by a polymer reaction after synthesis. Specifically, the hydroxyl group of polyvinyl alcohol is modified by etherification, esterification, or acetalization. Furthermore, crosslinked polyvinyl alcohol can also be used. As the cross-linking agent, an aldehyde, a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid, or an inorganic cross-linking agent (eg, boric acid) can be used. The molecular weight of the hydrophilic polymer is preferably in the range of 3000 to 500,000.

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

[Hydrophilic Polymer Having Acidic Group] The hydrophobic polymer having an acidic group is preferably crosslinkable. For crosslinking, it is preferable to introduce an ethylenically unsaturated bond into the main chain or side chain of the molecule. The crosslinkability may be introduced by copolymerization. Examples of polymers having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene, and natural and synthetic rubbers. Examples of the polymer having an ethylenically unsaturated bond in a side chain of a molecule include a polymer of an ester or amide of acrylic acid or methacrylic acid, wherein a residue of the ester or amide (R of —COOR or —CONHR) is used. A polymer having an ethylenically unsaturated bond can be mentioned. Examples of the residue having an ethylenically unsaturated bond (R described above) include-(CH ₂ ) _n -CR ¹ = CR ² R ³ and-(CH ₂ O) _n -CH ₂ CR ¹ = CR ² R ³ ,-
(CH ₂ CH ₂ O) _n -CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ¹ = CR
² R ³ ,-(CH ₂ ) _n -O-CO-CR ¹ = CR ² R ³ and-(CH ₂ CH ₂ O) ₂ -X (R
^{1 to} R ³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, and an aryloxy group, and R ¹ and R ² or R ³ are bonded to each other to form a ring; Wherein n is an integer from 1 to 10 and X is a dicyclopentadienyl residue.

Specific examples of the ester residue include —CH ₂ CH = CH
₂ (described in JP-B-7-21633), -CH ₂ CH ₂ O-CH ₂ C
H = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOC
H = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCOO-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ O-
X (X is a dicyclopentadienyl residue) is included. Specific examples of the amide residue include -CH ₂ CH = CH ₂ , -CH ₂ CH ₂ -1-Y (Y
Are included cyclohexene residue) and _{-CH 2 CH 2 -OCO-CH =} CH 2. In the crosslinkable polymer as described above, a free radical (a polymerization initiation radical or a growing radical in the polymerization process of an ethylenically unsaturated polymerizable compound) is added to the unsaturated bonding group, and the polymer is directly or polymerically unsaturated between the polymers. Addition polymerization is carried out via a polymerization chain of the polymerizable compound, and a crosslink is formed between polymer molecules to be cured. Alternatively, free radicals abstract atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to unsaturated bond groups) to form polymer radicals, which combine with each other to form crosslinks between polymer molecules. Being cured.

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

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

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

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

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

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

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

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

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

[Exposure Step] Image exposure is performed with light having a wavelength corresponding to the spectral sensitivity of silver halide. The wavelength is visible light,
Near-ultraviolet light and near-infrared light are generally used, but X-rays and electron beams may be used. Examples of light sources include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, and various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, YAG laser), light emitting diode, cathode ray tube and the like.

The exposure amount is generally 0.001 to 1000.
μJ / cm ² , preferably 0.01 to 100 erg /
cm ² . When the support is transparent, exposure can be performed through the support from the back side of the support. In the process of forming a latent image of silver halide, the sensitivity tends to change under the influence of temperature and humidity during exposure. Therefore, it is desirable that the temperature and humidity of the atmosphere of the photosensitive material and the light source be controlled within a certain range. Adjusting means of the image recording apparatus for achieving the above object are described in JP-A-3-63143 and JP-A-3-63637.

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

[Removing Step] In order to remove the uncured portion (non-image portion) to form an image, it is preferable to remove the uncured portion by elution. Before removing the uncured portion, it is preferable to remove the photosensitive layer, the adhesive layer, and other hydrophilic layers by washing with water or mechanical peeling. It is preferable to use an alkaline eluate as the eluate.
Examples of the alkaline compound used in the alkaline eluate include:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, ammonia and amino alcohols (eg,
Monoethanolamine, diethanolamine, and triethanolamine). As a solvent for the eluate, water is preferable. If necessary, an organic solvent may be added to water. As the organic solvent, alcohols or ethers are preferable. Examples of alcohols include lower alcohols (eg, methanol, ethanol, propanol, butanol), alcohols having 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 necessary.

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

[0096]

【Example】

[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 SA-1050 was grained with a nylon brush and an aqueous suspension of pamistone (400 mesh), and then thoroughly washed with water. Next, 10%
Was immersed in an aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. It was neutralized and washed with a 20% aqueous nitric acid solution, and then washed with water. The obtained aluminum plate was subjected to an alternating waveform current of a rectangular wave (condition: voltage at anode: 12.7 v, ratio of electricity at cathode to electricity at anode: 0.9, electricity at anode: 160 coulomb / dm ² ). The 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, the substrate 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 DC current in 20% sulfuric acid aqueous solution
Anodizing treatment was performed under the condition of / dm ² . Wash this,
After drying, a support was prepared.

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

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

[Formation of Curable Layer] The following coating solution was applied on a support and dried to form a curable layer having a dry film thickness of 1.8 μm.

{Coating solution for curable layer} ────────────────────────────── Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer (hydrophobic polymer, copolymer (Mol ratio = 70/30) 4.0 g Propylene glycol monomethyl ether 36.0 g The above pigment dispersion 18.0 g ────────────

[Formation of Adhesive Layer] The following coating solution was applied on the curable layer and dried to obtain an adhesive layer having a dry film thickness of 0.05 μm (dry film weight: 0.05 g / m ² ). Was provided.

<< Coating Solution for Adhesive Layer >> ────────────────────────────── 180 g of water 6.5 g of 10% by weight aqueous solution of copolymer CP-1 6.5 g of the following surfactant 2.0 g of 5% by weight aqueous solution

[0103]

Embedded image

"Preparation of silver halide emulsion" A solution containing gelatin, potassium bromide and water, adjusted to pH 9.5 at room temperature by adding sodium hydroxide, was heated to 55 ° C. The thioether compound was added in an amount equivalent to 2.0 × 10 ⁻³ mol based on the added amount of silver nitrate. Reaction vessel p
While maintaining the Ag value at 9.0, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing rhodium ammonium chloride such that the molar ratio of rhodium to the total amount of potassium iodide and silver nitrate was 4 × 10 ⁻⁸ mol were used. With pAg
Silver iodobromide grains were formed by the control double jet method. Next, sulfuric acid was added to adjust the pH to 6.0. Subsequently, at 55 ° C. and pAg = 8.6, the silver nitrate aqueous solution and the molar ratio of iridium to silver were 5 × 1.
A core / shell type silver iodobromide emulsion having the following composition was prepared by adding two steps of a potassium bromide solution to which hexachloroiridate (III) was added so as to be ^0-7 mol by a double jet method. .

[0105]

Embedded image

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

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

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"Preparation of a reducing agent dispersion" 90 g of a 10% by weight aqueous solution of polynivir alcohol (manufactured by Kuraray Co., Ltd.) was added to 10 g of the following reducing agent powder using a Dynomill disperser.
Dispersed inside. The particle size of the reducing agent was about 0.5 μm or less.

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[Formation of Photosensitive Layer] The following coating solution was prepared, applied on the adhesive layer, and dried to a dry film thickness of 1.3 μm.
m of photosensitive layers.

{Coating solution for photosensitive layer}ポ リ ビ ニ ル Polyvinyl alcohol with a saponification degree of 79.5% (PVA-405, manufactured by Kuraray Co., Ltd.) )) 10.5 g of a 0.11 wt% methanol solution of the following additive (S-1) 0.41 g 0.11 wt% aqueous solution of the following additive (S-2) 0.41 g of the above Silver halide emulsion 0.50 g 5% by weight aqueous solution of the above surfactant 0.40 g Water 7.80 g Reducing agent dispersion 1.20 g above ───────────────────

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

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"Formation of image formation accelerating layer" The following coating solution was prepared, coated on the photosensitive layer and dried to form an image formation accelerating layer having a dry film thickness of 3.5 µm.

塗布 Coating solution for image formation accelerating layer─────ポ リ ビ ニ ル Polyvinyl alcohol with a saponification degree of 98.5% (PVA-105, Kuraray Co., Ltd.) 200.0 g of the above-mentioned base precursor dispersion 1.25 g 5% by weight aqueous solution of the above-mentioned surfactant 4.0 g ──────────────────

(Evaluation of Adhesive Strength Between Layers) The adhesive strength between the curable layer and the photosensitive layer of the photosensitive material was evaluated by measuring the peel force as follows. The photosensitive material was cut into a width of 2 cm, and a commercially available adhesive tape was strongly adhered to the surface.
The tensile tester (Tensilon, Orientec Co., Ltd.)
180 ° at a pulling speed of 40 mm / min.
After peeling in the direction, the tensile force (adhesive force) was measured. The photosensitive material was peeled between the curable layer and the photosensitive layer, and the peel strength (adhesive strength) was 90 g / 2 cm.

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

──────────────────────────────────── Alkaline eluate ──────── << 28 wt% aqueous solution of potassium silicate 125.0 g potassium hydroxide 15.0 g water 750.0 g >> ───────────────────────────────────

(Image formation) The light-sensitive material was exposed to light at 670 nm with a sharp cut interference filter at an emission time of ² μJ / cm ² for a light emission time of 10 ⁻⁴ seconds by xenon flash. Next, thermal development was performed for 30 seconds by a method of transporting the photosensitive material while keeping the surface of the aluminum support in close contact with a heated hot plate. The photosensitive material was washed with water to remove the image formation accelerating layer, the photosensitive layer and the adhesive layer. Using the above-mentioned alkaline eluate, brush-developed by an automatic etching machine, and washed well with water. As a result, a relief image of a blue-colored polymer having good contrast was formed on the exposed portion.

[Examples 2 to 4 and Comparative Examples 1 to 11] Photosensitive materials were prepared in the same manner as in Example 1 except that the film weight of the adhesive layer used in Example 1 was changed as shown in Table 1 below. do it,
evaluated. Further, as Comparative Example 1, a photosensitive material having no adhesive layer was prepared and evaluated in the same manner. The results are shown in Table 1. Further, as Comparative Examples 2 to 11, photosensitive materials having an adhesive layer formed using a general-purpose adhesive polymer shown in Table 1 below were prepared and evaluated in the same manner. The results are shown in Table 1.

[0126]

[Table 1] Table 1 感光 Photosensitive materials Polymer Adhesive layer Film weight Peeling force Image formation 例 Example 1 CP-1 05g / m ² 90g / 2cm good example ^{2 CP-1 0.10g / m 2} 110g / 2cm good example ^{3 CP-1 0.50g / m 2} 320g / 2cm good example 4 CP-1 1.00g / m ² 480 g / 2 cm Good Comparative Example 1 None −20 g / 2 cm Bad * Comparative Example 2 X-1 0.50 g / m ² 22 g / 2 cm Bad * Comparative Example 3 X-2 0.50 g / m ² 25 g / 2 cm Bad * Comparative example ^{4 X-3 0.50g / m 2} 18g / 2cm poor * Comparative example ^{5 X-4 0.50g / m 2} 25g / 2c Poor * Comparative Example ^{6 X-5 0.50g / m 2} 35g / 2cm poor * Comparative Example ^{7 X-6 0.50g / m 2} 30g / 2cm poor * Comparative Example ^{8 X-7 0.50g / m 2} 25g / 2cm defective * Comparative Example 9 X-8 0.50 g / m ² 20 g / 2 cm defective * Comparative Example 10 X-9 0.50 g / m ² 24 g / 2 cm defective * Comparative Example 11 X-10 0.50 g / m ² 22 g / 2cm defective * ──────────────────────────────────── Note: defective * (white spots or dots Residual film occurs)

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Examples 5 to 10 A photosensitive material was prepared and evaluated in the same manner as in Example 1 except that the polymers shown in Table 2 below were used in place of the polymers used in the adhesive layer of Example 1. did. The results are shown in Table 2.

[0138]

[Table 2] Table 2 ──────────────────────────────────── Photosensitive material Polymer Adhesive layer Film weight Peeling force Image formation ──────────────────────────────────── Example 5 CP-5 0. 05g / m ² 140g / 2cm good example ^{6 I-16 0.05g / m 2} 95g / 2cm good example ^{7 I-17 0.05g / m 2} 170g / 2cm good example 8 CP-9 0.05g / m ² 100 g / 2 cm good Example 9 CP-12 0.05 g / m ² 120 g / 2 cm good Example 10 II-8 0.05 g / m ² 155 g / 2 cm good ──────────── ──────────────────────── Note: The polymers used in Examples 6, 7, and 10 Is a homopolymer consisting to unit I-16, I-17, II-8.

[Example 11] In the same manner as in Example 1, after forming a curable layer on an aluminum support, the following photosensitive layer coating solution was applied on the curable layer, and the dried film thickness was 1 .3μ
m of the photosensitive layer was formed. In the same manner as in Example 1, a photosensitive material was prepared by forming an image formation accelerating layer on the photosensitive layer, and evaluated. The results are shown in Table 3.

<< Coating solution for photosensitive layer >>ポ リ ビ ニ ル Polyvinyl alcohol with a saponification degree of 79.5% (PVA-405, manufactured by Kuraray Co., Ltd.) )) 5.25 g 0.11% by weight methanol solution of additive (S-1) of Example 1 0.41 g 0.11% by weight aqueous solution of additive (S-2) of Example 1 0 0.41 g Silver halide emulsion of Example 1 0.50 g 5% by weight aqueous solution of surfactant of Example 1 0.40 g Reducing agent dispersion of Example 1.20 g Water 7.80 g 1 weight of copolymer CP-1 % Aqueous solution 5.25g ────────────────────────────────────

[0141]

[Table 3] Table III ──────────────────────────────────── Photosensitive material Polymer addition amount ** Peeling force Image formation ──────────────────────────────────── Example 11 CP-1 10.0 weight % 105g / cm ² good ──────────────────────────────────── Note: Addition amount ** (polyvinyl Weight ratio to alcohol)

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a typical layer configuration of a photosensitive material of the present invention.

FIG. 2 is a schematic sectional view showing another typical layer configuration of the photosensitive material of the present invention.

[Explanation of symbols]

 Reference Signs List 1,21 Aluminum support 2,22 Curable layer 3 Adhesive layer 4,23 Photosensitive layer 5,24 Image formation accelerating layer 6,25 Ethylenically unsaturated polymerizable compound 7,26 Hydrophobic polymer having acidic group 8 , 29 water-soluble synthetic polymer 9, 27 silver halide 10, 28 reducing agent 11, 13, 30, 32 hydrophilic polymer 12, 31 base precursor

Claims (8)

[Claims] 1. A curable layer containing an ethylenically unsaturated polymerizable compound and a hydrophobic polymer having an acidic group, a photosensitive layer containing silver halide and a hydrophilic polymer, and a curable layer and a photosensitive layer on a support. A photosensitive material containing a reducing agent, wherein the adhesive layer comprises a repeating unit represented by the following formula (I) or (II): A light-sensitive material comprising a water-soluble synthetic polymer having 50 mol% or more. Embedded image Wherein R ¹ and R ² are each a hydrogen atom or methyl; R ¹¹ and R ¹² are each a hydrogen atom,
An aliphatic group or an aromatic group, or R ¹¹ and R ¹²
Are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring; R ²¹ and R ²² are each a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²² are Linked together to form a 5- or 6-membered nitrogen-containing heterocycle; and R ²³ is an alkylene or arylene group. 2. The photosensitive material according to claim 1, wherein the water-soluble synthetic polymer is a copolymer having a repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II) in an amount of 5 mol% or more. material. 3. The light-sensitive material according to claim 1, wherein the adhesive layer further contains a water-soluble polysaccharide. 4. The photosensitive material according to claim 1, further comprising an image formation accelerating layer containing a base or a base precursor on the photosensitive layer. 5. A support, on which a curable layer containing an ethylenically unsaturated polymerizable compound and a hydrophobic polymer having an acidic group, and a photosensitive layer containing silver halide are provided. Is a photosensitive material containing a reducing agent, wherein the photosensitive layer further contains a water-soluble synthetic polymer having a repeating unit represented by the following formula (I) or (II) in an amount of 50 mol% or more. . Embedded image Wherein R ¹ and R ² are each a hydrogen atom or methyl; R ¹¹ and R ¹² are each a hydrogen atom,
An aliphatic group or an aromatic group, or R ¹¹ and R ¹²
Are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring; R ²¹ and R ²² are each a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²² are Linked together to form a 5- or 6-membered nitrogen-containing heterocycle; and R ²³ is an alkylene or arylene group. 6. The photosensitive material according to claim 5, wherein the water-soluble synthetic polymer is a copolymer having a repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II) in an amount of 5 mol% or more. material. 7. The photosensitive material according to claim 5, wherein the photosensitive layer further contains a water-soluble polysaccharide. 8. The light-sensitive material according to claim 5, further comprising an image formation accelerating layer containing a base or a base precursor on the light-sensitive layer.