JPH09292712A - Photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material giving a clear image over a wide heat development temp. range by incorporating a precursor of a base made of the salt of carboxylic acid with a specified org. base. SOLUTION: This photosensitive material has a photosensitive curable layer contg. silver halide, a reducing agent, a polymerizable compd. or a crosslinkable polymer and a precursor of a base made of the salt of carboxylic acid with a biguanide compd. represented by the formula as an org. base on the substrate. In the formula, each of R<1> -R<7> is H, a monovalent group represented by -NR<8> R<9> , etc., each of R<8> and R<9> is H, a monovalent group such as a residue of a hetero ring, etc., the group may have a substituent and arbitrary two of R<1> -R<9> may bond to each other to form a 5- or 6-membered N-contg. hetero ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-sensitive material in which a support is provided with a light-sensitive curable layer containing a silver halide, a reducing agent, a polymerizable compound or a crosslinkable polymer and a base precursor.

[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, an inorganic or organic base or a base precursor thereof (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) is used. Considering the stability of the light-sensitive material during storage, a base precursor is preferably used rather than a base. A typical example of the base precursor is a decarboxylation type base precursor composed of a salt of a carboxylic acid and an organic base. Regarding a base precursor composed of a salt of a carboxylic acid and an organic base, first of all, a carboxylic acid salt has been proposed in which the decarboxylation reaction is likely to occur, focusing on the carboxylic acid side. Specific carboxylic acid salts include trichloroacetic acid salts (described in British Patent No. 998949), propiolic acid salts (described in JP-A-59-180537) and sulfonylacetic acid salts (JP-A-61-51139). U.S. Pat. No. 4,060,420) has been proposed.

Separately, a base precursor using a specific organic base has been proposed, focusing on the organic base side. For example, carboxylic acid salts of triazine compounds (US Pat.
3374), a diacid, triacid or tetraacid base of a carboxylic acid salt of amidines (JP-A-63-3167).
No. 60) and carboxylic acid salts of guanidines which are diacid, triacid or tetraacid bases (JP-A-64-6874).
No. 6 publication) is proposed. The base precursors using the latter two diacid, triacid or tetraacid bases have excellent storage stability and rapidly decompose to release the base when the temperature exceeds a certain value. That is, these diacid, triacid or tetraacid base precursors are excellent base precursors that satisfy the generally required conditions.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Studies on light-sensitive materials containing a diacid, triacid or tetraacid base precursor described in JP-A-3-316760 and 64-68746 have revealed some problems. The diacid, triacid or tetraacid base has a large molecular size and is slow to diffuse in the photosensitive material. Therefore, it was found that even if the base was rapidly produced, it took time before it actually worked. This problem,
This was remarkable when the photosensitive material was heated at low temperature (heat development). Further, when the base is polyvalent, it may cause a Michael addition reaction with the polymerizable compound or the crosslinkable polymer in the light-sensitive material, and a polymer having a three-dimensional crosslinked structure may be produced as a by-product. When a polymer having a three-dimensional crosslinked structure is formed in the uncured portion of the curable layer, fogging occurs in the obtained cured image. The problem is that the photosensitive material is heated at high temperature (heat development).
It was remarkable when it did.

Due to the above problems, in the light-sensitive material containing the above-mentioned base precursor, the proper developing temperature range in which a clear image can be obtained is narrow and the reproducibility of the image is low. An object of the present invention is to provide a light-sensitive material containing a novel base precursor which does not decompose during storage at room temperature and can be rapidly decomposed upon heating to release a base. It is also an object of the present invention to provide a light-sensitive material that is free from the possibility of by-products such as three-dimensional cross-linked polymer during thermal development. Further, an object of the present invention is to provide a light-sensitive material having a wide range of heat development temperature that can obtain a clear image.

[0008]

Means for Solving the Problems The present invention includes the following (1) to
The photosensitive material of (3) is provided. (1) A photosensitive material in which a photosensitive curable layer containing a silver halide, a reducing agent, a polymerizable compound or a crosslinkable polymer and a base precursor composed of a salt of a carboxylic acid and an organic base is provided on a support. A photosensitive material, wherein the organic base is a biguanide compound represented by the following formula (I).

[0009]

[Chemical 6]

In the above formula (I), R ¹ , R ² , R
³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue and -NR ⁸ R ⁹ . R ⁸ and R ⁹ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue, and each group is one or more. It may have a substituent and is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
Any two groups selected from ⁷ , R ⁸ and R ⁹ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle.

(2) On a support, a curable layer containing a polymerizable compound or a crosslinkable polymer, and a photosensitive layer containing a silver halide and a base precursor composed of a salt of a carboxylic acid and an organic base, A light-sensitive material containing a reducing agent in a light-sensitive layer or a curable layer, wherein the organic base is a biguanide compound represented by the above formula (I). (3) A curable layer containing a polymerizable compound or a crosslinkable polymer, a photosensitive layer containing silver halide, and an image formation promoting layer containing a base precursor composed of a salt of a carboxylic acid and an organic base on a support. A photosensitive material having a reducing agent contained in a photosensitive layer or a curable layer, wherein the organic base is a biguanide compound represented by the above formula (I). The carboxylic acid has the formula (I
It is preferably represented by I) or (III).

[0012]

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In the above formula (II), R ²¹ and R
²² is a hydrogen atom, an alkyl group, an alkenyl group,
A monovalent group selected from the group consisting of an aryl group and a heterocyclic residue, n is 1 or 2, and when n is 1, Y is an alkyl group, an alkenyl group, an alkynyl group,
A monovalent group selected from the group consisting of an aryl group and a heterocyclic residue, and when n is 2, Y is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue. And each group may have one or more substituents.

[0014]

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In the above formula (III), m is 1 or 2, and when m is 1, Z is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue and a carboxyl group. Is a monovalent group selected from the group consisting of, when m is 2, Z is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue, and each group is 1 It may have the above substituents.

[0016]

The base precursor used in the present invention is characterized in that it is a biguanide whose organic base moiety is a monoacid group. Biguanides have low molecular weight and form compact salts with carboxylic acids. Therefore, the crystals of the base precursor (salt) have a dense structure as a whole. Therefore, the base precursor has a stable crystal structure at room temperature. Further, generally, carboxylic acid has a hydrophobic group such as an aryl group in order to promote decarboxylation. In such a case, the crystal structure is further stabilized because the entire salt has a hydrophobic property. When this base precursor is heated, the decarboxylation reaction of the carboxyl does not occur while the above stable crystal structure is maintained, and the crystal structure collapses and the decarboxylation reaction rapidly progresses to form a base. To do. Therefore, the photographic material of the present invention can rapidly generate a base by rapidly decomposing it when heated by using a base precursor that does not decompose during storage at room temperature.

Further, since the organic base portion of the base precursor used in the present invention is a monoacid base having a small molecular weight, the base diffusion rate is rapid in addition to the base generation rate. Furthermore, since the light-sensitive material of the present invention produces a monoacid group, there is no possibility that a by-product such as a polymer is generated. As a result, the light-sensitive material of the present invention can form a clear image in a wide heat development temperature range. The base portion of the base precursor used in the present invention is a basic substance (biguanidine compound or an acid salt thereof) which can be added to a diazo heat-sensitive recording material, and is disclosed in JP-A-59-10699.
It is described in Japanese Patent No. 4 publication. A biguanidine compound represented by the following general formula is disclosed in the upper right column on page 2 of the publication.

[0018]

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In the formula, R _{1 to} R ₆ represent hydrogen, alkyl, cycloalkyl, hydroxy, alkoxy, aromatic group or heterocyclic group. In the lower right column of page 2 of the publication, "inorganic acid salts such as sulfuric acid, hydrochloric acid, carbonic acid and phosphoric acid and organic acid salts such as citric acid, tartaric acid and oxalic acid" are described as an acid salt of a biguanidine compound. Has been done. In the light-sensitive material of the present invention, unlike these acidic salts, by using a salt with a carboxylic acid having a decarboxylizable carboxyl, that is, a base precursor, the above-mentioned unexpected effect can be obtained.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION

[Base Precursor] The base precursor used in the present invention is characterized in that the organic base is a biguanide compound represented by the following formula (I).

[0021]

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In the formula (I), R ¹ , R ² , R ³ and R
⁴ , R ⁵ , R ⁶ and R ⁷ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue and -NR ⁸ R ^9. . Hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue and -NR ⁸ R ⁹ are preferred. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. The alkyl group may have any of a linear structure, a cyclic structure and a branched structure. Examples of alkyl groups include methyl, ethyl, butyl, octyl, cyclopentyl, cyclohexyl and decahydronaphthyl. The alkyl group may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), hydroxy, cyano, a halogen atom and a sulfonamide group. These substituents may be further substituted. Examples of substituted alkyl groups include benzyl, phenethyl and 1-hydroxy-1-cyclohexyl.

The alkenyl group has 2 to 20 carbon atoms.
Is preferred, 2 to 10 is more preferred, and 2 to 6 is most preferred. The alkenyl group may have a linear structure, a cyclic structure or a branched structure. Examples of alkenyl groups include propenyl and isopropenyl. An alkenyl group is
It may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), hydroxy, cyano, a halogen atom and a sulfonamide group. These substituents may be further substituted. Examples of the substituted alkenyl group include styryl. The alkynyl group has 2 to 2 carbon atoms.
It is preferably 0, more preferably 2 to 10, and most preferably 2 to 6. Examples of the alkynyl group include ethynyl. The alkynyl group may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), hydroxy, cyano, a halogen atom and a sulfonamide group. These substituents may be further substituted. Examples of substituted alkynyl groups include phenylethynyl.

The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and most preferably 6 to 15 carbon atoms. Examples of the aryl group include phenyl and naphthyl. The aryl group may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), cyano, nitro, amino, amido group, sulfonamide group,
Alkoxy group, aryloxy group, alkoxycarbonyl group, ureido group, carbamoyl group, acyloxy group,
Heterocyclic residues, alkylsulfonyl groups, carboxyls, sulfamoyl groups and halogen atoms can be mentioned. These substituents may be further substituted.
The heterocyclic residue preferably has a 5- or 6-membered heterocyclic ring. The hetero atom in the heterocycle is a nitrogen atom,
An oxygen atom or a sulfur atom is preferable. Examples of heterocycles include
A furan ring, a thiophene ring, a pyridine ring, a quinoline ring, and a thiazole ring are included. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Examples of the fused heterocycle include a benzothiazole ring. The heterocyclic residue may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), aryl group, cyano, nitro, amino, amido group, sulfonamide group, alkoxy group, aryloxy group, alkoxycarbonyl group, ureido group, carbamoyl group, An acyloxy group, a heterocyclic residue, an alkylsulfonyl group, a carboxyl, a sulfamoyl group and a halogen atom can be mentioned. These substituents may be further substituted.

--NR ⁸ R ⁹ means an amino or substituted amino group. R ⁸ and R ⁹ are each a hydrogen atom,
It is a monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue. For the definition, examples and substituents of each group, see R above.
^{It is the same as 1 to} R ⁷ . R ¹ , R ² , R ³ , R ⁴ , R
Any two groups selected from ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. An alkylene group is preferred as the linking group for forming a heterocycle. However, a hetero atom (eg, oxygen atom, nitrogen atom) may be present in the linking group. Particularly preferred organic bases are shown in formulas (Ia) and (Ib) below.

[0026]

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In the formula (Ia), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic residue. The group may have one or more substituents, and any two groups selected from R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be bonded to each other to form a 5- or 6-membered nitrogen-containing group. A heterocycle may be formed. The definition, examples and substituents of each group are the same as those of R ^{1 to} R ^{7 in} formula (I) described above. In formula (Ib), R ¹⁶ and R ¹⁷ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic residue, and each group has one or more substituents. Optionally, and R ¹⁶ and R
¹⁷ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. The definition, examples and substituents of each group are the same as those of R ^{1 to} R ⁷ described above. The biguanide compound represented by the formula (I) has a resonance structure and functions as a monoacid group. The simplest compounds (R ¹ , R ² , R
⁽³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are all hydrogen atoms)
The resonance structure is shown below by taking the ionization state of the above as an example.

[0028]

[Chemical 12]

Specific examples of the organic base will be given below.

[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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[0035]

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[0036]

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[0037]

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[0038]

[Chemical 21]

[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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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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The carboxylic acid must have a property that the carboxyl group is decarboxylated at a constant heating temperature.
The heating temperature required for decarboxylation is preferably 50 to 200 ° C, more preferably 70 to 170 ° C. As the carboxylic acid having such properties,
Trichloroacetic acid, sulfonylacetic acid and propiolic acid are known. The decarboxylation reaction can be promoted by introducing an aromatic group into the carboxylic acid. Sulfonylacetic acid represented by the following formula (II) is a carboxylic acid that is preferably used.

[0057]

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In the above formula (II), R ²¹ and R
²² is a hydrogen atom, an alkyl group, an alkenyl group,
It is a monovalent group selected from the group consisting of an aryl group and a heterocyclic residue. A hydrogen atom, an alkyl group and an aryl group are preferable, and a hydrogen atom is particularly preferable. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. The alkyl group may have any of a linear structure, a cyclic structure and a branched structure. Examples of alkyl groups include methyl, ethyl, butyl, octyl, cyclopentyl, cyclohexyl and decahydronaphthyl. The alkyl group may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), an alkylsulfonyl group, an arylsulfonyl group, an amido group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a cyano group, a halogen atom and a sulfonamide group. . These substituents are
It may be further substituted. Examples of substituted alkyl groups include benzyl, phenethyl and 1-hydroxy-1-
Includes cyclohexyl.

The alkenyl group has 2 to 20 carbon atoms.
Is preferred, 2 to 10 is more preferred, and 2 to 6 is most preferred. The alkenyl group may have a linear structure, a cyclic structure or a branched structure. Examples of alkenyl groups include propenyl and isopropenyl. An alkenyl group is
It may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), an alkylsulfonyl group, an arylsulfonyl group, an amide group,
There may be mentioned a carbamoyl group, a sulfamoyl group, a hydroxy group, a cyano group, a halogen atom and a sulfonamide group. These substituents may be further substituted. Examples of the substituted alkenyl group include styryl. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,
Most preferably, it is 6 to 15. Examples of the aryl group include phenyl and naphthyl. The aryl group may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), cyano, nitro, amino, an alkylsulfonyl group, an arylsulfonyl group, an amide group, a sulfonamide group, an alkoxy group,
Examples thereof include an aryloxy group, an alkoxycarbonyl group, a ureido group, a carbamoyl group, an acyloxy group, a heterocyclic residue, an alkylsulfonyl group, a carboxyl, a sulfamoyl group and a halogen atom. These substituents may be further substituted.

The heterocyclic residue preferably has a 5- or 6-membered heterocyclic ring. The hetero atom in the heterocycle is preferably a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the heterocycle include furan ring, thiophene ring, pyridine ring,
A quinoline ring and a thiazole ring are included. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Examples of the fused heterocycle include a benzothiazole ring. The heterocyclic residue may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), an aryl group, cyano, nitro, amino, an alkylsulfonyl group, an arylsulfonyl group, an amide group, a sulfonamide group, an alkoxy group, an aryloxy group, an alkoxycarbonyl. Group, ureido group, carbamoyl group,
Acyloxy group, heterocyclic residue, alkylsulfonyl group,
Mention may be made of carboxyl, sulfamoyl groups and halogen atoms. These substituents may be further substituted.

In the formula (II), n is 1 or 2. When n is 1, Y is a monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue. Aryl groups and heterocyclic residues are preferred, with aryl groups being especially preferred. The definition, examples and substituents of each group other than the alkynyl group are the same as the above R ³¹ and R ³² . The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 6 carbon atoms. Examples of the alkynyl group include ethynyl. The alkynyl group may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), an alkylsulfonyl group, an arylsulfonyl group, an amido group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a cyano group, a halogen atom and a sulfonamide group. . These substituents may be further substituted. Examples of substituted alkynyl groups include phenylethynyl.

When n is 2, Y is an alkylene group,
It is a divalent group selected from the group consisting of an arylene group and a heterocyclic residue. An arylene group and a divalent heterocyclic residue are preferable, and an arylene group is particularly preferable. The alkylene group preferably has 1 to 20 carbon atoms,
It is more preferably 1 to 10, and most preferably 1 to 6. The alkylene group may have any of a linear structure, a cyclic structure and a branched structure. Examples of alkylene groups include methylene and propylene. The alkylene group may have one or more substituents. Examples of the substituent include an aryl group, an alkoxy group (eg, methoxy), an alkylsulfonyl group, an arylsulfonyl group, an amido group, a carbamoyl group, a sulfamoyl group, a hydroxy group, a cyano group, a halogen atom and a sulfonamide group. . These substituents are
It may be further substituted. The arylene group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and most preferably 6 to 15 carbon atoms. Examples of the arylene group include phenylene and naphthylene. The arylene group may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), cyano, nitro, amino, alkylsulfonyl group, arylsulfonyl group, amide group, sulfonamide group, alkoxy group, aryloxy group, alkoxycarbonyl group, ureido group. Examples thereof include groups, carbamoyl groups, acyloxy groups, heterocyclic residues, alkylsulfonyl groups, carboxyls, sulfamoyl groups and halogen atoms. These substituents may be further substituted.

The divalent heterocyclic residue preferably has a 5- or 6-membered heterocyclic ring. The hetero atom in the heterocycle is preferably a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the heterocycle include a furan ring, a thiophene ring, a pyridine ring, a quinoline ring and a thiazole ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Examples of the fused heterocycle include a benzothiazole ring. The heterocyclic residue may have one or more substituents. Examples of the substituent include an alkyl group (eg, methyl, butyl), an aryl group, cyano, nitro, amino,
Alkylsulfonyl group, arylsulfonyl group, amide group, sulfonamide group, alkoxy group, aryloxy group, alkoxycarbonyl group, ureido group, carbamoyl group, acyloxy group, heterocyclic residue, alkylsulfonyl group, carboxyl, sulfamoyl group and halogen Atoms can be mentioned. These substituents may be further substituted.

The propiolic acid represented by the following formula (III) is also a carboxylic acid preferably used.

[0065]

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In the formula (III), m is 1 or 2. When m is 1, Z is a hydrogen atom, an alkyl group,
It is a monovalent group selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue and a carboxyl. Aryl groups are particularly preferred. For the definition, examples and substituents of each group, R ³¹ and R ^{32 in the} above-mentioned formula (II) are defined.
And Y. When m is 2, Z is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue. Arylene groups are particularly preferred. The definition, examples and substituents of each group are the same as those of Y in formula (II) described above. Specific examples of the carboxylic acid will be given below.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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The base precursor used in the present invention comprises a salt of the above-mentioned carboxylic acid and an organic base. There is no particular limitation on the combination of the carboxylic acid and the organic base. However, the melting point (or decomposition temperature) of salt is 50 to 2
The temperature is preferably 00 ° C, more preferably 70 to 170 ° C. Specific examples of the base precursor that can be used in the present invention are shown below.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

[Chemical formula 106]

[0134]

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[0135]

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[0136]

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[0137]

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[0138]

[Chemical 111]

Methods for synthesizing organic bases (biguanide compounds) are described in known literature (eg, The Chemistry of Functional).
Groups / The Chemistry of amidines and imidates (SP
The method described in ataiand Z. Rappoport) Vol. 2, (1991), p488-494) can be referred to. The synthesis examples of the base precursors (6) and (10) are shown below. Other base precursors can be synthesized by the same method.

[Synthesis Example 1] Isopropyl alcohol 70
A solution in which 4.2 g of dimethylthiourea and 8.5 g of octyl bromide were dissolved in ml was heated under reflux for 5 hours.
Separately, a solution prepared by dissolving 3.6 g of guanidine carbonate in 70 ml of isopropyl alcohol was neutralized by adding 7.7 g of 28% by weight sodium methoxide solution, and then filtered. The obtained guanidine solution was added to the above heated and refluxed solution, and the mixture was further heated and refluxed for 4 hours. The product was reprecipitated by adding dropwise to 500 ml of ethyl acetate in the reaction solution to obtain 5.0 g (yield: 59%) of a base (B-3) hydrobromide.
Next, 3.2 g of the obtained base hydrobromide was neutralized with 1.0 g of potassium hydroxide in methanol, and the free base obtained by filtration was added to carboxylic acid (A-7) in 160 ml of ethanol. A solution in which 5.1 g was dissolved was slowly added dropwise at 60 ° C. Two hours after the completion of the dropwise addition, the mixture was stirred at room temperature, filtered and separated, and 3.2 g of the base precursor (6) (yield:
46%). The melting point was 123.2 ° C. (decomposition).

[Synthesis Example 2] Butylthiourea was condensed with octyl bromide in the same manner as in Synthesis Example 1 except that butylthiourea was used instead of dimethylthiourea used in Synthesis Example 1. The hydrobromide obtained by treating in the same manner as in Synthesis Example 1 was neutralized with potassium hydroxide to form a salt with sulfuric acid, and a sulfate of the base (B-7) was obtained with a yield of 53%. Then, by forming a salt with a carboxylic acid (A-7) in the same manner as in Synthesis Example 1, a base precursor (10) was obtained with a yield of 58%. The melting point was 127.4 ° C. (decomposition). Base (B
5.0 g (yield: 59%) of the bromic acid salt of -3) was obtained.

The base precursor is preferably used in the range of 0.1 to 20 mol, and more preferably in the range of 0.2 to 10 mol, per mol of silver halide. You may use together two or more types of base precursors. Hereinafter, the layer structure of the photosensitive material, components other than the base precursor, and each step of the image forming method using the photosensitive material will be sequentially described.

[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 precursor is added to the photosensitive curable layer, the photosensitive layer or the image formation promoting layer. Even if a base precursor is added to a layer other than the photosensitive layer, such as the image formation promoting layer, the base generated during heat development diffuses into the photosensitive layer.

[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. By adding a component that promotes image formation to the overcoat layer (eg, base precursor, reducing agent, heat development accelerator), in addition to the protective function as an overcoat layer, it has the function of promoting image formation. Good. 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 0.
It is preferably 3 to 20 μm, and 0.5 to 10
More preferably, it is μm. The overcoat layer is generally formed using a hydrophilic polymer. However,
Hydrophobic polymers can also be used. For example, it can be formed by dissolving a hydrophobic polymer in a solvent and coating it. It can also be formed by coating a polymer latex. If a hydrophobic polymer is used for the etching treatment, these layers must be removed by peeling after thermal development and prior to etching.

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

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

By adjusting the type and amount of the reducing agent, the polymerizable compound in either the latent image formed portion or the latent image not formed portion of the silver halide 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 an ester or amide of acrylic acid or methacrylic acid, to which a specific residue (R group of --COOR or --CONHR) is bonded, can be used as the crosslinkable polymer. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ² = CR ³ R
⁴ ,-(CH ₂ O) _n -CH ₂ CR ² = CR ³ R ⁴ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ² = CR ³
R ⁴ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ² = CR ³ R ⁴ ,-(CH ₂ ) _n -O-CO-CR ²
= CR ³ R ⁴ and-(CH ₂ CH ₂ O) ₂ -X (R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or aryl. Is an oxy group, R ² and R ³ or R ⁴ may combine with each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue). Can be mentioned. Specific examples of the ester residue, -CH ₂ CH = CH ₂ (JP 64-17
047 JP allyl (meth) corresponding to the polymer of the _{acrylate), - CH 2 CH 2 O} -CH 2 CH = CH 2, -CH 2 C (CH 3) = CH 2,
-CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCO
O-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) are included. Specific examples of amide residues include -C
H ₂ CH = CH ₂ , -CH ₂ CH ₂ -1-Y (Y is a cyclohexene residue) and -CH ₂ CH ₂ -OCO-CH = CH ₂ are included.

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

Examples of non-crosslinkable polymers (polymers that are not crosslinkable or weakly crosslinkable) are polyacrylic acid ester, polymethacrylic acid ester, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, Polymethacrylonitrile, polyethylene,
Polyvinyl pyridine, polyvinyl imidazole, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, chlorinated polyethylene, chlorine polypropylene,
Polyester, polyamide, polyurethane, polycarbonate, ethyl cellulose, triacetyl cellulose,
Mention may be made of diacetyl cellulose and cellulose acetate butyrate. Of these repeating units of the polymer, those which can be copolymerized can be arbitrarily combined and used as a copolymer. Examples of specific binders include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), polycondensation type synthetic homopolymers and copolymers (eg, polyester, polyamide, polyurethane, Polyester-polyamide).

When the uncured curable layer is removed by elution with an alkaline aqueous solution after curing, the (crosslinkable or non-crosslinkable) polymer used for the curable layer may have an acidic functional group in its molecule. preferable. Examples of the acidic functional group include a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group and a sulfonimide group. Specifically, monomers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride can be copolymerized at the time of synthesizing the above-mentioned polymer to incorporate these acidic groups into the polymer of the curable layer. The molar content of the monomer having an acidic group in the copolymer is preferably 1 to 60%, more preferably 5 to 40%. The polymer of the curable layer is most preferably a copolymer obtained by copolymerizing the above-mentioned monomer having a crosslinkable group and a monomer having an acidic functional group. The molecular weight of the polymer of the curable layer is preferably in the range of 1,000 to 500,000.
You may use together 2 or more types of polymers. The content of the polymer in the curable layer is 10 to 90% by weight based on the whole curable layer.
Is preferable, and more preferably 30 to 80% by weight.

[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 heat 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.

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

[Development Stopping Agent] In the present invention, various development stopping agents can be used for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during heat development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the layer and to inhibit development by interacting with a compound or silver and silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Thermal development terminators are disclosed in JP-A-62-2531.
No. 59, JP-A-2-42447 and 2-26
No. 2661, each of which is described.

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

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

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

[Exposure Step] Image exposure is carried out using a light source which emits light having a wavelength corresponding to the spectral sensitivity of silver halide (sensitizing dye) which is a photosensor. Examples of light sources include tungsten lamps, halogen lamps, xenon lamps,
Lamps such as xenon flash lamps, mercury lamps, carbon arc lamps, various lasers (eg semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser),
A light emitting diode, a cathode ray tube, etc. can be mentioned.
The exposure wavelength is generally visible light, near ultraviolet light, or near infrared light, but X-rays or electron beams may be used. The exposure dose is generally in the range of 0.01 to 10000 erg / cm ² , more preferably 0.1 to 1000 erg / cm ² . When the 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 exposure process of silver halide, that is, the process of forming a latent image is affected by the 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 .

[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.

[0191]

【Example】

 [Example 1] Preparation of photosensitive material "Creation of aluminum support" JI with a thickness of 0.24 mm
The surface of the aluminum plate according to S-A-1050 is
Water suspension of Ronbrush and Pamiston (400 mesh)
After graining with and washed well with water. Next, 10%
Immerse in the aqueous sodium hydroxide solution at 70 ℃ for 60 seconds
After etching, it was washed with running water. 20% nitric acid water
The solution was neutralized, washed, and then washed with water. Obtained al
Alternate the square wave alternating current (condition: anode current
Pressure 12.7v, ratio of electricity quantity at cathode to electricity quantity at anode
0.9, electric quantity at anode 160 coulomb / dm^Two )
And 1% nitric acid aqueous solution containing 0.5% aluminum nitrate
Electrolytic surface roughening treatment was performed in the liquid. Surface roughness of the obtained plate
Was 0.6 μm (Ra indication). Following this process
Then, in a 1% aqueous sodium hydroxide solution at 40 ° C for 30 seconds
After soaking, it was treated in a 30% aqueous solution of sulfuric acid at 55 ° C for 1 minute.
I understood. Next, the thickness is 2.5g / dm^Two So that
Current density 2A using direct current in 20% sulfuric acid aqueous solution
/ Dm^Two Anodizing treatment was performed under the conditions of. Obtained al
The minium plate was washed with water and dried to prepare a support.

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

──────────────────────────────────── Pigment dispersion ──────── ───────────────────────────── Pigment (Chromophtal red A2B) 18g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80 / 20) 12g cyclohexanone 30g propylene glycol monomethyl ether 40g ─────────────────────────────────────

[Formation of Curable Layer] The following coating liquid was coated on the aluminum support and dried to form a curable layer having a dry coating amount of 1.8 g / m ² .

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

[Preparation of Silver Halide Emulsion] Gelatin, potassium bromide and water were added and sodium hydroxide was added to adjust the pH at room temperature to 9.5 and the solution was heated to 55 ° C. The thioether compound was added in an amount corresponding to 2.0 × 10 ⁻³ mol based on the total amount of silver nitrate added. P of reaction vessel
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 so that the molar ratio of rhodium to the total amount of potassium iodide and silver nitrate was 2 × 10 ^-8 mol. Is pAg
The silver iodobromide grains were formed by addition by the control double jet method. Then, sulfuric acid was added to adjust the pH to 6.0.
At 55 ° C. and pAg = 9.3,
The aqueous solution of silver nitrate and the molar ratio of iridium to silver are 10
^A potassium / bromide solution containing hexachloroiridium (III) in an amount of ⁻⁷ mol was added in two stages by the double jet method to prepare a core / shell type silver iodobromide emulsion having the following composition.

[0197]

[Chemical 112]

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

The resulting emulsion grains were monodisperse and 98% of all grains were present within ± 40% of the average grain size. Then, after desalting this emulsion, the two types of spectral sensitizing dyes A and B shown below were kept at 40 ° C. with stirring.
2: 1 molar ratio mixed methanol solution was added in an amount corresponding to 8 × 10 ⁻⁴ mol / mol Ag and held for 15 minutes. Furthermore, 6 × 10 ⁻⁴ mol / mol of sodium salt of thiol having the structure
An equivalent amount of mol Ag was added, and the mixture was stirred and held for 5 minutes. Then, the emulsion pH was adjusted to 6.5 and pAg to 8.8 to obtain a silver halide emulsion.

[0200]

[Chemical 113]

[0201]

Embedded image

[0202]

[Chemical 115]

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

[0204]

Embedded image

[Formation of Photosensitive Layer] The following coating solution was prepared, coated on the curable layer and dried to form a photosensitive layer having a dry coating amount of 2.0 g / m ² .

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol with a saponification degree of 79.5% (PVA-405, manufactured by Kuraray Co., Ltd.) ) 10 wt% aqueous solution 10.5 g 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 Silver halide emulsion 0.50 g 5% by weight aqueous solution of the following surfactant (SA-1) 0.40 g Water 7.80 g The above reducing agent dispersion 1.20 g ───────────── ────────────────────────

[0207]

[Chemical 117]

[0208]

Embedded image

[0209]

[Chemical formula 119]

[Preparation of Base Precursor Dispersion] 50 g of powder of the base precursor (10) was dispersed in 150 g of a 3% by weight aqueous solution of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) using a Dynomill disperser. The particle size of the base precursor was 0.5 μm or less.

[Formation of Image Formation Accelerating Layer] The following coating solution was prepared, coated on the above-mentioned photosensitive layer and dried to provide an image forming promoting layer having a dry coating amount of 4.0 g / m ² . .

──────────────────────────────────── Coating solution for the image formation promoting layer ──── ──────────────────────────────── Polyvinyl alcohol with a saponification degree of 98.5% (PVA-105, Kuraray Co., Ltd. A) 10% by weight aqueous solution 200.0 g of the above base precursor dispersion 1.25 g 5% by weight aqueous solution of the above surfactant (SA-1) 4.0 g ───────────── ────────────────────────

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

──────────────────────────────────── Alkaline eluent ──────── ──────────────────────────── 28 wt% potassium silicate aqueous solution 125.0 g potassium hydroxide 15.0 g water 750.0 g ─ ───────────────────────────────────

(Image formation) The obtained light-sensitive material was subjected to an argon ion laser (XLP-400 manufactured by Optronics Co., Ltd.).
0), exposure was performed with an energy amount of ² μJ / cm ² .
Next, the aluminum support surface of the light-sensitive material was heat-developed for 30 seconds by a method in which it was conveyed while being brought into close contact with a heated hot plate. As a result, a silver image was formed on the exposed portion under the temperature range of 130 ° C to 160 ° C. I was seen. Using the above alkaline eluate, this was brush-developed with an automatic etching machine, the photosensitive layer and the image formation promoting layer were completely eluted and removed at the same time, and the curable layer in the unexposed area was removed at the same time. A relief image of a red colored polymer with good contrast was obtained. The maximum density (Dmax) and the minimum density (Dmin) of the printing plate thus obtained are
Evaluation was carried out under the condition of heat development in steps of 10 ° C in the temperature range of 0 ° C to 160 ° C. The results are summarized in Table 1.

[Examples 2 to 6, Comparative Examples 1 and 2] Instead of the base precursor (10) used in Example 1, base precursors (6, (8), (11), (22), (2).
A photosensitive material was prepared and evaluated in the same manner as in Example 1 except that 3), (X) and the basic substance (Y) were used. The results are shown in Table 1.

[0219]

[Table 1] Table 1 ──────────────────────────────────── Photosensitive materials Basic decomposition temperature Heat Development temperature (upper: Dmax, lower: Dmin) Substance (℃) 130 ℃ 140 ℃ 150 ℃ 160 ℃ ──────────────────────────── ───────── Example 1 (10) 127.4 1.56 1.68 1.69 1.71 0.33 0.33 0.33 0.33 Example 2 (6) 123. 2 1.52 1.64 1.67 1.69 0.33 0.33 0.33 0.33 Example 3 (8) 123.7 1.48 1.71 1.71 1.72 0.33 0 .33 0.33 0.33 Example 4 (11) 123.1 1.53 1.67 1.66 1.70 0.33 0.33 0.33 0.33 Example 5 (22) 1.2 1.60 1.71 1.73 1.75 0.33 0.33 0.34 0.34 Example 6 (23) 95.5 1.57 1.77 1.78 1.78 0. 33 0.34 0.34 0.34 ──────────────────────────────────── Comparative Example 1 ( X) 127.7 0.33 0.78 1.71 1.73 0.33 0.33 0.34 0.68 Comparative Example 2 (Y) * 192.5 0.33 0.35 0.52 0. 65 0.33 0.33 0.33 0.33 ──────────────────────────────────── Note : (*) Y shows a melting point because it does not decompose. The minimum concentration of 0.33 is the same as the concentration on the support surface.

[0218]

Embedded image

[0219]

[Chemical 121]

Example 7 “Preparation of Pigment Dispersion” A mixed solution having the following composition was dispersed in a Dynomill disperser at 300 rpm at 45 ° C. for 1 hour.
A pigment dispersion having an average particle size of 0.10 μm was obtained.

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

Example 1 except that the above pigment dispersion was used.
A curable layer was formed on the support in the same manner as in.

[Preparation of Silver Halide Emulsion] The spectral sensitizing dyes A and B used in Example 1 were replaced by the following spectral sensitizing dyes C and D (molar ratio: 1: 1). A silver halide emulsion was prepared in the same manner as in Example 1.

[0224]

[0122]

[0225]

[0123]

A photosensitive layer and an image formation promoting layer were formed in the same manner as in Example 1 except that the silver halide emulsion prepared as described above was used.

(Image formation) The light-sensitive material thus obtained was exposed to light having a plate surface energy of 2 μJ / cm ² by dispersing light of 670 nm with a sharp cut interference filter with a light emission time of 10 ⁻⁴ seconds using a xenon flash. Solid exposure was carried out. Next, the aluminum support surface of the photosensitive material,
When heat development was carried out for 30 seconds by a method of transporting while being brought into close contact with a heated hot plate, a silver image was observed in the exposed portion under the condition of a temperature range of 130 ° C to 160 ° C. Then, using the alkaline eluent used in Example 1, brush development was performed with an automatic etching machine to elute and remove all of the photosensitive layer and the image formation promoting layer and the curable layer in the unexposed area at the same time. After thorough washing with water, a relief image of a polymer colored in blue with good contrast was formed on the exposed area. 1 in the temperature range from 130 ℃ to 160 ℃
The maximum density of the printing plate obtained by heat development at 0 ° C increments (Dma
x) and minimum density (Dmin) are measured by a densitometer (X-RIT
E) was used to measure the blue reflection density. Second result
It is shown in the table.

[0228]

[Table 2] Table 2 ──────────────────────────────────── Photosensitive materials Basic decomposition temperature Heat Development temperature (upper: Dmax, lower: Dmin) Substance (℃) 130 ℃ 140 ℃ 150 ℃ 160 ℃ ──────────────────────────── ───────── Example 7 (10) 127.4 1.80 1.82 1.83 1.83 0.33 0.33 0.33 0.33 ───────── ────────────────────────────

Example 8 A curable layer was formed on a support in the same manner as in Example 1. The following coating liquid was prepared, coated on the curable layer and dried to provide a photosensitive layer having a dry coating amount of 4.0 g / m ² .

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol with a saponification degree of 79.5% (PVA-105, manufactured by Kuraray Co., Ltd.) 10% by weight aqueous solution of 1) 10.5 g 0.11% by weight methanol solution of the additive (S-1) of Example 1 0.41 g 0.11% by weight aqueous solution of the additive (S-2) of Example 1 0 .41 g Silver halide emulsion of Example 1 0.50 g 5% by weight aqueous solution of the surfactant (SA-1) of Example 1 0.40 g Water 7.80 g Reducing agent dispersion of Example 1 1.20 g Example 1 base precursor (10) dispersion 1.25 g ────────────────────────────────── ──

(Image formation) The obtained photosensitive material was used in Example 1.
An image was formed and evaluated in the same manner as in. The results are shown in Table 3.

[0232]

[Table 3] Table 3 ──────────────────────────────────── Photosensitive materials Basic decomposition temperature Heat Development temperature (upper: Dmax, lower: Dmin) Substance (℃) 130 ℃ 140 ℃ 150 ℃ 160 ℃ ──────────────────────────── ───────── Example 8 (10) 127.4 1.52 1.55 1.57 1.58 0.33 0.33 0.33 0.33 ───────── ────────────────────────────

[Chemical formula 122]

Embedded image

Claims (4)

[Claims] 1. A photosensitive material comprising a support and a photosensitive curable layer comprising a silver halide, a reducing agent, a polymerizable compound or a crosslinkable polymer and a base precursor composed of a salt of a carboxylic acid and an organic base. A light-sensitive material, wherein the organic base is a biguanide compound represented by the following formula (I). Embedded image In the above formula (I), R ¹ , R ² , R ³ , R ⁴ , R
^5, R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a monovalent group selected from the group consisting of heterocyclic residues and -NR ⁸ R ^9, R ⁸ And R ⁹ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue,
Each group may have one or more substituents and R
Any two groups selected from ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. May be formed. 2. A support, on which a curable layer containing a polymerizable compound or a crosslinkable polymer and a photosensitive layer containing a silver halide and a base precursor composed of a salt of a carboxylic acid and an organic base are contained, and which is reduced. A photosensitive material in which the agent is contained in a photosensitive layer or a curable layer, wherein the organic base is a biguanide compound represented by the following formula (I). Embedded image In the above formula (I), R ¹ , R ² , R ³ , R ⁴ , R
^5, R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a monovalent group selected from the group consisting of heterocyclic residues and -NR ⁸ R ^9, R ⁸ And R ⁹ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue,
Each group may have one or more substituents and R
Any two groups selected from ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. May be formed. 3. An image formation promoting process comprising a curable layer containing a polymerizable compound or a crosslinkable polymer, a photosensitive layer containing silver halide, and a base precursor composed of a salt of a carboxylic acid and an organic base on a support. A photosensitive material having a layer and a reducing agent contained in the photosensitive layer or the curable layer,
A photosensitive material, wherein the organic base is a biguanide compound represented by the following formula (I). Embedded image In the above formula (I), R ¹ , R ² , R ³ , R ⁴ , R
^5, R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a monovalent group selected from the group consisting of heterocyclic residues and -NR ⁸ R ^9, R ⁸ And R ⁹ are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue,
Each group may have one or more substituents and R
Any two groups selected from ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. May be formed. 4. A carboxylic acid represented by the following formula (II) or (III)
The photosensitive material according to any one of claims 1 to 3, represented by: Embedded image In the above formula (II), R ²¹ and R ²² are each a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group and a heterocyclic residue, and n
Is 1 or 2, and when n is 1, Y is a monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic residue, and n
When is 2, Y is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue, and each group may have one or more substituents. Embedded image In the above formula (III), m is 1 or 2, and m is 1
Is Z is a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic residue and a carboxyl, and when m is 2, Z is Is a divalent group selected from the group consisting of an alkylene group, an arylene group and a heterocyclic residue,
And each group may have one or more substituents.