JP2001075232A - Heat developable photographic sensitive material and rolled heat developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-contrast heat developable photosensitive material less liable to a dimensional change due to heat development, having high precision of overlapping and excellent in grazing resistance in conveyance for exposure and/or development, to process the heat developable photosensitive material and to obtain an ultrahigh-contrast rolled heat developable photosensitive material for a photomechanical process which improves a rising curl on the photosensitive layer side after development as a roll product, does not cause defective conveyance, is less liable to a dimensional change due to heat development and has high precision of overlapping. SOLUTION: The heat developable photographic sensitive material contains a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a binder and one or more compounds selected from among a hdyrazine derivative, a quatenary onium salt compound, an amine compound and a vinyl compound as a contrast enhancer on the substrate, has a polyvinyl formal- containing polymer layer on an organic silver salt-containing layer and has 0.001-0.04% dimensional change rate under heating at 120 deg.C for 30 sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable photographic light-sensitive material, and more particularly to a black-and-white heat-developable photographic light-sensitive material for printing plate making and a roll-shaped heat-developable photographic light-sensitive material suitable for roll making.

[0002]

2. Description of the Related Art In the past several years, plate making operations have changed greatly from manual operations to electronic plate collection. In such a flow, plotters such as imagesetters are rapidly spreading. A processing machine for a conventional silver halide photographic material is connected online to such precision equipment, and gas and moisture from the processing solution corrode the base, and failure of expensive equipment is increasing.

In conventional silver halide photographic materials, a water supply pipe is required for development, dilution of a fixing solution and washing with water, and it is troublesome to have a contractor handle waste liquid.

[0004] From such a background, a dry treatment system that does not use water is expected. Of the dry systems, thermal development is most suitable for practical use in terms of manufacturing cost and performance.

[0005] These photothermographic materials (hereinafter also referred to as photothermographic materials) are stable at room temperature, but are developed by heating to a high temperature (for example, 80 ° C to 140 ° C) after exposure. That is, heating produces silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas forms a black image, which is in contrast to the unexposed areas, where the image is formed. This reaction process proceeds without supplying a processing liquid such as water from the outside.

When these photothermographic materials are used as printing plate-making materials, since the product is in a roll form, a curl tends to be formed. Conventionally, in a photothermographic material for printing plate making, which is used as a heat-developable newspaper facsimile photosensitive material, especially in a roll-shaped photothermographic material for printing plate making, the curl before processing affects the rising curl after processing, so that the curl after development is It was difficult to adjust the rise curl. Therefore, there has been a problem in that when an automatic printing plate machine is used in the subsequent process of making a printing plate, conveyance failure occurs. Further, in the photothermographic material, the dimensional change of the photothermographic material after the heat development is larger than that of the conventional photothermographic material, which has been a practical problem.

Further, the dimensional change rate often changes in the process of adjusting the curl, and there has been no sufficient balance between the conventional photosensitive materials.

On the other hand, in the photographic light-sensitive material for printing plate making, a screening method for forming an image with a smaller halftone dot than before has begun to spread. For such a screening method, a super-hard contrast type photosensitive material in which the density of minute halftone dots is easy to be applied is preferable.

As a photographic technique for obtaining such a super-high contrast image, there is disclosed, for example, US Pat. No. 4,269,929 in which a hydrazine derivative is contained in a silver halide photographic light-sensitive material or JP-A-Hei. No. 4-98239 is disclosed.

However, in the conventional photothermographic material as described above, a sufficiently high contrast image has not been obtained.
Further, the ultra-high contrast type photosensitive material has a problem that a scratch is likely to occur at the time of exposure and / or development transportation, and the problem of overlay accuracy due to the dimensional change becomes remarkable.

Conventionally, it is common to provide a polymer layer containing polyvinyl formal for the purpose of improving the adhesive strength of a protective film and solving the problem of bleeding (a phenomenon in which additives such as a colorant are deposited in a powder form on the surface). Is known. (Japanese Unexamined Patent Publication (Kokai) No. 53-141613, etc.) Conventionally, in the above-described photothermographic material, a sufficiently high-contrast image has not been obtained. There is a problem that the problem of the overlay accuracy becomes remarkable.

[0012]

Accordingly, the first aspect of the present invention is as follows.
The purpose of the constitution (Claims 1 to 4) is to provide a high-contrast photothermographic material having a small dimensional change due to thermal development, high overlay accuracy, and excellent scratch resistance during transportation of exposure and / or development processing. The purpose is to provide a processing method.
Further, an object of the second configuration (claims 5 to 8) of the present invention is that
Roll-type photothermographic material for printing plate making with ultra-high contrast, improved rise curl on the photosensitive layer side after development processing as a roll product, no transport failure, little dimensional change due to thermal development, and high overlay accuracy Is to provide.

[0013]

The above object of the present invention is achieved by the following constitution.

(1) Photosensitive silver halide on a support,
In a photothermographic material containing at least one compound selected from hydrazine derivatives, quaternary onium salt compounds, amine compounds and vinyl compounds as an organic silver salt, a reducing agent for silver ions, a binder and a contrast agent, A polymer layer containing polyvinyl formal is provided on the layer containing an organic silver salt, and a thermal dimensional change at 120 ° C. for 30 seconds is 0.001% or more and 0.04% or less. Heat-developable photographic photosensitive material.

(2) The photothermographic material as described in (1) above, wherein the thickness of the support of the photothermographic material is 110 μm or more and 150 μm or less.

(3) The photothermographic material according to the above item (1) or (2), which forms a hard image having a gamma of 10 or more.

(4) The photothermographic material according to any one of the above (1) to (3), wherein the photothermographic material is processed by a heat developing machine in which the temperature of the heat developing section is 100 ° C. or more and 150 ° C. or less. A method for processing a heat-developable photographic light-sensitive material.

(5) Photosensitive silver halide on a support,
A roll for printing plate making containing at least one compound selected from hydrazine derivatives, quaternary onium salt compounds, amine compounds or vinyl compounds as organic silver salts, silver ion reducing agents, binders and contrast agents The heat-developable photographic photosensitive material is characterized in that the rising curl on the photosensitive layer side after the development processing is 0 to 60 mm, and the thermal dimensional change at 120 ° C. for 30 seconds is 0.001% or more and 0.04% or less. Rolled photothermographic material.

(6) The roll-form photothermographic material as described in (5) above, wherein the high contrast agent is at least one selected from hydrazine derivatives and vinyl compounds.

(7) The thickness of the support is 110 μm or more and 1
7. The roll-form photothermographic material according to the above item 5 or 6, wherein the thickness is 50 μm or less.

(8) The roll-form photothermographic material according to any one of the above items (5) to (7),
A method for processing a roll-form photothermographic material comprising processing at 0 to 60% RH.

Hereinafter, the present invention will be described in detail. The photothermographic material according to claim 1 of the present invention is a layer containing a compound or a composition which forms a photosensitive silver compound by reacting with an organic silver salt, a photosensitive silver halide or an organic silver salt. An overcoat layer (surface protective layer) containing polyvinyl formal is provided thereon.

The present inventors have surprisingly found that providing a polymer layer containing polyvinyl formal on a layer containing an organic silver salt improves thermal dimensional stability and scratch resistance. Further, they have found that the present invention is particularly effective in a photothermographic material using a high contrast agent such as a hydrazine derivative, and have made the present invention.

The coating thickness of the overcoat layer (surface protective layer) containing polyvinyl formal is 0.5 to 7 when dried.
μm is an appropriate thickness.

In the photothermographic material of the invention and / or its processing method, the absolute value of the thermal dimensional change at 120 ° C. for 30 seconds is 0.001% or more and 0.04% or less, more preferably 0.002% or less. Not less than 0.03%. This thermal dimensional change rate must satisfy both the longitudinal direction (application direction) and the width direction.

The dimensional stability is also related to the thickness of the support, and the thicker the support, the better the dimensional stability.
Thicker than 0 μm is better. However, if the thickness is too large, a conveyance failure occurs, and a scratch is generated accordingly. Therefore, the thickness is preferably from 110 μm to 150 μm, and more preferably from 110 μm to 130 μm.

The temperature of the heat developing section is preferably from 100 ° C. to 150 ° C., more preferably from 110 ° C. to 130 ° C. Outside this range, either development does not occur sufficiently and no high contrast is obtained, or fog becomes too large to be practical.

The roll-form photothermographic material for printing plate making according to claims 5 to 8 of the present invention has a rising curl of 0 to 60 mm on the photosensitive layer side after the development processing, and particularly a humidity of 10 to 60 mm during the heat development. ~ 60% RH (relative humidity) is preferred, the curl on the photosensitive layer side after development processing as a roll product is improved, and poor conveyance in the process of making a printing plate with an automatic printing machine is remarkably improved. Is what is done.

In the present invention, "measuring the rising curl on the photosensitive layer side after the development processing" means "after developing the sample, which has been entirely exposed to light, at 23 ° C. and 55% RH.
(Relative humidity), and then measure the rise curl when the sample is placed flat on a flat table.

The photosensitive silver halide in the present invention functions as an optical sensor. In the present invention,
In order to suppress white turbidity after image formation, and to obtain good image quality, the photosensitive silver halide preferably has a small average grain size, and the average grain size is 0.1 μm or less,
More preferably 0.01 μm to 0.1 μm, especially 0.0 μm
2 μm to 0.08 μm is preferred. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. If the crystal is not normal, for example, spherical, rod-like,
Alternatively, in the case of tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The particles are more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.

Monodispersity (%) = (standard deviation of particle size) /
(Average value of grain size) × 100 In the present invention, the silver halide grains have an average grain size of 0.1.
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means that the square root of the projected area is defined as a particle size rμm, and the thickness in the vertical direction is defined as hμ.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. These are disclosed in U.S. Pat. Nos. 5,264,337;
Nos. 314,798 and 5,320,958, and the like, and the desired tabular grains can be easily obtained. When these tabular grains are used in the present invention,
Further, the sharpness of the image is improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements, for the purpose of improving or adjusting the illuminance failure. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source, particularly a long chain (10 to 30, preferably 15 to 25) And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
And salts thereof: organic acid salts (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (Eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid ( For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5
-Dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-
Carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene and 3-carboxymethyl-
4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver with a nitrogen acid selected from 2,4-triazole and benzotriazole; saccharin, 5-
Silver salts such as chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate and / or silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and includes a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
Sodium behenate, sodium arachidate, etc.)
The soap and silver nitrate are added to produce organic silver salt crystals. At that time, silver halide grains may be mixed.

The photothermographic material of the present invention incorporates a reducing agent for silver ions. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512, 3,593,863, and Research Dis.
Closure Nos. 17029 and 29996, and include: Aminohydroxycycloalkenones (for example, 2-hydroxypiperidino-2)
-Cyclohexenone); aminoreductone esters (e.g., piperidinohexose reductone monoacetate) as precursors of reducing agents; N-hydroxyurea derivatives (e.g., N-p-methylphenyl-N-hydroxy) Aldehydes or ketone hydrazones (e.g., anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone, and (2) , 5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid);
Sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); Tetrahydroquinoxalines (Eg, 1,2,3,4-tetrahydroquinoxaline); amideoxins; azines (eg, a combination of an arylcarboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / Or hydrazine; hydroxanoic acids; combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; Phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-
Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t)
-Butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0042]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, t- butyl ).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0045]

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[0046]

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The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer can be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, in order to increase the speed of thermal development, the amount of the binder in the photosensitive layer is 1.5 to 10 g / m ^2.
It is preferable that More preferably, 1.7 to 8 g
/ M ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

The photothermographic material of the present invention contains a high contrast agent. Examples of the high contrast agent include a hydrazine derivative, an amine compound, a vinyl compound represented by the following general formula (G), and a compound represented by the following general formula (P). And quaternary onium compounds.

[0052]

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In the general formula (G), X and R are represented in the form of cis, but the general formula (G) includes the form of X and R in a trans form. This is the same in the structural representation of a specific compound.

Examples of the hydrazine derivative include a compound represented by the following general formula [H].

[0055]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent;
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Preferred D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group and the like.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.). .

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, Examples include a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent. Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

Further, in the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inactive alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl Group,
Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

In the general formula [H], examples of the silver halide adsorption accelerating group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group and special groups. 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. Preferred G ₀ is -CO-
Group, -COCO- group, G ₁ is a mere bond,
—O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D ₁ are present in the molecule If so, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (Such as an ethoxalyl group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but it should not be construed that the invention is limited thereto.

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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More preferred hydrazine derivatives are represented by the following formulas (H-1), (H-2), (H-3) and (H-4)
It is represented by

[0071]

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In the general formula (H-1), R ₁₁ , R ₁₂ and R ₁₃ each independently represent a substituted or unsubstituted aryl group or heteroaryl group. Specific examples of the aryl group include phenyl, p-Methylphenyl, naphthyl and the like. Specific examples of the heteroaryl group include, for example, a triazole residue, an imidazole residue,
Examples include a pyridine residue, a furan residue, and a thiophene residue. Further, R ₁₁ , R ₁₂ and R ₁₃ may be bonded via an arbitrary linking group. When R ₁₁ , R ₁₂ and R ₁₃ have a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a quaternary heterocyclic group containing a nitrogen atom ( For example, a pyridinio group), a hydroxy group, an alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a urethane Group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, (alkyl,
Aryl or heterocycle) thio group, mercapto group,
(Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonyluureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano Group, nitro group, phosphoric acid amide group and the like. Each of R ₁₁ , R ₁₂ and R ₁₃ is preferably a substituted or unsubstituted phenyl group, and more preferably, each of R ₁₁ , R ₁₂ and R ₁₃ is an unsubstituted phenyl group.

R ₁₄ represents a heteroaryloxy group or a heteroarylthio group. Specific examples of the heteroaryloxy group include a pyridyloxy group, a pyrimidyloxy group,
Examples include an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group, a furyloxy group, a thienyloxy group, a pyrazolyloxy group, and an imidazolyloxy group. Specific examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

A ₁ and A ₂ are both a hydrogen atom, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Ethoxalyl). Preferably, A ₁ and A ₂ are both hydrogen atoms.

In the general formula (H-2), R ₂₁ represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. Specific examples of the alkyl group include a methyl group, an ethyl group and a t-butyl group. Group, 2-octyl group, cyclohexyl group, benzyl group, diphenylmethyl group and the like. Specific examples of the aryl group and the heteroaryl group include the same groups as R ₁₁ , R ₁₂ and R ₁₃ . When R ₂₁ has a substituent, specific examples of the substituent include those similar to the substituents of R ₁₁ , R ₁₂ and R ₁₃ . R ₂₁ is preferably an aryl group or a heteroaryl group, and particularly preferably a substituted or unsubstituted phenyl group.

R ₂₂ represents hydrogen, an alkylamino group, an arylamino group, or a heteroarylamino group. Specific examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and a dimethylamino group. Examples include an amino group, a diethylamino group, and an ethylmethylamino group. As the arylamino group, an anilino group,
Examples of the heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. Preferably the R ₂₂ is dimethylamino group or diethylamino group.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2.

In the general formula (H-3), R ₃₁ and R ₃₂ represent a monovalent substituent, and examples of the monovalent substituent include R ₁₁ and R ₁₁ .
The groups exemplified as the substituents of R ₁₂ and R ₁₃ are exemplified, and preferably, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, and an amino group are exemplified. More preferably, it is an aryl group or an alkoxy group. Particularly preferred is that at least one of R ₃₁ and R ₃₂ is tert.
-Butoxy group, another preferred structure is
When R ₃₁ is a phenyl group, R ₃₂ is a tert-butoxy group.

G ₃₁ and G ₃₂ represent a — (CO) p— group, and —C (=
S)-, a sulfonyl group, a sulfoxy group, -P (= O) R
Represents a ₃₃ -group or an iminomethylene group, p represents an integer of 1 or 2, R ₃₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Represents an amino group. However, when G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. G ₃₁ and G ₃₂ are preferably -CO
—, —COCO—, sulfonyl or —CS—, more preferably —CO— or mutually sulfonyl.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2.

In formula (H-4), R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₁₁ , R ₁₂ and R ₁₃ in formula (H-1). Preferably, all of R ₄₁ , R ₄₂ and R ₄₃ are substituted or unsubstituted phenyl groups, and more preferably, all of R ₄₁ , R ₄₂ and R ₄₃ are unsubstituted phenyl groups. R ₄₄ and R ₄₅ represent an unsubstituted or substituted alkyl group, and specific examples include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, and a diphenylmethyl group. No. R ₄₄ and R ₄₅ are preferably each an ethyl group.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2.

The following formulas (H-1) to (H-
Specific examples of the compound represented by 4) will be given, but the present invention is not limited thereto.

[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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[0090]

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The compounds represented by the general formulas (H-1) to (H-
The compound represented by 4) can be easily synthesized by a known method. For example, US Pat. No. 5,464,73
No. 8 or U.S. Pat. No. 5,496,695.

Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in columns 11 to 20 of US Pat. No. 5,545,505 and column 9 of US Pat. No. 5,464,738. Compounds 1 to 12 described in Nos. 1 to 11. These hydrazine derivatives can be synthesized by a known method.

In the present invention, the following general formula [Na] is used in order to effectively promote the contrast enhancement by the hydrazine derivative.
It is preferable to use an amine compound represented by

[0094]

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In the general formula [Na], R ¹¹ , R ¹² , R
¹³ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ¹¹ , R ¹² and R ¹³ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable.

Preferred silver halide adsorptive groups include heterocyclic group-containing compounds, mercapto groups, thioether groups, thione groups, thiourea groups and the like. General formula [Na]
Particularly preferred are compounds having at least one thioether group as a silver halide adsorptive group in the molecule.

Specific examples of these amine compounds of the general formula [Na] will be given below.

[0098]

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[0099]

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[0100]

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[0101]

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Specific examples of other preferred amine compounds are described in JP-A-6-258755, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and “006” on page 15
7 ”to (16),“ 0068 ”(3-
1) to (3-6).

The above-mentioned amine compound preferably used in the present invention may be a photographic constituent layer on the side of a silver halide emulsion layer.
It may be used for any layer, and can be used in the same manner as the above-mentioned hydrazine derivative. Also, two or more kinds may be used in combination.

The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like, but is generally 10 ^-6 per mol of silver halide.
The range is preferably 10 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

The vinyl compound of the present invention has the general formula (G)
The compound represented by is described. In the general formula (G),
X represents an electron-withdrawing group, W represents a hydrogen atom, an alkyl group,
Alkenyl, alkynyl, aryl, heterocyclic, halogen, acyl, thioacyl, oxalyl, oxyoxalyl, thiooxalyl, oxamoyl, oxycarbonyl, thiocarbonyl, carbamoyl, thiocarbamoyl , Sulfonyl group, sulfinyl group, oxysulfinyl group, thiosulfinyl group, sulfamoyl group, oxysulfinyl group, thiosulfinyl group, sulfinamoyl group, phosphoryl group,
Nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group,
Represents an immonium group.

R represents a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group,
Organic or inorganic salts of an alkylthio group, an arylthio group, a heterocyclic thio group, an alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, a hydroxy group or a mercapto group (for example, sodium salt, potassium salt, silver salt) Etc.), an amino group, an alkylamino group, a cyclic amino group (for example, a pyrrolidino group), an acylamino group, an oxycarbonylamino group, a heterocyclic group (5-
A 6-membered nitrogen-containing heterocycle, for example, a benztriazolyl group,
Imidazolyl group, triazolyl group, tetrazolyl group, etc.), ureido group, and sulfonamide group. X and W,
X and R may be bonded to each other to form a cyclic structure. Examples of the ring formed by X and W include pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β-ketolactam and the like.

The general formula (G) will be further described.
The electron-withdrawing group represented by is a substituent whose substituent constant σp can take a positive value. Specifically, a substituted alkyl group (eg, halogen-substituted alkyl), a substituted alkenyl group (eg, cyanovinyl), a substituted / unsubstituted alkynyl group (eg, trifluoromethylacetylenyl, cyanoacetylenyl),
Substituted aryl group (cyanophenyl, etc.), substituted / unsubstituted heterocyclic group (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atom, cyano group, acyl group (acetyl, trifluoroacetyl, formyl, etc.), thioacetyl group (Thioacetyl, thioformyl, etc.), oxalyl group (methyloxalyl, etc.), oxyoxalyl group (ethoxalyl, etc.), thiooxalyl group (ethylthiooxalyl, etc.), oxamoyl group (methyloxamoyl, etc.), oxycarbonyl group (ethoxycarbonyl, etc.) , Carboxyl group, thiocarbonyl group (such as ethylthiocarbonyl),
Carbamoyl group, thiocarbamoyl group, sulfonyl group,
Sulfinyl group, oxysulfonyl group (ethoxysulfonyl, etc.), thiosulfonyl group (ethylthiosulfonyl, etc.), sulfamoyl group, oxysulfinyl group (methoxysulfinyl, etc.), thiosulfinyl group (methylthiosulfinyl, etc.), sulfinamoyl group, sphinamoyl group, phosphoryl Group, nitro group, imino group, N-carbonylimino group (N-acetylimino, etc.), N-sulfonylimino group (N-methanesulfonylimino, etc.), dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group And an immonium group, and a heterocyclic group in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, and the like form a ring is also included. A substituent having a σp value of 0.30 or more is particularly preferred.

The alkyl group represented by W is methyl, ethyl, trifluoromethyl and the like, the alkenyl group is vinyl, halogen-substituted vinyl, cyanovinyl and the like, the alkynyl group is acetylenyl and cyanoacetylenyl and the like. Examples of the group include nitrophenyl, cyanophenyl, and pentafluorophenyl, and examples of the heterocyclic group include pyridyl, pyrimidyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, and benzoxazolyl. W is σ
A p-value is preferably a positive electron-withdrawing group, and more preferably, the value is 0.30 or more.

Among the above substituents for R, hydroxy, mercapto, alkoxy, alkylthio,
Halogen atom, an organic or inorganic salt of a hydroxy group or a mercapto group, and a heterocyclic group, more preferably a hydroxy group, an alkoxy group, an organic or inorganic salt of a hydroxy group or a mercapto group, a heterocyclic group, Particularly preferred is an organic or inorganic salt of a hydroxy group, a hydroxy group or a mercapto group.

Of the substituents X and W, those having a thioether bond in the substituent are preferable.

Next, specific examples of the compound represented by formula (G) are shown below, but it should not be construed that the invention is limited thereto.

[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]

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[0134]

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[0135]

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In the general formula (P), Q represents a nitrogen atom or a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Note that R _{1 to} R
₄ may be connected to each other to form a ring.

Examples of the substituent represented by R _{1 to} R ₄ include an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like.

The ring which may be formed by linking R _{1 to} R ₄ includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

[0141] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0143]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, and an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group,
Represents a ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A ¹ , A ² , A ³ , A ⁴ and A
Preferred examples of ⁵ include a 5- to 6-membered ring (each ring of pyridine, imidazole, thiozole, oxazole, pyrazine, pyrimidine and the like), and more preferred examples include a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0148] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0149]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σp) indicating electron-withdrawing degree.

The Hammett's sigma value for the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
chemistry, 20, 304, 1977. The group having a particularly preferable negative sigma value is, for example, a methyl group (σp = −0.17 or less, σp value), and an ethyl group (−). 0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxy group (-0.37), methoxy group (-0.27), ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews vol. 55
p. 335-483 can be referred to.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, at least one photosensitive layer may be formed on the photosensitive layer.
Preferably, a non-photosensitive layer is formed. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer on the opposite side, a so-called backing layer, may be formed. Dyes or pigments may be included.

These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin.

In the photothermographic material of the present invention, various surfactants are used as a coating aid. Among them, a fluorine-based surfactant is preferably used for improving charging characteristics and preventing spot-like coating failure.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

Examples of suitable toning agents used in the present invention include:
Research Disclosure No. 17029
Issue.

The photothermographic material of the present invention contains a mercapto compound, a disulfide compound, and a thione compound for controlling development, improving spectral sensitization efficiency, and improving storage stability before and after development. be able to.

The photothermographic material of the present invention may contain an antifoggant. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. These additives and the other additives mentioned above are available from Research Disclosure It.
The compounds described in em17029 (pp. 9-15, June 1978) can be preferably used.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. , Polyethylene naphthalate).

Among them, a preferred support is a support of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene polymer having a syndiotactic structure. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

A heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, preferably an undercoat layer,
A backing layer, a layer between a photosensitive layer and an undercoat layer, and the like.

[0176]

EXAMPLES Example 1 (Preparation of PET support) PET pellets were
After drying for an hour, it was melted at 300 ° C., extruded from a T-die, and quenched to prepare an unstretched film. This was longitudinally stretched 3.0 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After this, 240 ° C
After heat setting for 20 seconds, the film was relaxed 4% in the horizontal direction at the same temperature. Thereafter, the chuck portion of the tenter was slitter, and both ends were knurled and wound at 4 kg / cm ² . Thus, a roll of a PET film having a width of 2.4 m, a length of 800 m and a thickness of 100 μm was obtained. 125μ
For a PET film support having a thickness of m, the film thickness of the unstretched film was adjusted, and the rest was performed in the same manner as in the preparation of the 100 μm film support. The glass transition point of any thickness PET was 79 ° C.

Biaxially stretched and heat-fixed thickness 100 μm, 110, 120, 150, 17 prepared as described above
A PET film support having a thickness of 5 μm is subjected to a corona discharge treatment of 8 W / m ² · min on both surfaces thereof, and the following undercoating solution a-1 is coated on one surface to a dry film thickness of 0.8 μm. It is applied and dried to form an undercoat layer A-1. On the opposite side, an undercoat coating liquid b-1 which has been subjected to an antistatic treatment as described below is applied so as to have a dry film thickness of 0.8 μm, dried and charged. Prevention processing was used as an undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g polystyrene fine particles (average particle diameter 3 μm) 0.05 g colloidal silica (average particle diameter 90 μm) 0 0.1 g Finished to 1 L with water << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) Styrene ( 20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g hexa Styrene-1,6-bis (ethyleneurea) subsequently finished into 1L with 0.8g water, the undercoat layer A-1 and the upper surface undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
The lower coating layer B-2 is coated with the following coating liquid b-2 on the lower coating layer B-1 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating solution a-2 for lower undercoat >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 L with water << Lower upper coating liquid b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5g (C-6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish to 1L with water

[0180]

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[0181]

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<< Heat Treatment of Support >> In the above-mentioned undercoat drying step of the five types of undercoated support, the support was heated at 140 ° C. and then gradually cooled.

(Preparation of silver halide emulsion A) 900 m of water
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and 370 ml of an aqueous solution containing 74 g of silver nitrate (60/3
The molar ratio of potassium iodide sodium chloride and potassium bromide and [Ir (NO) Cl _5] salt per mole silver 1 × 10 ^-6 mol and 1 mol of silver per 1 × rhodium chloride salt 8/2) 370 ml of an aqueous solution containing 10 ^-6 mol was added to pAg7.
While maintaining at 7, the addition was performed by the controlled double jet method. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene was added, the pH was adjusted to 8 with NaOH, and the pAg was adjusted to 6.5 to perform reduction sensitization. The average grain size was 0.06 μm, and the coefficient of variation of the projected diameter area with a monodispersity of 10% was 8%. Thus, cubic silver iodobromide grains having a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting, and then 0.1 g of phenoxyethanol.
Was adjusted to pH 5.9 and pAg 7.5 to obtain a silver halide emulsion A.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. After the adjustment, 147 ml of a 1M silver nitrate solution was added over 7 minutes, the mixture was further stirred for 20 minutes, and ultrafiltration was performed to remove water-soluble salts. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed with water six times and water was removed, and dried.

(Preparation of Photosensitive Emulsion) The preform emulsion thus prepared was divided into halves, and 544 g of a solution of polyvinyl butyral (average molecular weight: 3,000) in methyl ethyl ketone (17 wt%) and 107 g of toluene were gradually added and mixed. After that, 30 minutes at 4000 psi with a media disperser using a 0.5 mm size ZrO ₂ bead mill.
The dispersion was performed at 10 ° C. for 10 minutes.

The following layers were simultaneously coated on each of the five types of supports on both sides to prepare Samples 101 to 110 shown in Table 1. The drying was performed at 60 ° C. for 15 minutes.

(Back surface side coating) A liquid having the following composition was coated on layer B-1 of the support.

Cellulose acetate butyrate 15 ml / m ² (10% methyl ethyl ketone solution) Dye-A 7 mg / m ² Dye-B 7 mg / m ² Matting agent: monodispersity 15% Average particle size 8 μm monodisperse silica 90 mg / m ² _{C 8 F 17 (CH 2 CH} 2 O) 12 C 8 F 17 50mg / m 2 C 9 F 19 -C 6 H 4 -SO 3 Na 10mg / m 2

[0190]

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(Coating on Photosensitive Layer Side) A solution having the following composition was coated on the A-1 layer of the support so that the coated silver amount was 2.4 g / m ² .

The above photosensitive emulsion 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Oxidizing agent (10% methanol solution) 1.2 ml 2-4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml Hydrazine derivative H-1-1 0.4 g Vinyl compound 11-7 0.3 g Phthalazine 0.6 g 4-methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate having an average particle size of 3 μm 0.1 g 1,1- Bis (2-hydroxy-3,5-dimethylphenyl)- 2-methylpropane (20% methanol solution) 20.5 ml Isocyanate compound 0.5 g (Desmodur N3300 manufactured by Mobay Corporation)

[0193]

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(Coating of Surface Protective Layer) A solution having the following composition was simultaneously coated on the photosensitive layer.

[0195] Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Table 1 shows the polymer 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² Matting agent: monodisperse degree of 10% average particle size 4μm monodisperse silica 5mg _{^{/ m 2 CH 2 = CHSO 2}} CH 2 CH 2 OCH 2 CH 2 SO 2 CH = CH 2 35mg / m 2 fluorine-based surfactant _{C 12 F 25 (CH 2 CH} 2 O) 10 C 12 F 25 10mg / m Using a sample after forming a ² C ₈ F ₁₇ -C ₆ H ₄ -SO ₃ Na 10 mg / m ² coating film, removing the binder, and observing by an electron microscope observation using a replica method, the measurement was performed.
The organic silver salt particles have a monodispersity of 0.5 ± 0.05 μm in major axis, 0.4 ± 0.05 μm in minor axis, and 0.01 μm in thickness, and 90% of all organic silver salt particles. % Particles.

Each of the photothermographic materials produced above was rolled into a roll of 590 mm × 61 m, and packed in a bright room.

<< Exposure and development processing >> 780 n as a light source
1.5 × with a laser sensitometer using a semiconductor laser
Step exposure is performed while changing the amount of light in 10 ^-7 seconds.
The film was thermally developed at 0 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

The obtained developed sample was subjected to PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).
The following evaluation was performed using these.

Evaluation Method (Evaluation of Gamma) Gamma is represented by a tangent between densities of 0.1 and 3.0, and indicates that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

(Thermal Dimensional Change) The length of the sample before thermal development was measured after humidity control for 2 hours or more in an environment of 23 ° C. and 55% RH (L)
1) After performing heat development, the humidity was controlled for 2 hours or more in an environment of 23 ° C. and 55% RH, and the measurement was performed again (L2) to calculate a shrinkage ratio.

Thermal dimensional change rate = [100 × (L1-L2)
/ L1] Absolute value of 590 mm × 440 mm sheet was measured only on the side processed to 440 mm (the longitudinal direction of the roll).

If the thermal dimensional change exceeds 0.04%, the dimensional deviation after thermal development is so large that it is not suitable for practical use.

(Evaluation of Scratch Resistance) 590 mm × 61
One m-roll sample was processed, and the total number of blackening flaws generated was counted. Naturally, the smaller the number, the better. If it exceeds 8, it is a practically problematic level. Table 1 shows the results.

[0204]

[Table 1]

As is clear from Table 1, it can be seen that the form of the present invention has an ultra-high contrast, excellent dimensional stability, and good scratch resistance.

Example 2 A sample was prepared using a support having a thickness of 120 μm in the same manner as in Example 1 except that the toning agent was changed to that shown in Table 2 and the polymer of the surface protective layer was changed to polyvinyl formal. . The obtained sample was exposed in the same manner as in Example 1,
Thermal development was performed at the temperatures shown in Table 2, and the results are shown in Table 2.

[0207]

[Table 2]

As is clear from Table 2, it can be seen that the form of the present invention has an ultra-high contrast, excellent dimensional stability, and good scratch resistance.

Example 3 A photothermographic material was prepared in the same manner as in Example 1. However,
Preparation of support, undercoating, heat treatment of support and silver halide emulsion A were the same as in Example 1, except that the preparation of the organic fatty acid silver emulsion and the preparation of the photothermographic material were changed as follows. Sample No. of a roll-form photothermographic material 301
To 310 were produced.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
10.6 g of behenic acid was put therein, heated to 90 ° C., 31.1 ml of 1N sodium hydroxide was added with sufficient stirring, and left as it was for 1 hour. Then 30 ° C
Then, 7.0 g of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the above-prepared silver halide emulsion A was added with stirring while heating at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid.
Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

To the emulsion, polyvinyl butyral dissolved in ethyl acetate was added, and the mixture was sufficiently stirred and allowed to stand to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (spherical) manufactured by Tosoh Corporation and 22 cc of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 cc of isopropyl alcohol were added, and the mixture was sufficiently stirred at 35 ° C. at a high speed for dispersion to complete the preparation of the organic fatty acid silver emulsion.

Preparation of Photothermographic Material (Composition of Photosensitive Layer) Silver Emulsion of Organic Fatty Acid 1.75 g (in silver) / m ² Perfluoronium Human Perromit 1.5 × 10 ⁻⁴ mol / m ² Calcium Bromide 1.8 × 10 ⁻⁴ mol / m ² 2- (4-chlorobenzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² sensitizing dye 1 4.2 × 10 ⁻⁶ mol / m ² 2-mercaptobenzimidazole 3 0.2 × 10 ⁻³ mol / m ² 2-tribromomethylsulfonylquinoline 6.0 × 10 ⁻⁴ mol / m ² Hydrazine derivative H-1-1 0.4 g / m ² Vinyl compound 11-7 0.3 g / As the m ² solvent, methyl ethyl ketone, acetone, and methanol were appropriately used.

[0213]

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(Surface Protective Layer Composition) A surface protective layer coating solution was prepared as follows.

Cellulose acetate 2 g / m ² Polyvinylformal 2 g / m ² 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (developer, general formula (A) Exemplified compound A-4) 4.8 × 10 ⁻³ mol / m ² Phthalazine 3.2 × 10 ⁻³ mol / m ² 4-methylphthalic acid 1.6 × 10 ⁻³ mol / m ² Tetrachlorophthalic acid 7 9.9 × 10 ⁻⁴ mol / m ² Tetrachlorophthalic anhydride 9.1 × 10 ⁻⁴ mol / m ² Silicon dioxide (particle size: 2 μm) 20 mg / m ² Colloidal silica Suitable amount Solvent: methyl ethyl ketone, acetone, methanol Was used as appropriate.

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows.

Cellulose acetate 4 g / m ² Dye-A 0.06 g / m ² Dye-B 0.018 g / m ² Silicon dioxide (particle size: 10 μm) 50 mg / m ² Colloidal silica Appropriate amount Solvents include methyl ethyl ketone, acetone and methanol Was used as appropriate.

The photosensitive layer, the surface protective layer,
On the opposite side, a backing layer was applied to the support prepared as described above, and dried to obtain a roll-form photothermographic material.

<< Evaluation Method >> (Measured value of rise curl after processing) After the obtained photothermographic material was cut into a size of 455 mm × 588 mm, the entire surface was exposed to light and exposed to light.
Using an automatic processor having a heat drum with a cylindrical diameter of
Heat development was performed at 10 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 55% RH (relative humidity).

Thereafter, the humidity was controlled for 3 hours under the condition of 23 ° C. and 55% RH, and the rising curl when the sample was placed flat on a flat table was measured. Those standing on the photosensitive layer side are indicated by +, and those standing on the backing layer side are indicated by-.

(Transport defect rate in automatic printing machine) Samples having different rising curls were prepared (adjusted by the amount of colloidal silica added), and a transport test was performed by an automatic printing machine NCP manufactured by Otoko Seisakusho. 100 at 23 ° C and 55% RH
After transporting 00 sheets, the defective transport rate was determined. A transport failure rate of 1% or more is not suitable for practical use.

(Rate of thermal dimensional change) Evaluation was made in the same manner as in Example 1.

Table 3 shows the results.

[0224]

[Table 3]

As is clear from Table 3, it can be seen that the embodiment of the present invention can improve the conveyance failure and the dimensional stability.

Example 4 The toning agent of Example 3 was changed to that shown in Table 4 and
A sample was prepared using a 0 μm support.

With respect to the obtained sample, 780 was used as a light source.
1.5 nm with a laser sensitometer using a semiconductor laser
Step exposure was performed while changing the amount of light at × 10 ⁻⁷ seconds, and the processing was performed in the same manner as in Example 3 except that the humidity during heat development was adjusted as shown in Table 4.

The obtained developed sample was subjected to PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

(Evaluation of gamma) Evaluation was performed in the same manner as in Example 1.

[0230]

[Table 4]

As is evident from Table 4, it can be seen that the embodiment of the present invention can improve the ultra-high contrast and improve the poor conveyance and dimensional stability.

[0232]

According to the present invention, there is provided a high-contrast photothermographic material having a small dimensional change due to heat development, high overlay accuracy, and excellent scratch resistance during exposure and / or development processing and a method for processing the same. A roll-type photothermographic material for printing plate making with super-high contrast, improved curl on the photosensitive layer side after development processing as a roll product, no transport failure, little dimensional change due to thermal development, and high overlay accuracy Material could be provided.

Claims (8)

[Claims] 1. A hydrazine derivative, a quaternary onium salt compound, an amine compound or a vinyl compound as a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a binder and a high contrast agent on a support. In a photothermographic material containing at least one compound, a polymer layer containing polyvinyl formal is provided on a layer containing an organic silver salt, and the thermal dimensional change at 120 ° C. for 30 seconds is 0%. 0.001% or more and 0.04% or less. 2. The thickness of the support of the photothermographic material is 1
2. The photothermographic material according to claim 1, wherein the thickness is 10 μm or more and 150 μm or less. 3. The photothermographic material according to claim 1, wherein a high-contrast image having a gamma of 10 or more is formed. 4. The heat-developable photographic material according to claim 1, wherein the temperature of the heat-development part is 100 ° C. or higher.
A method for processing a heat-developable photographic light-sensitive material, wherein the processing is performed by a heat developing machine at 50 ° C. or lower. 5. A hydrazine derivative, a quaternary onium salt compound, an amine compound or a vinyl compound as a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a binder and a high contrast agent on a support. In a roll-form photothermographic material for printing plate making containing at least one or more compounds, the rising curl on the photosensitive layer side after the development processing is 0 to 60 mm, and the thermal dimensional change at 120 ° C. for 30 seconds is less. A roll-form photothermographic material comprising 0.001% or more and 0.04% or less. 6. The roll-form photothermographic material according to claim 5, wherein the high contrast agent is at least one selected from hydrazine derivatives and vinyl compounds. 7. The support has a thickness of 110 μm or more and 150 μm or more.
7. The roll-form photothermographic material according to claim 5, wherein m is equal to or less than m. 8. The roll-form photothermographic material according to claim 5, wherein the humidity at the time of heat development is 10 to 10.
A method for processing a roll-form photothermographic material, wherein the material is processed at 60% RH.