JP2001330921A - Heat developable photosensitive material and image forming method using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material excellent in conveyability during processing in an automatic heat developing machine, free of the rise of fog after development and having improved stability under a change of development conditions, and to provide an image forming method using the photosensitive material. SOLUTION: The sensitivity of the heat developable photosensitive material containing silver halide, an organic silver salt and a reducing agent on the base has the relation of the inequality log(S0/S11)<0.7 (where S0 is sensitivity obtained by heat-developing the heat developable photosensitive material at 120 deg.C in 25 sec and S11 is sensitivity obtained by heat-developing the heat developable photosensitive material at 120 deg.C in 20 see). Sensitivity expresses the reciprocal of light exposure giving a density of 2.5 when the heat developable photosensitive material is heat-developed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material having excellent transportability in an automatic thermal processor, no fog increase after development, and improved stability under fluctuations in development conditions, and an image forming method thereof. About.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As this technique, for example, US Pat.
Nos. 52,904, 3,487,075 and D.I. "Dry Silver Photographic" by Morgan
Materials) "(Handbook of I
Managing Materials, MarcelDe
kker, Inc. 48, 1991), a photothermographic material containing an organic silver salt, photosensitive silver halide particles, a reducing agent and a binder on a support is known.

[0004] The photothermographic materials described above have a problem in raw storability, particularly at high temperatures, because a reducing agent is contained in the material. Also, since no fixing process is performed after thermal development,
There is a problem that fog increases with time.

As described above, in the photothermographic material, improvement of the above problems has been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material which has excellent transportability in an automatic thermal developing machine, has no fog increase after development, and has improved stability under fluctuations in development conditions. And an image forming method therefor.

[0007]

The above objects of the present invention have been attained by the following constitutions.

[0008] 1. A photothermographic material containing a silver halide, an organic silver salt and a reducing agent on a support, wherein the sensitivity is represented by the formula (1).

[0009] 2. A photothermographic material containing a silver halide, an organic silver salt and a reducing agent on a support, wherein the gamma value of the photothermographic material is represented by the formula (2).

[0010] 3. A photothermographic material containing a silver halide, an organic silver salt and a reducing agent on a support, wherein the maximum density of the photothermographic material is represented by the formula (3).

4. A photothermographic material containing a silver halide, an organic silver salt and a reducing agent on a support, wherein the sensitivity is represented by the formula (4).

5. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the gamma value has a relationship represented by the above formula (5).

6. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the maximum concentration of the photothermographic material is represented by the formula (6).

7. 7. The photothermographic material according to any one of the above items 1 to 6, wherein a hardening agent is contained in the constituent layer containing the organic silver salt.

[8] 8. The photothermographic material according to any one of the above items 1 to 7, wherein the constituent layer on the side containing the organic silver salt contains an acid anhydride.

9. The composition layer on the side containing an organic silver salt contains the compound represented by the general formula (1) or the general formula (2) according to claim 9, wherein The photothermographic material according to the above.

10. The equilibrium water content of the photothermographic material is 2
10. The photothermographic material according to any one of the above items 1 to 9, wherein the content is within mass%.

11. 11. An image forming method, comprising: exposing the photothermographic material according to any one of the above items 1 to 10 and performing a heat development process to form an image.

Hereinafter, the present invention will be described in more detail. In the present invention, the term "development temperature and development time" means a temperature obtained by heating the photothermographic material of the present invention at a predetermined temperature for a predetermined time when an oven is heated to a predetermined temperature.

In order to satisfy the above-mentioned expressions (1) to (6), the present invention can be achieved by combining the following means.

1) The equilibrium water content of the photothermographic material is within 2% by mass 2) The silver halide grains contain silver halide grains of less than 0.01 μm 3) The average grain size of the organic silver salt is 2 μm or less and containing monodisperse tabular grains 4) Containing a high contrast agent on the image forming layer side 5) Containing an acid anhydride on the image forming layer side 6) General on the image forming layer side It contains a compound represented by the formula (1) or (2). The equilibrium water content (D) of the photothermographic material is 25 ° C., 60 ° C.
It is expressed by the following formula using the mass W of the photothermographic material and the moisture content w of the photothermographic material which are in the humidity control equilibrium under the atmosphere of% RH.

D (% by mass) = (w / W) × 100 In the present invention, the equilibrium water content of the photothermographic material at 25 ° C. and 60% RH is preferably 2% by mass or less.
More preferably 0.005 mass% or more and 2 mass% or less,
More preferably, the content is 0.01% by mass or more and 1% by mass or less.

The equilibrium water content of 2% by mass or less can be achieved by coating with an organic solvent having a water solubility of 2% by mass or less. Specific examples of the organic solvent include benzene, toluene, xylene, hexane, cyclohexane, diethyl ether, diisopropyl ether, hydrofluoroether, methylene chloride, chloroform, and trichloroethylene. The organic solvent having a water solubility of 2% by mass or less may be used alone or in combination. Further, as long as the water content of the coating solution satisfies the condition of 2% by mass or less, it may be used in combination with a water-miscible solvent described below.
As another method, using a water-miscible solvent, the equilibrium water content of the polymer latex described below at 25 ° C. and 60% RH is 0.01% by mass or more and 2% by mass or less, more preferably 0% by mass or less. It can be achieved by using a material having a content of 0.01% by mass or more and 1% by mass or less. For the definition and measurement method of the equilibrium moisture content, for example, “Polymer Engineering Course 14, Polymer Material Testing Method (edited by the Society of Polymer Science, Jinjinshokan)” can be referred to. As still another method, after coating and drying the photothermographic material, it is stored in a packaging form in which a desiccant for removing moisture is enclosed and covered with a packaging material impermeable to water.
The drying agent for removing moisture is not particularly limited as long as the moisture is removed by contact, and examples thereof include silica gel, molecular sieves, anhydrous magnesium sulfate, anhydrous sodium sulfate, pure iron, and iron compounds.
More preferably, it is silica gel.

The actual measurement of the equilibrium moisture content is performed by the following method. After the photothermographic material is conditioned for 24 hours in an environment of 25 ° C. and 60% RH, a film area of 46.3 cm ² is cut out under the same atmosphere, the mass is measured, and this is finely cut into about 5 mm. After storing in a dedicated vial and sealing with a septum and aluminum cap,
Packard Headspace Sampler HP7694
Set in the mold. 120 headspace samplers
The mixture was heated at 20 ° C. for 20 minutes, and the evaporated water was quantified by the Karl Fischer method.

In the present invention, the particle size is 0.01 μm
It is preferable to contain silver halide grains of less than 0.0005 to 0.01 μm. 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. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. In order to further provide photosensitivity, it is preferable to have silver halide grains having a grain size of 0.01 μm to 0.1 μm.

As a method for producing the silver halide grains having a grain size of less than 0.01 μm, a silver halide forming component is added to a previously prepared solution or dispersion of an organic silver salt or a sheet material containing the organic silver salt. It is preferably used to convert a part of the organic silver salt into photosensitive silver halide. The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action.
A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak specific to silver halide. Silver halide-forming components confirmed to be effective by such a test include inorganic halides, onium halides, halogenated hydrocarbons, N-
There are halogen compounds and other halogen-containing compounds, and specific examples thereof are described in US Pat. No. 4,009,039.
Nos. 3,457,075 and 4,003,749, British Patent No. 1,498,956 and JP-A-53-270.
Nos. 27 and 53-25420, examples of which are shown below.

(1) Inorganic halide: for example, MX _n
(Where M represents H, NH ₄ and a metal atom, n represents 1 when M is H and NH ₄ , and represents its valency when M is a metal atom. Metal atom as,
Lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc,
Cadmium, mercury, tin, antimony, chromium, manganese, iron, cobalt, nickel, rhodium, cerium, etc.). Further, halogen molecules such as bromine water are also effective.

(2) Onium halides: For example, quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide and trimethylbenzylammonium bromide, and quaternary phosphoniums such as tetraethylphosphonium bromide There are halides and tertiary sulfonium halides such as trimethylsulfonium iodide.

(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like.

(4) N-halogen compound: For example, N-halogen compound
Chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazone, N-bromooxazolinone, N-chlorophthalazone, N-bromoacetanilide, N , N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide,
1,3-dibromo-4,4-dimethylhydantoin, N
-Bromourazole and the like.

(5) Other halogen-containing compounds: for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.

The particle size is 0.01 μm to 0.1 μm.
In order to prepare silver halide grains of m, aside from the organic silver grains, any method known in the field of photographic technology such as a single jet or double jet method may be used in advance. Silver halide grains can be prepared by any of the methods described above. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, U.S. Pat. Nos. 3,706,564 and 3,70 as protective polymers for preparing photosensitive silver halide.
6,565, 3,713,833 and 3,74
No. 8,143, British Patent No. 1,362,970, which uses a polymer other than gelatin such as polyvinyl acetal, and British Patent No. 1,354,186.
For enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in U.S. Pat.
By preparing photosensitive silver halide grains in the presence of a surfactant as described in US Pat.
Various means such as a means for omitting the use of the protective polymer can be applied. Particle size is 0.01μm ~ 0.1μ
It is preferred that the silver halide grains of m have photosensitivity and function as an optical sensor. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, or non-normal crystals, such as spherical, rod-shaped, or tabular grains. The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The amount of silver halide grains having a grain size of less than 0.01 μm is preferably 1% or more based on the total amount of silver halide grains, and more preferably 5% or more and 70% or less is 0.01 μm or less. It is particularly preferred that the number of silver halide grains is less than.

The photosensitive silver halide used in the photothermographic material of the present invention is also disclosed in British Patent No. 1,447,454.
As described in (1), when an organic silver salt is prepared, a halogen component such as a halide ion coexists with an organic silver salt forming component, and silver ions are implanted into the organic silver salt-forming component. Can be done.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is 0.001 to 0.7 mol, preferably 0.03 to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. However, usually, the reaction temperature is 20 to 70 ° C,
The reaction time is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure. This reaction also
It is preferably carried out in the presence of a polymer used as a binder described below. The amount of polymer used at this time is
The amount is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be achieved by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, US Pat. No. 4,036,650, British Patent 1,518,850, JP-A-51-22430,
Nos. 51-78319 and 51-81124. Also, when a part of the organic silver salt is converted to a photosensitive silver halide by a silver halide forming component, as described in U.S. Pat. An amide compound having a molecular weight may coexist.

In addition, these photosensitive silver halides are required to have illuminance failure and to adjust the gradation, so that the photosensitive silver halides of Group 6 to 10 of the periodic table can be used.
Metals belonging to group III, such as Rh, Ru, Re, Ir, O
It is preferable to contain ions such as s and Fe, complexes thereof and complex ions. In particular, it is preferable to add as a complex ion. For example, it is preferable to add an Ir complex ion such as [IrCl ₆ ] ²⁻ because of illuminance failure.

The photosensitive silver halide grains in the present invention may be chemically sensitized. Preferred chemical sensitization methods include
As is well known in the art, a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, a noble metal sensitization method such as a gold compound, platinum, palladium, and iridium compound and a reduction sensitization method can be used. . As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent No. 618,061. The compounds described in, for example, can be preferably used. Specific compounds for the reduction sensitization method include, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like. it can. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

In the present invention, the organic silver salt is a reducible silver source, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10 to 30, preferably 15 to 30). Aliphatic carboxylic acids having up to 25 carbon atoms) and nitrogen-containing heterocycles are 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 (hereinafter referred to as RD) No. 17
029 and 29996, and include the following.

Salts of organic acids (for example, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid and the like); carboxyalkylthiourea salts of silver (for example, 1- (3-carboxy) Propyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, Butyraldehyde), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid)), silver salts or complexes of thiones (eg, 3- (2-carboxy) Ethyl) -4
-Hydroxymethyl-4- (thiazoline-2-thione,
And 3-carboxymethyl-4-thiazoline-2-thione)), imidazole, pyrazole, urazole, 1,
Complexes or salts of silver with a nitrogen acid selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides. Of these, preferred silver sources are silver behenate, arachidic acid and / or stearic acid.

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 normal 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.

In the present invention, the organic silver salt has an average particle size of 2 μm.
m or less and monodispersion. Here, the monodispersion means that the degree of dispersion obtained by the following equation is 50%.
Refers to the following. The particle size is more preferably 40% or less, and particularly preferably 0.1% or more and 35% or less.

The degree of dispersion (%) = (standard deviation of particle size) / (average value of particle size) × 100 The average particle size of the organic silver salt means that the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular. In the case of the particles of the above, the diameter refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles. The average particle size is preferably 0.05 to 1.5 μm, particularly 0.05 to 1.5 μm.
1.0 μm is preferred. Further, in the organic silver salt of the present invention, it is preferable that 60% or more of the total organic silver salt is tabular grains. In the present invention, the tabular grains refer to the ratio of the average grain size to the thickness, that is, the aspect ratio (AR
Abbreviation) means three or more.

AR = average particle size (μm) / thickness (μm) In order to form the organic silver salt into these shapes, the organic silver salt crystal is dispersed and pulverized together with a binder, a surfactant and the like by a ball mill or the like. Obtained by: Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the photothermographic material, the total amount of silver halide and organic silver salt is converted to silver and is 0.5 g or more and 2.2 g or less per m ^2. It is preferred that

In order to more effectively exhibit the effects of the present invention, it is preferable that a layer on the image forming layer side of the photothermographic material contains a high contrast agent. As the high contrast agent, it is preferable to include at least one of a hydrazine derivative, a vinyl compound, and a quaternary onium compound. The vinyl compound is represented by the following general formula (G), and the quaternary onium compound is represented by the following general formula (P).

[0047]

Embedded image

In the general formula (G), X and R are represented in the form of cis. However, the general formula (G) also includes the form in which X and R are trans. 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].

[0050]

Embedded image

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 examples of D ₀ include a hydrogen atom, an alkyl group, an alkoxy group, and an amino group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl group, cyclohexyl group, benzyl group, and the like, and further suitable substituents (for example, aryl group,
Alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamido, sulfamoyl, acylamino, ureido, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, such as 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.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or 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 And a phenoxy group, an alkylphenoxy group, and the like. 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.

[0058]

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[0059]

Embedded image

More preferred hydrazine derivatives are represented by the following general formulas (H-1), (H-2), (H-3) and (H-
4) and (H-5).

[0061]

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In the general formula (H-1), R₁₁, R₁₂Passing
And R₁₃Is independently substituted or unsubstituted aryl
Represents a group or a heteroaryl group.
Specifically, for example, phenyl, p-methylphenyl, na
Futil and the like. As a heteroaryl group,
Physically, triazole residues, imidazole residues,
Residues, furan residues, thiophene residues, etc.
You. Also, R₁₁, R₁₂And R₁₃Is any linking group
May be combined via R₁₁, R₁₂And R₁₃Is a substituent
When having, as the substituent, for example, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group,
Heterocyclic group containing quaternized nitrogen atom, hydroxyl
Group, alkoxy group (ethyleneoxy group or propylene
Oxy group unit)
Xy, acyloxy, acyl, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
Group, urethane group, carboxyl group, imide group, amino
Group, carbonamido group, sulfonamido group, ureido
Group, thioureido group, sulfamoylamino group, semica
Rubazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium groups, (alkyl, aryl, or
Terrorist ring) thio group, mercapto group, (alkyl or ant
)) Sulfonyl group, (alkyl or aryl) sulf
Finyl group, sulfo group, sulfamoyl group, acyl sulf
Famoyl group, (alkyl or aryl) sulfoni
Luureido group, (alkyl or aryl) sulfoni
Rucarbamoyl group, halogen atom, cyano group, nitro
Group, phosphoric acid amide group and the like. R ₁₁, R₁₂as well as
R₁₃Are preferably substituted or unsubstituted
And more preferably R₁₁, R₁₂And R
₁₃Is 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, an indolyloxy group, a benzothiazolyloxy group,
Examples include 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 hydrogen atoms, 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, etc.). ). 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 those similar to 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. R ₂₂ is preferably a dimethylamino group or a diethylamino group. A ₁ and A ₂ are represented by the general formula (H
The same as A ₁ and A ₂ described in -1).

In the general formula (H-3), R ₃₁ and R ₃₂ each 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.

G₃₁, G₃₂Is a -CO- group, -COCO-
Group, -C (= S)-, sulfonyl group, sulfoxy group,-
P (= O) R₃₃-Or an imino methylene group;₃₃
Is an alkyl group, alkenyl group, alkynyl group, aryl
Group, alkoxy group, alkenyloxy group, alkynylo
Represents an xy group, an aryloxy group, or an amino group. Where G
₃₁Is a sulfonyl group, G₃₂Is not a carbonyl group
No. G₃₁, G₃₂Is preferably a -CO- group, -CO
CO-, sulfonyl or -CS-, more preferably
Preferably they are -CO- groups or sulfonyl groups each other.
is there. A₁, A_TwoIs A described in the general formula (H-1)₁, A_Two
Is the same as

In the general formula (H-4), R₄₁, R₄₂You
And R₄₃Is R in general formula (H-1)₁₁, R₁₂And
And R₁₃Is synonymous with R₄₁, R₄₂And R₄₃As preferred
Or both are substituted or unsubstituted phenyl groups.
And more preferably R₄₁, R ₄₂And R₄₃None of
It is a substituted phenyl group. R₄₄, R₄₅Is unsubstituted or replaced
Represents a substituted alkyl group, but specific examples include a methyl group,
Ethyl group, t-butyl group, 2-octyl group, cyclohexyl
A sil group, a benzyl group, a diphenylmethyl group and the like.
You. R₄₄, R₄₅Are preferably ethyl groups
You. A₁, A_TwoIs A described in the general formula (H-1)₁, A_TwoWhen
The same is true.

In the general formula (H-5), R ₅₁ represents a monovalent substituent, and the structure of R ₅₁ is optional, but is preferably an alkyl group, a phenyl group, a nitrogen-containing heterocyclic group, or a sulfur-containing heterocyclic group. Is mentioned. Specific examples of R ₅₁ include alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group and nonyl group, cyclopentyl group, cyclohexyl Groups such as cycloalkyl group, phenyl group, substituted phenyl group, naphthyl group, maleimide group, phthalimide group, succinimide group, morpholino group, piperidyl group, pyridyl group, heterocyclic group such as tenoyl group, trityl group, ethoxycarbonyl group, Examples thereof include a methylthiomethyl group, a diisopropylamino group and a diphenylamino group, and these substituents may be further substituted.

The general formulas (H-1) to (H) of the present invention are described below.
Specific examples of the compound represented by -5) are shown below, but the present invention is not limited thereto.

[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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The compounds represented by the general formulas (H-1) to (H-
The compound represented by 5) can be easily synthesized by a known method. For example, US Pat. No. 5,464,7
No. 38 and 5,496,695 can be synthesized.

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 general formula (G), X represents an electron-withdrawing group, W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom,
Acyl group, thioacyl group, oxalyl group, oxyoxalyl group, thiooxalyl group, oxamoyl group, oxycarbonyl group, thiocarbonyl group, carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, thiosulfonyl group, sulfamoyl Group, oxysulfinyl group, thiosulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group,
An N-carbonylimino group, an N-sulfonylimino group, a dicyanoethylene group, an ammonium group, a sulfonium group,
Represents a phosphonium group, a pyrylium group, or an immonium group.

R represents a halogen atom, a hydroxyl 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, an alkylthio group, an arylthio group, Organic or inorganic salts of ring thio group, alkenylthio group, acylthio group, alkoxycarbonylthio group, aminocarbonylthio group, hydroxyl group or mercapto group (for example, sodium salt, potassium salt, silver salt, etc.), amino group, alkyl Amino group, cyclic amino group (for example, pyrrolidino group), acylamino group, oxycarbonylamino group, heterocyclic group (5 to 6-membered nitrogen-containing heterocycle, for example, benztriazolyl group, imidazolyl group, triazolyl group, tetrazolyl group Etc.), ureido groups, It represents a Ruhon'amido group. X and W, and X and R may be bonded to each other to form a cyclic structure. The ring formed by X and W includes, for example, pyrazolone, pyrazolidinone, cyclopentanedione, β-
Ketoractone, 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, 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, immonium group, but heterocyclic ring in which ammonium group, sulfonium group, phosphonium group, immonium group, etc. form a ring Also included. σp
Substituents having a value of at least 0.30 are particularly preferred.

Examples of the alkyl group represented by W include methyl, ethyl, trifluoromethyl and the like, examples of the alkenyl group include vinyl, halogen-substituted vinyl and cyanovinyl, and examples of the alkynyl group include acetylenyl and cyanoacetylenyl. Examples of the aryl 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, preferred are hydroxyl, mercapto, alkoxy, alkylthio, halogen, hydroxyl or mercapto organic or inorganic salts, and heterocyclic groups. Examples include an organic or inorganic salt of a hydroxyl group, an alkoxy group, a hydroxyl group or a mercapto group, and a heterocyclic group, and particularly preferably an organic or inorganic salt of a hydroxyl group, a hydroxyl group or a mercapto group.

Among the substituents of 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.

[0087]

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[0088]

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[0089]

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[0090]

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[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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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.

As the substituent represented by R _{1 to} R ₄ , 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.

[0111] 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 formula (Pa):
A compound represented by (Pb) or (Pc); and a compound represented by the following general formula [T].

[0113]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, which 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 carboxyl group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, 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 preferred examples of A ⁵ are, 5-6 membered ring can be mentioned (pyridine, imidazole, Chiozoru, oxazole, pyrazine, each ring of the pyrimidine, and the like), 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.

R¹, R^TwoAnd R^FiveAre each having 1 to 20 carbon atoms
Represents an alkyl group. Also, R¹And R ^TwoAre the same but different
May be. An alkyl group is a substituted or unsubstituted alkyl group.
Represents a kill group, and the substituent is A¹, A^Two, A^Three, A^FourPassing
And A^FiveAre the same as the substituents exemplified as the substituent of

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.

[0118] 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 counterions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0119]

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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 has been reported 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, hereinafter referred to as a σp value), an ethyl group ( -0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), i
So-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 include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid root 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.

[0124]

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[0125]

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[0126]

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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 synthesized in Chemical Reviews vol. 55
p. 335-483 can be referred to. The amount of the above-mentioned toning agent is in the range of 10 ^-5 to 1 mol, preferably 10 ^{-4 to} 5 × 10 ^-1 mol, per 1 mol of the organic silver salt.

The acid anhydrides usable in the present invention include those in which two molecules of a monocarboxylic acid are dehydrated and condensed to have an A-CO-O-CO-B structure in the molecule. It may be a substituent having a molecular structure like a ring, or a substituent having a cyclic structure in which A and B are partially bonded. The linear one is formed by dehydration of two molecules of aliphatic monocarboxylic acid, such as acetic anhydride, propanoic anhydride, butanoic anhydride, amylic anhydride, caproic anhydride, lauric anhydride, stearic anhydride. Examples thereof include acids, sebacic anhydride, arachidic anhydride, and behenic anhydride, and the aliphatic carboxylic acid preferably has 1 to 30 carbon atoms. Examples of the cyclic structure include aromatic carboxylic acids, for example, benzoic anhydride, pyridine carboxylic anhydride, or acid anhydrides represented by the general formulas (3) and (4), including derivatives thereof. Is mentioned. In the present invention, acid anhydrides represented by the following general formulas (3) and (4) are preferable as the acid anhydride having a cyclic structure.

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In the general formula (3), Z ₁ and Z ₂ each represent a group of atoms constituting an acid anhydride nucleus, and R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom (a chlorine atom, a fluorine atom, etc.), a nitrile Group, hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, butoxy group) or an aliphatic group, an aromatic group, or a heterocyclic group which may have a substituent;
Represents an integer of 4, and when n is 2 or more, adjacent substituents may form a condensed ring. L ¹¹ represents a divalent linking group that links the Z ₁ and Z ₂ rings.

The atomic group constituting the acid anhydride nucleus in Z ₁ and Z ₂ is a saturated or unsaturated ring or hetero ring having 4 to 12 carbon atoms, and a carboxylic acid group on the ring is adjacent to the saturated or unsaturated ring or hetero ring. It is a condensed one, and represents a hexyl ring and a benzene ring as a saturated ring, a benzene ring and a naphthalene ring as an unsaturated ring, and a pyridine ring, an imidazole ring, a pyrimidine ring, an oxazole ring, a triazole ring and the like as a hetero ring.

Examples of the aliphatic group which may have a substituent in R ¹¹ and R ¹² include an alkyl group such as a methyl group, an ethyl group and a butyl group, an ethylene group, a propylene group, a butylene group,
Alkenyl groups such as octene group, alkyne groups such as acetylene group and biacetin group, ethyl, sulfonamide group, octyl sulfonamide group, ethyl carbamide group, butyl carbamide group and the like.Also, as the aromatic group, phenyl group, A naphthyl group further has an alkyl group (methyl group, ethyl group, butyl group, octyl group, etc.), an alkenyl group (ethylene group, butylene group, octene group, etc.), a halogen atom (chlorine atom, bromine atom, fluorine atom) on the ring. Etc.), a nitrile group, an alkoxy group (a methoxy group, an ethoxy group, etc.), a hydroxyl group and an amino group, and the heterocyclic group includes a pyridine ring, a pyrimidine ring, an imidazole ring, a triazole ring, and an oxazole ring. , A thiazole ring,
Examples include a furan ring and a thiophene ring.

The substituents R ¹¹ and R ¹² on Z ₁ and Z ₂ are n
Is 2 or more, adjacent substituents may form a ring.

As the substituent which may be substituted on R ¹¹ and R ¹² , an optionally substituted alkoxy group (a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, an octoxy group, a dodecanooxy group, a docosanoxy group, -Ethylhexanoxy group), halogenated alkoxy groups (trifluoromethoxy group, perfluorooctanoxy group), cycloalkoxy groups (cyclohexanoxy group, cyclooctanoxy group, cyclopentanoxy group, etc.), aromatic Group (phenoxy group, naphthenoxy group, etc.), heterocyclic group (pyridyl group, furyl group, thiophenyl group, piperazyl group, imidazolyl group, triazole group, tetrazole group, etc.), alkylamino group (methylamino group, propylamino group, Octylamino group, tetradecyl group), dialkylamino group (dimethylamino , Diethylamino group, di-octyl amino group), an alkylthio group (methylthio group, ethylthio group, butylthio group, octylthio group), with the alkyl group moiety preferably have 1 to 25 carbon atoms. When the adjacent substituents R ¹¹ and R ¹² form a ring, examples of the ring include a benzene ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a furyl ring, a thiophene ring, and a piperazine ring.

L ¹¹ represents a —SO ₂ — group, a —SO— group, a —S—S
O ₂ —, —S—, —O—, —CONH—, —SO ₂ NH
-, -CONH- group or these and an aliphatic group, an aromatic group,
Combinations of heterocyclic groups and the like can be given.

In the general formula (4), Z represents an atom group necessary for forming a monocyclic or polycyclic system. These ring systems may be unsubstituted or substituted. Examples of the substituent include an alkyl group (for example, methyl, ethyl, hexyl), an alkoxy group (for example, methoxy, ethoxy,
Octyloxy), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxy group, an aryloxy group (eg, phenoxy), an alkylthio group (eg, methylthio, butylthio), an arylthio group (eg, phenylthio), an acyl group (eg, Acetyl, propionyl, butyryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group, sulfonylamino group, acyloxy group (eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, halogen group (eg, Chloro, bromo) and amino groups.

Preferred examples of the acid anhydrides represented by formulas (3) and (4) are shown below.

[0138]

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[0139]

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[0140]

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[0141]

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As the acid anhydride, a compound having a carboxylic acid group can be synthesized by ordinary dehydration condensation, or a commercially available product can be obtained. Also, when added to the heat developing material,
It can be added according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion, or homogenizer dispersion, and then added. Many techniques have been disclosed for fine particle dispersion techniques, and the average particle size is 0.05 to 1 according to these techniques.
A fine particle dispersion of 0 μm can be added.

In the present invention, the layer adjacent to the photosensitive layer preferably contains the acid anhydrides represented by the above formulas (3) and (4).

In the general formulas (1) and (2), the divalent linking group comprising an aliphatic hydrocarbon group represented by T ₁ is a straight-chain, branched or cyclic alkylene group (preferably having 1 to 1 carbon atoms). 20, more preferably 1 to 16, still more preferably 1 to 12, an alkenyl group (preferably having 2 to 2 carbon atoms).
0, more preferably 2 to 16, even more preferably 2 to 1
2) an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 12 carbon atoms), and may have a substituent.

Examples of the divalent linking group containing at least one oxygen atom, sulfur atom or nitrogen atom represented by J ₁ include the following. Also, a combination of these may be used.

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In the formula, Re and Rf each represent Ra to
This is synonymous with the content defined for Rd. The aromatic hydrocarbon group represented by Ar is preferably a monocyclic or condensed aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among them, a phenyl group is particularly preferably used.

The aromatic heterocyclic group represented by Ar includes a group containing at least one atom of N, O and S.
And a 10-membered unsaturated heterocyclic group. The heterocyclic ring in these groups may be a single ring or may form a condensed ring with another ring. The heterocyclic ring in such a heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic ring and a benzo-fused ring thereof, and more preferably a 5- or 6-membered heterocyclic ring containing a nitrogen atom.
Or a 6-membered aromatic heterocyclic ring and a benzo-fused ring thereof, and more preferably a 5 to 6-membered heterocyclic ring containing 1 to 2 nitrogen atoms.
And a 6-membered aromatic heterocycle and a benzo-fused ring thereof.

Specific examples of the aromatic heterocyclic group include, for example, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, Phthalazine, naphthyridine, quinoxaline, quinazoline,
Examples include groups derived from cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, benzothiazoline, benzotriazole, tetrazaindene, carbazole, and the like.

In the above description, imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phenazine, tetrazole, thiazole, oxazole,
A group consisting of benzimidazole, benzoxazole, benzothiazole, benzothiazoline, benzotriazole, tetrazaindene, carbazole is preferred, and more preferably imidazole, pyridine, pyrazine, quinoline, phenazine, tetrazole, thiazole, benzoxazole, benzimidazole, Examples include groups derived from benzothiazole, benzothiazoline, benzotriazole, and carbazole.

The aromatic hydrocarbon group and the aromatic heterocyclic group represented by Ar may have a substituent, and examples of the substituent include those similar to the groups exemplified as the substituent for T _1. And the preferred range is also the same. These substituents may be further substituted, and when there are two or more substituents, each may be the same or different.

Further, an aromatic heterocyclic group is preferably used as the group represented by Ar.

As the aliphatic hydrocarbon group represented by Ra, Rb, Rc, Rd, Re and Rf, a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms)
More preferably 1 to 16, more preferably 1 to 12, an alkenyl group (preferably having 2 to 20, more preferably 2 to 16, and still more preferably 2 to 12), an alkynyl group (preferably Having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 12 carbon atoms)
Wherein the aryl group is a monocyclic or condensed aryl group having 6 to 20 carbon atoms (for example, phenyl, naphthyl, etc., preferably phenyl), and the heterocyclic group is 3 to 10 membered. A saturated or unsaturated heterocyclic group (e.g., 2-thiazolyl, 1-piperazinyl, 2-pyridyl, 3-pyridyl, 2-furyl, 2-thienyl, 2-benzimidazolyl, carbazolyl, etc.). The heterocyclic ring therein may be a single ring or may form a condensed ring with another ring.

The acyl group represented by each of Ra, Rb, Rc, Rd, Re and Rf is an aliphatic or aromatic group having 1 to 12 carbon atoms, specifically, acetyl, benzoyl, formyl, And groups such as pivaloyl.

The nitrogen-containing heterocyclic group formed by bonding between Ra and Rb, Rc and Rd, Ra and Rc or Rb and Rd is a 3- to 10-membered saturated or unsaturated heterocyclic group (for example, piperidine Ring, piperazine ring, acridine ring, pyrrolidine ring, pyrrole ring, morpholine ring and the like).

Specific examples of the acid anion used as an ion necessary to neutralize the intramolecular charge represented by M ₁ include, for example, a halogen ion (eg, a chloride ion, a bromine ion, an iodine ion), Toluenesulfonate, perchlorate, boron tetrafluoride, sulfate, methylsulfate, ethylsulfate, methanesulfonate, trifluoromethanesulfonate and the like can be mentioned.

Specific examples of the compounds represented by formulas (1) and (2) are shown below, but the present invention is not limited thereto.

[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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As the compounds represented by formulas (1) and (2) according to the present invention, commercially available compounds may be used, or they can be synthesized by referring to known methods. For example, The Chemical Society of Japan, New Experimental Chemistry, Vol. 14 (III) 1739-1
It can be synthesized by the method described on page 741 (1978) and the like.

The compounds represented by formulas (1) and (2) according to the present invention can be added to the photothermographic material of the present invention in either the photosensitive layer or the non-photosensitive layer.
The photosensitive layer, which is preferably an image forming layer, is preferably used as the additive layer.

The compounds represented by the general formulas (1) and (2) according to the present invention vary depending on the desired purpose, but are expressed in terms of the amount added per mol of Ag, from 10 ^-4 to 1 mol / Ag, preferably from 10 to ⁴ mol / Ag. ^{-3 to} 0.3 mol / Ag, more preferably 10 ^-3
It is preferable to add ０．１0.1 mol / Ag.

The compounds of the general formulas (1) and (2) may be used alone or in combination of two or more.
Compounds of the general formulas (1) and (2) are prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethylformamide, dimethyl It can be used by dissolving it in sulfoxide, methyl cellosolve and the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder can be dispersed in water by a method known as a solid dispersion method using a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves. When dispersing the solid fine particles, a dispersing aid may be used.

The photothermographic material of the present invention has at least one image forming layer on a support. Although only the image forming layer may be formed on the support, it is preferable to form at least one non-image forming layer on the image forming layer. In order to control the amount or wavelength distribution of light passing through the image forming layer, a filter dye layer on the same side as the image forming layer and / or an antihalation dye layer on the opposite side, a so-called backing layer may be formed, The image forming layer may contain a dye or a pigment. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range. Examples thereof include JP-A-59-6481 and JP-A-59-182436, and U.S. Pat. No. 4,271,263.
No. 4,594,312, European Patent Publication 533,0
08, European Patent Publication 652,473, JP-A-2-2-2
No. 16140, No. 4-348339, No. 7-1914
Compounds described in Nos. 32 and 7-301890 are preferably used.

These non-image forming 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. The image forming layer may have a plurality of layers, and the image forming layer may have a high sensitivity layer / low sensitivity layer or a low sensitivity layer / high sensitivity layer for adjusting the gradation.

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. It is preferable that the photothermographic material usually contains a color tone agent which suppresses the color tone of the present invention in a state of being dispersed in a (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is exposed to high temperature (for example, 80 to 14).
(0 ° C.). Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This redox reaction is
It 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 provides a black image, which contrasts with the unexposed areas to form an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention contains a reducing agent. Examples of suitable reducing agents are described in U.S. Pat.
0,448, 3,773,512, 3,59
No. 3,863 and RD17029 and 29963, and include the following.

Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (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-tetrahydro) Amide oximes; azines (for example, a combination of an aliphatic carboxylic 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; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, 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).

[0172]

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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.

[0175]

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

In the photothermographic material of the present invention, it is desirable to use an additive (hereinafter referred to as a color tone agent) called a color tone agent, a color tone imparting agent or an activator toner together with the above-mentioned components. The color tone agent participates in the oxidation-reduction reaction between the organic silver salt and the reducing agent, and has a function of making the resulting silver image dark, particularly black. Examples of suitable toning agents for use in the present invention are disclosed in RD17029 and include the following.

Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2 , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Of these, phthalazone or phthalazine is preferred as a color tone agent.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175, and 4,835. No. 096 can be used. Useful sensitizing dyes for use in the present invention include, for example, RD
17643 IV-A (p. 23, December 1978) and Item 1831X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-80
No. 679 is preferably used.

In the case of supersensitization, the photosensitivity becomes particularly high. If the reducing agent is not deactivated, the printout silver after development tends to be large, which is particularly effective for the present invention. In the case of infrared sensitization, the infrared sensitizing dye further has a redox potential capable of reducing silver halide or an organic silver salt to some extent. In the presence of a reducing agent that can reduce the organic silver salt, silver clusters that become fogged silver are easily formed. The generated silver clusters also act as catalyst nuclei and induce fog, so that when stored in a dark place, the storage stability decreases,
Further, when exposed to a light place after development, a phenomenon such as an increase in printout silver occurs. Further, the sensitivity of the infrared-sensitive material extends to a heat radiation region outside the range of visible light, so that it is effective in increasing printout silver by heat radiation even in a dark place. In particular, in the case of a photothermographic material which has been enhanced in sensitivity by a supersensitizer and which has been subjected to infrared spectral sensitization, the effect is large.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD17643 (issued in December 1978), No. 2.
Section J on page 3, IV, or Japanese Patent Publication No. 9-25500, 4
3-4933, JP-A-59-19032, and JP-A-59-19032.
192,242 and JP-A-5-341432.

In the present invention, a heteroaromatic mercapto compound represented by the general formula (5) is preferred as a supersensitizer.

Formula (5) Ar-SM In the formula, M is a hydrogen atom or an alkali metal atom;
r is a heteroaromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably,
Benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotetrazole, imidazole, oxazole, pyrazole, triazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, pudding, quinoline or quinazoline .

The present invention also includes a disulfide compound which, when contained in a dispersion of an organic silver salt and / or silver halide grain emulsion, substantially forms the above-mentioned mercapto compound. In particular, a disulfide compound represented by the following general formula can be mentioned as a preferred example.

Ar in the formula (6) Ar-SS-Ar has the same meaning as in the formula (5).

The above heteroaromatic ring includes, for example, a halogen atom (eg, Cl, Br, I), a hydroxyl group, an amino group, a carboxyl group, and an alkyl group (eg, one or more carbon atoms, preferably 1 to 4 carbon atoms). And alkoxy groups (e.g., one or more carbon atoms,
(Preferably having 1 to 4 carbon atoms).

The mercapto-substituted heteroaromatic rings are listed below. However, it is not limited to these.

M-1 2-Mercaptobenzimidazole M-2 2-Mercaptobenzoxazole M-3 2-Mercaptobenzothiazole M-4 5-Methyl-2-mercaptobenzimidazole M-5 6-Ethoxy-2-mercaptobenzo Thiazole M-6 2,2'-dithiobis (benzothiazole) M-7 3-Mercapto-1,2,4-triazole M-8 4,5-Diphenyl-2-mercaptoimidazole M-9 2-Mercaptoimidazole M- 10 1-ethyl-2-mercaptobenzimidazole M-11 2-mercaptoquinoline M-12 8-mercaptopurine M-13 2-mercapto-4 (3H) -quinazolinone M-147-trifluoromethyl-4-quinolinethiol M-15 2,3,5,6-tetrachloro 4-pyridine thiol M-16 4 amino-6-hydroxy-2-mercaptopyrimidine monohydrate M-17 2-amino-5- mercapto-1,3,4
Thiadiazole M-18 3-Amino-5-mercapto-1,2,4-
Triazole M-19 4-Hydroxy-2-mercaptopyrimidine M-20 2-Mercaptopyrimidine M-21 4,6-Diamino-mercaptopyrimidine M-22 2-Mercapto-4-methylpyrimidine hydrochloride M-23 3-Mercapto- 5-phenyl-1,2,4
-Triazole M-24 2-mercapto-4-phenyloxazole The supersensitizer is used in the emulsion layer containing the organic silver salt and the silver halide grains in the range of 0.001 to 1.0 mol per mol of silver. Is preferred. Particularly preferably, the amount is in the range of 0.01 to 0.5 mol per mol of silver.

The photothermographic material of the present invention may contain an antifoggant. As effective antifoggants, mercury compounds known from, for example, U.S. Pat. No. 3,589,903 are environmentally undesirable. For this reason, non-mercury antifoggants have been studied for a long time. Non-mercury antifoggants include, for example, US Pat. No. 4,546,075.
No. 4,452,885 and JP-A-59-572.
No. 34 is preferred.

In the present invention, in order to further improve the density fluctuation during storage with time, an oxidizing agent for reducing fog after development is used. Preferred examples of such an oxidizing agent include, for example, JP-A-50-119624 and JP-A-50-12.
No. 0328, No. 51-121332, No. 54-580
No. 22, 56-70543, 56-99335
No., 59-90842, 61-129,624,
62-129845, JP-A-6-208191,
No. 7-5621, No. 7-2781, No. 8-1580
9, U.S. Patent Nos. 5,340,712 and 5,36
No. 9,000, No. 5,464,737, No. 3,87
4,946, 4,756,999, 5,34
0,712, European Patent Nos. 605,981A1, 6
Compounds described in JP-A Nos. 22,666A1, 631,176A1, JP-B-54-165, JP-A-7-2781, U.S. Pat. Nos. 4,180,665 and 4,442,202 can be used. Although it can be used, a polyhalogen compound represented by the following general formula (I) is preferable.

[0191]

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In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and X ₁ , X ₂ and X ₃ each represent a hydrogen atom or an electron-withdrawing group, and may be the same or different. .
Y represents a divalent linking group. n represents 0 or 1.

The electron-withdrawing group represented by X ₁ , X ₂ and X ₃ is preferably a substituent having a σp value of 0.01 or more, more preferably 0.1 or more. Regarding the Hammett's substituent constant, Journal of M
edininal Chemistry, 1973, V
ol. 16, No. 11, 1207 to 1216 can be referred to.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp value
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (eg, C ₃ H) ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.45)), carbamoyl group ( σp value:
0.36), a sulfamoyl group (σp value: 0.57) and the like.

X ₁ , X ₂ and X ₃ are preferably an electron-withdrawing group, more preferably a halogen atom (fluorine atom (σ
p value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value:
0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value:
0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (eg, C ₃
H ₃ (σp value: 0.09)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.45)), carbamoyl group (σp value: 0.3
6), a sulfamoyl group (σp value: 0.57) and the like. Particularly preferred is a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

Y represents a divalent linking group, specifically, -S
O ₂ —, —SO—, —CO—, —N (R ₁₀₁ ) —SO
_{2 -, - N (R 101} ) -CO -, - N (R 101) -COO
-, -COCO-, -COO-, -OCO-, -OCO
O -, - SCO -, - SCOO -, - C (Z 11)
(Z ₁₂₎ -, represents an alkylene, arylene, a divalent heterocyclic, and divalent linking group formed by any combination thereof. R ₁₀₁ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. Z ₁₁ and Z ₁₂ represent a hydrogen atom or an electron-withdrawing group, but they are not a hydrogen atom at the same time. The electron-withdrawing group is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably a substituent of 0.1 or more. Preferred as the electron-withdrawing group for Z ₁₁ and Z ₁₂ are the aforementioned X
Same as ₁ , X ₂ and X ₃ .

Preferred as Z ₁₁ and Z ₁₂ are a halogen atom, a cyano group and a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred. Y is preferably -SO
_2- , -SO-, -CO-, more preferably -S
Represents O ₂ —. n is preferably 1.

The aliphatic group represented by A is a linear, branched or cyclic alkyl group (preferably having 1 to 30, more preferably 1 to 20, more preferably 1 to 12; Ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, etc., and an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, furthermore Preferably it is 2-12, for example, vinyl, allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (preferably having 2-3 carbon atoms)
0, more preferably 2 to 20, even more preferably 2 to 12
And for example, propargyl, 3-pentenyl and the like. ), And may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and a ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group. A
The aromatic group represented by is preferably an aryl group, and the aryl group is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably A phenyl group having 6 to 20 carbon atoms, more preferably a phenyl group having 6 to 12 carbon atoms. The aryl group may have a substituent, for example, a carboxyl group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group,
An oxycarbonylamino group or a ureido group;
The heterocyclic group represented by A is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, which may be a single ring, And a fused ring may be formed.

The heterocyclic group represented by A is preferably a 5- or 6-membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom, and further preferably Represents 1 to 2 nitrogen atoms
And a 6-membered aromatic heterocyclic group. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole,
Quinoline, phthalazine, naphthyridine, quinoxaline,
Examples include quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine and the like. Preferably as a heterocycle, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine,
Pyrazine, pyridazine, triazole, triazine, indole, indazole, quinoline, thiadiazole,
Oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, more preferably pyridine, triazine, quinoline, thiadiazole, benzine. Thiazole and oxadiazole are particularly preferable, and pyridine, quinoline, thiadiazole and oxadiazole are particularly preferable.

Of the above polyhalogen compounds, the compounds represented by the general formula (Ia) are more preferably used.

[0201]

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In the general formula (Ia), A, X ₁ , X ₂ ,
X ₃ and n have the same meanings as those in formula (I), and their preferred ranges are also the same.

The following are specific examples of the polyhalogen compound used in the present invention, but are not limited thereto.

[0204]

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[0205]

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[0206]

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In the present invention, the oxidizing agent is 10 mg / m ²
３3 g / m ^2, preferably 50 mg / m ² 〜
1 g / m ² is more preferred.

In the present invention, the oxidizing agent may be added by any method such as a solution, a powder or a solid fine particle dispersion, and it is particularly preferable that the solid fine particles are dispersed in the image forming layer. At the time of dispersion, a dispersion aid may be used. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent.

In addition to the above-mentioned oxidizing agents, suitable antifoggants include compounds disclosed in US Pat. Nos. 3,874,946 and 4,756,999; -288328 paragraph number [0030] ~
Compound described in [0036], JP-A-9-90
No. 550, compounds described in paragraph numbers [0062] to [0063], which are disclosed in U.S. Pat. No. 5,028,523 and European Patent Nos. 600,587, 631,176 and 605,981. Are preferably used.

Binders suitable for the photothermographic material of the present invention are transparent or translucent and 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) ), Poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or hydrophobic, but 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.

Other preferred binders are the polymer latexes described below. The polymer latex is preferably contained in the image forming layer. The polymer latex preferably contains at least 50% by mass of the entire binder. In the present invention, the “polymer latex” is obtained by dispersing a water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used.

The polymer latex in the present invention is described in "Synthetic Resin Emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (1978))", "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Edited by Keiji Kasahara, published by the Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, published by the Society of Polymer Publishing (197)
0))).

The dispersed particles have an average particle size of 1 to 50,000 n.
m, more preferably in the range of about 5 to 1,000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution. As the polymer latex, a so-called core / polymer latex other than an ordinary polymer latex having a uniform structure is used.
Shell type latex may be used. In this case, it may be preferable to change the glass transition temperature of the core and the shell. Minimum film formation temperature (MFT) of the polymer latex of the present invention
Is preferably -30 to 90C, more preferably about 0 to 70C. In order to control the minimum film forming temperature, a film forming auxiliary may be added. The film-forming aid is also called a plasticizer, and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex. For example, the above-mentioned “Synthetic latex chemistry (Souichi Muroi, published by Kobunshi Kankokai (197)
0)) ".

Examples of the polymer used for the polymer latex include an acrylic resin, a vinyl acetate resin, a polyester resin, a polyurethane resin, a rubber resin, a vinyl chloride resin, a vinylidene chloride resin, a polyolefin resin, and a copolymer thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. Also, the polymer may be a so-called homopolymer in which a single monomer is polymerized,
A copolymer obtained by polymerizing two or more monomers may be used. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is 5,000 to 1,000,000, preferably 10,000, in number average molecular weight.
About 100 to 100,000 is preferable. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the image forming layer of the photothermographic material of the present invention include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / 2-ethylhexyl acrylate / styrene / acryl. Acid copolymer latex, styrene / butadiene / acrylic acid copolymer latex, styrene / butadiene / divinylbenzene / methacrylic acid copolymer latex, methyl methacrylate / vinyl chloride / acrylic acid copolymer latex, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid Latex of a copolymer and the like.

Further, such polymers are commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635, 465
83, 4601 (all manufactured by Daicel Chemical Industries, Ltd.);
Nipol Lx811, 814, 821, 820, 8
Polyester resins such as 57 (both manufactured by Nippon Zeon Co., Ltd.) include FINETEX ES650, 611,
675, 850 (all manufactured by Dainippon Ink and Chemicals, Inc.),
Examples of polyurethane resins such as WD-size and WMS (all manufactured by Eastman Chemical) include HYDRAN.
Examples of rubber-based resins such as AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR.
7310K, 3307B, 4700H, 7132C
(Dai Nippon Ink Chemical Co., Ltd.), Nipol L
x416, 410, 438C, 2507, and the like (all manufactured by Nippon Zeon Co., Ltd.)
51, G576 (all manufactured by Zeon Corporation); vinylidene chloride resins such as L502 and L513 (all manufactured by Asahi Chemical Industry Co., Ltd.); olefin resins include Chemipearl S120 and SA100 (all manufactured by Mitsui Oil) Chemical Co., Ltd.). These polymers may be used alone or as a mixture of two or more as necessary.

The polymer latex preferably contains a carboxylic acid component such as an acrylate or methacrylate component in an amount of about 0.1 to 10% by mass. When a polymer latex is used for the image forming layer, the image forming layer is preferably such that at least 50% by mass of the total binder is the above polymer latex, and more preferably at least 70% by mass is the above polymer latex. In that case, if necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose is added to the image forming layer in a range of 50% by mass or less of the entire binder. Is also good. The addition amount of these hydrophilic polymers is preferably 30% by mass or less of the total binder in the image forming layer.

When a polymer latex is used for the image forming layer, the image forming layer is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 50% by mass or more of the solvent (dispersion medium) of the coating liquid is water, and preferably 65% by mass or more of the solvent is water. As components other than water of the coating liquid, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide =
80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent mass%.) A crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added to the image forming layer. When the image forming layer contains a polymer latex, the coating solution for the thermal image forming layer is preferably a so-called thixotropic fluid. The thixotropic property refers to a property in which the viscosity decreases as the shear rate increases. Although any apparatus may be used for the viscosity measurement, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used, and the viscosity is measured at 25 ° C. The organic silver salt-containing fluid or the thermal image forming layer coating solution in the invention has a shear rate of 0.1.
The viscosity in S-1 is 400 mPa · s or more, 100,
000 mPa · s or less, more preferably 5 mPa · s or less.
It is not less than 00 mPa · s and not more than 20,000 mPa · s. At a shear rate of 1000 S-1, 1 mP
It is preferably not less than a · s and not more than 200 mPa · s, and more preferably not less than 5 mPa · s and not more than 80 mPa · s.

Various systems exhibiting thixotropic properties are known, and are described in, for example, “Lecture / Rheology” edited by Polymer Publishing Association and “Polymer Latex” (published by Polymer Publishing Association), co-authored by Muroi and Morino. In order for the fluid to exhibit thixotropic properties, it is necessary to contain a large amount of solid fine particles. In order to enhance the thixotropic property, the thickening linear polymer is contained, the aspect ratio is increased by the anisotropic solid fine particles contained, alkali thickening,
Use of a surfactant is effective.

The total amount of the binder in the image forming layer is from 0.2 to 3
0 g / m ^2, more preferably in the range of 1 to 15 g / m ^2.

In order to protect the surface of the photothermographic material and prevent abrasion, a non-image forming layer may be provided outside the image forming layer. The binder used for these non-image forming layers may be the same or different from the binder used for the image forming layers.

In the present invention, the amount of the binder in the photosensitive layer is preferably 0.5 to 30 g / m ² in order to increase the speed of thermal development. More preferably, 1 to 15 g / m
² If it is less than 0.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the image forming layer side, and a matting agent is preferably disposed on the surface of the photothermographic material in order to prevent damage to the image after heat development. It is preferable that the matting agent is contained in a mass ratio of 0.5 to 30% based on all binders on the image forming layer side. When the non-image forming layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-image forming layer side contains a matting agent. Any of the fixed shapes may be used, but a fixed shape and a spherical shape are preferably used.

In the photothermographic material of the present invention, only an image forming layer may be formed on a support, but it is preferable to form at least one non-image forming layer on the image forming layer. In order to control the amount or wavelength distribution of light passing through the image forming layer, a filter dye layer on the same side as the image forming layer and / or an antihalation dye layer on the opposite side, a so-called backing layer may be formed, The image forming layer may contain a dye or a pigment.

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

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

In the present invention, the antihalation layer can be provided on the side farther from the light source than the image forming layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.1 or more and 2 or less, more preferably 0.2 or more and absorption of an exposure wavelength of 1.5 or less, and after treatment. 0.0 absorption in the visible region
It is preferably from 01 to less than 0.2, more preferably from 0.001 to less than 0.15. When used for plate making, the absorption at 400 nm is not less than 0.001 and not more than 0.2.
Is preferably less than 0.00, more preferably 0.00
It is particularly preferred that the layer has an optical density of 1 or more and less than 0.15.

When antihalation dyes are used in the present invention, these dyes have the desired absorption in the wavelength range, have a sufficiently low absorption in the visible region after treatment, and have the desired absorbance spectrum of the antihalation layer. Any compound can be used, if possible.

For example, the following are disclosed, but the present invention is not limited to them. As a single dye, JP-A-59-56458, JP-A-2-
No. 216140, No. 7-13295, No. 7-1143
No. 2, U.S. Pat. No. 5,380,635;
No. 8539, page 13, lower left column, line 1 to page 14, lower left column, line 9; 3-24539, page 14, lower left column, line 1
The compounds described in the lower right column on page 6 include the dyes which can be decolorized by the treatment, as described in JP-A Nos. 52-139136 and 53-132.
No. 334, No. 56-501480, No. 57-1606
No. 0, 57-68831, 57-101835
No. 59-182436, JP-A-7-36145
No. 7-199409, JP-B-48-33692
No. 50-16648, Tokiko 2-41734,
U.S. Pat. Nos. 4,088,497 and 4,283,48
No. 7, 4,548,896, 5,187,049
No. etc.

The photothermographic material of the present invention is preferably a so-called single-sided recording material having at least one image forming layer on one side of a support and a back layer on the other side.

In the present invention, suitable binders for the back layer are transparent or translucent, generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (vinyl) Alcohol), hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), 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) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or an emulsion.

In the present invention, the back layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range, more preferably 0.5 or more and 2 or less, and after the treatment. Absorption in the visible region of 0.00
It is preferably at least 1 and less than 0.5, more preferably a layer having an optical density of at least 0.001 and less than 0.3. When used for printing plate making, the absorption at 400 nm is preferably 0.001 or more and less than 0.2, and more preferably a layer having an optical density of 0.001 or more and less than 0.15. Is particularly preferred. Examples of the antihalation dye used in the back layer are the same as the antihalation layer described above.

Various additives may be added to any of the image forming layer, the non-image forming layer, and other forming layers. In the photothermographic material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used. These additives and the other additives described above are described in RD17029 (pp. 9-1 of June 1978).
The compounds described in 5) can be preferably used.

The support used in the present invention may be a plastic film (eg, polyethylene terephthalate (PET), polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate) in order to prevent deformation of the image after development processing. preferable. 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 the support is formed into a film and before the image forming layer is applied, the glass transition point of the support is 30 ° C.
At a high temperature, preferably at least 35 ° C,
More preferably, heating is performed at a temperature higher than 40 ° C. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

Known methods can be used for the method of forming a support and the method of producing an undercoat according to the present invention. Preferably, the method is described in paragraphs [0030] to JP-A-9-50094.
[0070] is to use the method described in [0070].

The photothermographic material of the present invention may be developed by any method, but is usually developed by elevating the temperature of the photothermographic material exposed imagewise. The preferred development temperature is 105 to 145C, more preferably 107 to 140C. The development time is 1 to 18
0 second, more preferably 7 to 50 seconds, and particularly preferably 8 to 25 seconds.

The photothermographic material of the present invention is preferably heat-developed by a heat developing machine. The photothermographic material is susceptible to temperature variations in the photothermographic section, and development unevenness tends to occur. Therefore, Japanese Patent Application Laid-Open Nos. 9-297384 and 9-297
No. 385, No. 9-297386, a heat drum type automatic heat developing machine, WO 98/27
No. 458, a flat transport type automatic thermal developing machine is used. In particular, the photothermographic material used for printing plate making is preferably processed by a flat transport type automatic thermal developing machine in order to improve dimensional stability. Further, an automatic thermal developing machine having a preheating section in front of the thermal developing section and having a preheating temperature of 80 to 120 ° C. is preferably used. The preheating advances development and reduces density unevenness, so that it is also effective for scanning unevenness. Further, one surface of the photosensitive material is brought into contact with a fixed heating member as described in JP-A-11-133572, and the photosensitive material is conveyed while pressing the other surface of the photosensitive material against the heating member with a plurality of rollers. It is also preferable to carry out a heat development treatment using an apparatus for performing the heat development.

The photothermographic material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source. As the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Among them, in order to prevent interference fringes and uneven exposure of halftone dots, vertical multi-exposure or oblique exposure is preferable.

The vertical multi-exposure in the present invention is performed by using a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi. To achieve vertical multiplication, a method such as combining, using return light, or superimposing a high frequency is preferable. Specifically, the method described in JP-A-59-10964 is preferably used. Note that the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5
nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually 60 nm.
It is about. The oblique exposure means that the exposure is performed by using a laser scanning exposure machine in which the angle between the exposure surface of the photothermographic material and the scanning laser beam does not become substantially perpendicular. Specifically, the method described in JP-A-5-113548 is preferably used. Here, "not substantially perpendicular" means that the angle is most perpendicular during laser scanning, preferably 55 degrees or more and 88 degrees or less, more preferably 60 degrees or more and 86 degrees or less, furthermore Preferably 6
5 degrees or more and 84 degrees or less, most preferably 70 degrees or more and 8 degrees or less.
It means that it is twice or less.

When the laser beam is scanned on the photothermographic material, the beam spot diameter on the exposed surface of the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. Note that the lower limit of the beam spot diameter is 5 μm.
By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of interference fringe-like unevenness.

[0241]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Photothermographic Material >><Preparation of Subbed Photographic Support> Polyethylene terephthalate (hereinafter abbreviated as PET) was prepared as follows. A commercially available biaxially stretched heat-fixed PET film having a thickness of 125 μm is subjected to a corona discharge treatment of 8 W / m ² · min on both surfaces, and the following undercoating solution a is applied to one surface.
-1 is applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1. 0.8 μm, and dried to obtain an antistatic subbing layer B-1.

(Undercoating coating liquid a-1) Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Styrene (25% by mass) 2-hydroxyethyl acrylate (25% by mass) 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 1. Make up to 1 L with water.

(Undercoat Coating Solution b-1) SnO ₂ / Sb (mass ratio of 9/1, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (40% by mass) Styrene (20% by mass) ) Glycidyl acrylate (40% by mass) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 L with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
8 W / m ² · min. Of corona discharge is applied to the surface of the undercoating layer A-1, and the undercoating upper layer coating solution a-2 shown below is coated on the undercoating layer A-1 so as to have a dry film thickness of 0.1 μm. A-2, and the undercoating layer B-1 having an antistatic function was coated on the undercoating layer B-1 such that the following undercoating layer coating solution b-2 had a dry film thickness of 0.8 μm. 2 was applied. (Coating solution a-2 for lower layer) Gelatin 0.4 g / m ² Mass (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 Finish to 1 L with water. (Undercoat upper layer coating solution b-2) (C-4) 60 g Latex liquid containing (C-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol (mass average molecular weight) 600) Finish to 1L with 6g water.

[0246]

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[0247]

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<Heat treatment of the support> In the above-mentioned undercoat drying step of the undercoated support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled. At that time, it was transported under a tension of ² kg / cm ² .

<Preparation of silver halide emulsion A>
7.5 g of inert gelatin and 1 part of potassium bromide
After dissolving 0 mg and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide, [Ir (NO) Cl
_5] a 1 × 10 ^-6 mol and 1 × 10 ^-6 mol per mol of silver rhodium chloride salt per mole of silver salt, was added by a controlled double jet method. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the [100] face ratio with an average particle size of 0.06 μm and a dispersity of 45% was added. 87%
Of non-monodispersed cubic silver iodobromide grains of This emulsion is subjected to coagulation sedimentation using a gelatin coagulant, and after desalting treatment, 0.1 g of phenoxyethanol is added, pH 5.9, pAg7.
Adjusted to 5. Further, the resultant was chemically sensitized with chloroauric acid, inorganic sulfur, thiourea dioxide, and 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide to obtain a silver halide emulsion A.

<Preparation of Sodium Behenate Solution> 945
8 ml of pure water, 32.4 g of behenic acid, and 9 of arachidic acid.
9 g and stearic acid 5.6 g were dissolved at 90 ° C. Next, 98 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at a high speed. Next, after adding 0.93 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.

<Preparation of Preform Emulsion A of Sodium Behenate Solution and Silver Halide Emulsion A> The obtained silver halide emulsion A was added to the above sodium behenate solution at 15.
After adding 1 g and adjusting the pH to 8.1 with a sodium hydroxide solution, 147 ml of a 1 M silver nitrate solution was added over 1 minute, and the mixture was further stirred for 15 minutes, and ultrafiltration was performed to remove water-soluble salts. The resulting silver behenate has a long side average size of 0.8μ
m of acicular particles. 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 A containing organic silver salt A> To the obtained preform emulsion A, 544 g of a solution of polyvinyl butyral (average molecular weight: 3,000) in methyl ethyl ketone (17% by mass) and 107 g of toluene were added. After slowly adding and mixing, it was dispersed at 4000 psi.
After the dispersion, the organic silver salt particles were observed with an electron microscope photograph. It was a non-monodispersed organic silver salt having an average particle size of 0.7 μm and a degree of dispersion of 60%. When the organic silver salt particles were similarly observed after coating and drying, the same particles were confirmed. 240g of this emulsion
Then, 4.7 ml of a 0.01% methanol solution of calcium bromide was added to obtain a photosensitive emulsion A. When the silver halide therein was observed with an electron microscope, 0.01 μm
m or less were not visible.

<Preparation of silver halide emulsion B>
7.5 g of inert gelatin and 1 part of potassium bromide
After dissolving 0 mg and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide, [Ir (NO) Cl
_5] a 1 × 10 ^-6 mol and 1 × 10 ^-6 mol per mol of silver rhodium chloride salt per mole of silver salt, pAg 7.7
, And added by a controlled double jet method. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added and the pH was adjusted to 5 with NaOH.
Adjusted to an average particle size of 0.06 μm and a dispersity of 12%
To obtain monodispersed cubic silver iodobromide grains having a [100] face ratio of 49%. This emulsion was coagulated and precipitated using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added.
The pH was adjusted to 5.9 and pAg to 7.5. Furthermore, chloroauric acid,
Chemical sensitization was performed with inorganic sulfur, thiourea dioxide, and 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide to obtain a silver halide emulsion B.

<Preparation of Sodium Behenate Solution> 945
8 ml of pure water, 32.4 g of behenic acid, and 9 of arachidic acid.
9 g and stearic acid 5.6 g were dissolved at 90 ° C. Next, 98 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at a high speed. Next, after adding 0.93 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.

<Preparation of Preform Emulsion B of Sodium Behenate Solution and Silver Halide Emulsion B> The obtained silver halide emulsion B was added to the above-mentioned sodium behenate solution.
After adding 1 g and adjusting the pH to 8.1 with a sodium hydroxide solution, 147 ml of a 1M silver nitrate solution was added over 7 minutes, and the mixture was further stirred for 20 minutes, and ultrafiltration was performed to remove water-soluble salts. The resulting silver behenate has a long side average size of 0.8μ
m of acicular particles. After the floc of the dispersion was formed, the water was removed, and the resultant was washed with water six times and removed, and then dried.

<Preparation of Photosensitive Emulsion B Containing Organic Silver Salt B> To the obtained preform emulsion B, 544 g of a solution of polyvinyl butyral (average molecular weight: 3000) in methyl ethyl ketone (17% by mass) and 107 g of toluene were gradually added. After being added and mixed, it was dispersed at 4000 psi. After the dispersion, the organic silver salt particles were observed with an electron microscope photograph. 30
As a result of measuring the particle size and thickness of 0 organic silver salt particles, 20
Five were monodispersed tabular organic silver salts having an AR of 3 or more and a dispersity of 25%. Incidentally, the average particle size was 0.7 μm. When the organic silver salt particles were similarly observed after coating and drying, the same particles were confirmed. To 240 g of this emulsion, photosensitive emulsion B was obtained by adding 3 ml of a 6% methanol solution of pyridinium bromide perbromide and 1.7 ml of a 0.1% methanol solution of calcium bromide. When the silver halide in this was observed with an electron microscope, 0.01 μm
Less than silver halide grains could be observed. The silver halide grains were observed with an electron microscope photograph. When the particle size of 500 organic silver salt particles was measured, the number of particles having a particle size of less than 0.01 μm was 45% of the total number of silver halide particles.

<Back layer surface side coating> A back layer coating solution having the following composition was filtered using a filter having a quasi-absolute filtration accuracy of 20 μm, and the above support was subjected to an antistatic treatment by an extrusion coater. On the surface side, a total wet film thickness of 3
It was applied to a thickness of 0 μm and dried at 60 ° C. for 15 minutes.

(Back Layer Coating Solution) Cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² Dye-A 7 mg / m ² Dye-B 7 mg / m ²

[0259]

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(Coating solution for back protective layer) Cellulose acetate butyrate (10% methyl ethyl ketone solution) 5 ml / m ² matting agent (monodispersion degree 15%, monodisperse silica having an average particle size of 8 μm) 15 mg / m ² fluorinated surfactant Agent C ₁₂ F ₂₅ (CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 10 mg / m ² <Coating on the surface of the image forming layer> The coating solution for the image forming layer having the following composition and the coating solution for the protective layer thereon were subjected to semi-absolute filtration. After filtration using a filter having an accuracy of 20 μm, the layers in the combinations shown in Table 1 were applied to the undercoat layer A-2 side of the support by an extrusion coater at a rate of 70 m / min. At that time, the amount of silver applied was 1.
The composition was adjusted to 5 g / m ² and applied. Thereafter, the sample 101 was dried at 65 ° C. for 1 minute, and the sample 102 was dried at 55 ° C.
Drying was performed at 10 ° C. for 10 minutes. Thereafter, the sample 101 was coated with the surface protective layer coating solution 1, and the sample 102 was coated with the surface protective layer coating solution 2.

(Image Forming Layer Coating Solution A) Photosensitive Emulsion A (obtained above) 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml 2- (4-chlorobenzoyl) benzoic acid (12 % Methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml O-25 0.4 g A-2 (20% methanol solution) 29.5 ml phthalazine 0.2 g 4-methylphthalic acid 0.25 g tetrachloro Phthalic acid 0.2 g Hexamethylene diisocyanate (10% methanol solution) 1.2 ml (Image forming layer coating solution B) Photosensitive emulsion B (obtained above) 240 g Sensitizing dye (0.1% methanol solution) 1 0.7 ml 2- (4-chlorobenzoyl) benzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenz Midazole (1% methanol solution) 11 ml Vinyl compound 1-5 0.5 g Hydrazine derivative H-1-4 0.5 g Quaternary onium compound P-17 0.1 g Compound of general formula (1) or (2) 5 g acid anhydride 3-4 0.5 g O-25 0.4 g A-1 (20% methanol solution) 29.5 ml phthalazine 0.2 g 4-methylphthalic acid 0.25 g tetrachlorophthalic acid 0.2 g hexamethylene diisocyanate ( 1.2 ml (Surface protective layer coating solution 1) Acetone 5 ml / m ² Methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² Matting agent: average particle size 5.5μm silica 10 mg / m ² vinyl sulfone compounds VS-1 35m / M ² Fluorine-based surfactant _{C 12 F 25 (CH 2 CH} 2 O) 10 C 12 F 25 10mg / m 2 ( surface protective layer coating solution 2) Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² colloidal silica 50 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 10 mg / m ² vinyl sulfone compound VS-1 35 mg / m ² fluorine system surfactant _{C 12 F 25 (CH 2 CH} 2 O) 10 C 12 F 25 10mg / m 2 C 8 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2

[0262]

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Thus, as shown in Table 1, Sample 1
01 and 102 were obtained. The amount of the remaining solvent methyl ethyl ketone (MEK) in the obtained sample was 70 mg / m ² . The Vickers hardness of the surface of the sample 102 on the image forming layer side was 100. In addition, 25 samples were obtained.
After humidity control for 24 hours in an environment of 60 ° C. and 60% RH, a film area of 46.3 cm ² was cut out under the same atmosphere.
After measuring the mass, this was finely chopped to about 5 mm, stored in a dedicated vial, sealed with a septum and an aluminum cap, and then set in a Hewlett-Packard HP7694 headspace sampler, and the headspace sampler was heated to 120 ° C. After heating for 20 minutes and evaporating water, the equilibrium water content of the sample was determined by the Karl Fischer method. As a result, the sample 101 was 6% and the sample 102 was 0.7%.

The photothermographic material prepared above was treated with a wavelength of 78.
0 nm semiconductor laser is disclosed in Japanese Patent Application Laid-Open No. Sho 59-130494.
Exposure was performed from the image forming surface side through a wedge by a laser operation using an exposure machine having an exposure source in a vertical multi-mode using the high-frequency superposition method described in the above publication.

(1) Method for Determining Relationship Obtained by Log (S ₀ / S ₁₁ ) The exposed sample was heated in an oven at 120 ° C. for 20 seconds and 2 hours.
The heat development was performed in 5 seconds. The optical density of the obtained sample was measured and the sensitivity was calculated. The sensitivity was represented by the reciprocal of the exposure amount giving a density of 2.5. The sensitivity obtained by thermal development at 120 ° C. for 25 seconds is S ₀ , and the sensitivity obtained by thermal development at 120 ° C. for 20 seconds is S ₀ .
₁₁ was calculated according to equation (1).

Formula (2) How to determine the relationship obtained by γ ₁₁ / γ _{0 The} exposed sample was placed in an oven at 120 ° C. for 20 seconds and 2
The heat development was performed in 5 seconds. The optical density of the obtained sample was measured and the gamma value was calculated. The gamma value was represented by the slope of a straight line connecting the densities 0.1 and 2.5 of the characteristic curve when the photothermographic material was heated and developed. The gamma value obtained by thermal development at 120 ° C. for 25 seconds was γ ₀ , and the gamma value obtained by thermal development at 120 ° C. for 20 seconds was γ ₁₁ , which was calculated according to equation (2).

Formula (3) How to determine the relationship obtained by Dmax ₁₁ / Dmax _{0 The} exposed sample was placed in an oven at 120 ° C. for 20 seconds and 2 minutes.
The heat development was performed in 5 seconds. The optical density of the obtained sample was measured and the maximum density was calculated. The maximum density obtained by thermal development at 120 ° C. for 25 seconds was Dmax ₀ , and the maximum density obtained by thermal development at 120 ° C. for 20 seconds was Dmax ₁₁ , which was calculated according to equation (3).

Test Method for Raw Storage Property The photothermographic material prepared above was divided into two parts,
Stored at 3 ° C., 50% RH for 3 days. 55 on the other
The samples were subjected to high-humidity high-temperature forced deterioration at 80 ° C. and 80% RH for 3 days. After that, a semiconductor laser having a wavelength of 780 nm was used in
Exposure was performed from the image forming surface side through a wedge by a laser operation using an exposure machine having an exposure source in a vertical multi-mode using a high-frequency superposition method described in JP-A-130494.

Then, heat development was performed at 121 ° C. for 20 seconds by using a dry view processor 2771, a thermal developing machine for dry film for plate making, manufactured by Kodak Polychrome Graphics Co., Ltd. In addition, this automatic processing machine for dry film,
This is a thermal developing machine of a plane transport type having a preheating section of about 110 ° C., and the total time from when the sample tip enters the thermal developing machine to when the tip exits is 48 seconds. The optical density of the obtained sample was measured and the sensitivity was calculated. The sensitivity is 2.
It was expressed by the reciprocal of the exposure amount giving 5. 23 ° C, 50% RH
The sensitivity of the sample stored for 3 days at S ₀₀ , 55 ° C., 80% R
Sensitivity of high humidity and high temperature forced deterioration for 3 days at H
₁₀₁ was calculated by log (S ₀₀ / S ₁₀₁ ). As for this value, 0 is the best, and when it is far from 0, the raw preservability is poor.

Evaluation of storage stability after thermal development The photothermographic material exposed and thermally developed as described above was divided into two parts.
40 ° C, 60% while irradiating one side for evaluation for the age
For 5 days. Using a densitometer, it was measured how much the concentration was 3.5 before it was put into the thermo-hygrostat, and how much the density changed after putting into the thermo-hygrostat.

Evaluation of Black Pot The unexposed portion of the heat-developable photothermographic material was
It was visually observed with a double magnifier, and the black pots were evaluated with a rank of 1 to 5. If no black spots were seen, the rank was set at 5 ranks.
The rating dropped to 2,1. Less than three ranks are not practical. Table 1 shows the results of the evaluation.

[0272]

[Table 1]

Table 1 shows that the sample of the present invention is superior to the comparative sample in all evaluation items.

Example 2 <Preparation of silver halide grains C> Phthalate was added to 700 ml of water.
Dissolve 22g of gelatinized gelatin and 30mg of potassium bromide
After adjusting the pH to 5.0 at a temperature of 40 ° C.,
159 ml of an aqueous solution containing 18.6 g and potassium bromide
Water solution for 10 minutes by controlled double jet method
Added over time. K_Three[IrCl₆]^3-To 8 × 10^-6Mo
1 mol / l and potassium bromide at 1 mol / l
Dissolve the aqueous solution for 15 minutes by the controlled double jet method
And added. Then adjusted to pH 5.9 and pAg 8.0
did. The obtained particles have an average particle size of 0.08 μm,
Non-monodisperse cubic with a dispersion degree of 45% and (100) area ratio of 40%
Were silver halide grains. This silver halide grain C
Was raised to a temperature of 60 ° C. and 8.5 × 10
^-FiveMolar sodium thiosulfate, 1.1 × 10^-FiveMole of
2,3,4,5,6-pentafluorophenyldiphenyl
Lufosfin selenide, 1 × 10^-6Mole tellurium compound
Object-1, 3.3 × 10 ^-6Molar chloroauric acid, 2.3 × 10
^-FourRipened by addition of molar thiocyanic acid. Then warm
8 x 10 at a temperature of 50 ° C^-FourStirring moles of sensitizing dye C
While adding 3.5 × 10^-2Molar potassium iodide
And stir for 30 minutes.
Preparation of silver halide grains was completed.

[0275]

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<Preparation of Microcrystal Dispersion of Organic Silver Salt C> 40 g of behenic acid, 7.3 g of stearic acid, 500 ml of distilled water
Was mixed at 90 ° C. for 15 minutes, 187 ml of a 1 mol / l-NaOH aqueous solution was added over 15 minutes with vigorous stirring, and 61 ml of a 1 mol / l-nitric acid aqueous solution was added, followed by cooling to 50 ° C. Next, 124 ml of a 1 mol / liter silver nitrate aqueous solution was added, and the mixture was stirred for 5 minutes as it was. Thereafter, the solid content was filtered by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. The solid content thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol and 1 liter of water were added to a wet cake equivalent to 34.8 g of dry solid content.
50 ml was added and mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put in a vessel together with the slurry, and use a dispersing machine (1/4).
(G-Sand grinder mill: manufactured by Imex Co., Ltd.) for 30 minutes to obtain a non-monodispersed organic silver salt C microcrystal dispersion having a volume weighted average of 1.6 μm and a degree of dispersion of 55%.
Particle size measurements are available from Malvern Instrument
ents Ltd. Performed by MasterSaizerX.

<Preparation of silver halide grains D>
1 g of phthalated gelatin 22 g and potassium bromide 30
After dissolving mg and adjusting the pH to 5.0 at a temperature of 40 ° C., 159 ml of an aqueous solution containing 18.6 g of silver nitrate and an aqueous solution containing potassium bromide were prepared by a controlled double jet method while maintaining the pAg at 7.7. Added over 10 minutes. An aqueous solution containing 8 × 10 ⁻⁶ mol / L of K ₃ [IrCl ₆ ] ^3- and 1 mol / L of potassium bromide was added to pA
While maintaining g7.7, it was added over 30 minutes by the controlled double jet method. Then pH 5.9, pAg
It was adjusted to 8.0. The obtained particles had an average particle size of 0.07 μm and a [100] plane ratio of 85% with a dispersity of 15%.
Of cubic silver halide grains.

The silver halide grains D were heated to a temperature of 60 ° C. to give 8.5 × 10 ^-5 mol of sodium thiosulfate and 1.1 × 10 ^-5 mol of 2,3,4 per mol of silver. , 5,6
-Pentafluorophenyldiphenylphosphine selenide, 2 × 10 ^-6 mol of tellurium compound-1, 3.3 × 1
0 ^-6 mol of chloroauric acid and 2.3 × 10 ^-4 mol of thiocyanic acid were added and the mixture was aged for 120 minutes. Then, the temperature is set to 5
At 0 ° C., 8 × 10 ⁻⁴ mol of sensitizing dye C was added with stirring, and further 3.5 × 10 ⁻² mol of potassium iodide was added, followed by stirring for 30 minutes, and quenched to 30 ° C. Thus, the preparation of silver halide grains was completed.

<Preparation of organic silver salt D microcrystal dispersion> 40 g of behenic acid, 7.3 g of stearic acid, 500 ml of distilled water
Was mixed at 90 ° C. for 15 minutes, 187 ml of a 1 mol / l-NaOH aqueous solution was added over 15 minutes with vigorous stirring, and 61 ml of a 1 mol / l-nitric acid aqueous solution was added, followed by cooling to 50 ° C. Next, 124 ml of a 1 mol / liter silver nitrate aqueous solution was added, and the mixture was stirred as it was for 30 minutes. Thereafter, the solid content was filtered by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. The solid thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol and 150 ml of water were added to a wet cake equivalent to 34.8 g of dry solid, and mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and use a dispersing machine (１ ／ G).
-Sand grinder mill: manufactured by Imex Co., Ltd.)
For 4 hours at a volume-weighted average of 1.2 μm and a degree of dispersion of 2
A 0% monodispersed organic silver salt D crystallite dispersion was obtained. Particle size measurements are available from Malvern Instruments
Ltd. The measurement was performed by Master SaizerX manufactured by the company. To this dispersion was added 6 parts of phenylbromide perbromide.
3 ml of a 3% methanol solution was added. When the silver halide therein was observed with an electron microscope, silver halide grains of less than 0.01 μm could be observed.

<Preparation of Material Solid Fine Particle Dispersion> Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
Solid fine particle dispersions were prepared for 5-trimethylhexane, phthalazine, and tribromomethylsulfonylbenzene.

With respect to 5.4 g of tetrachlorophthalic acid,
0.81 g of hydroxypropylcellulose and 94.2 of water
Then, the mixture was stirred well and left as a slurry for 10 hours. Thereafter, 100 ml of the zirconia beads having an average diameter of 0.5 mm and the slurry were put together in a vessel, and dispersed for 5 hours using a disperser of the same type as that used for preparing the organic silver salt microcrystal dispersion. A solid microcrystalline dispersion of tetrachlorophthalic acid was obtained. The particle size of the solid fine particles is
70% by mass was 1.0 μm or less. With respect to other materials, in order to obtain a desired average particle size, the amount of the dispersant used and the dispersion time were appropriately changed to obtain a solid fine particle dispersion.

(Image Forming Layer Coating Solution C) The following components were added to the organic silver salt microcrystal dispersion prepared above to prepare an image forming layer coating solution C.

Organic silver salt microcrystal dispersion 1 mol Silver halide particles C 0.05 mol Binder: SBR latex (LACSTAR 3307B, manufactured by Dainippon Ink and Chemicals, Inc.) 430 g Tetrachlorophthalic acid 5 g 1,1-bis ( 2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g phthalazine 9.0 g tribromomethylphenylsulfone 12 g 4-methylphthalic acid 7 g vinyl compound 8-3 8 g hydrazine derivative H-6 5 g LACSTAR 3307B is a latex of a styrene-butadiene copolymer, the average particle size of the dispersed particles is 0.1 to 0.15 μm,
The equilibrium moisture content at 0% RH was 0.6%.

(Image Forming Layer Coating Solution D) The following components were added to the previously prepared organic silver salt microcrystal dispersion to prepare an image forming layer coating solution D.

Organic silver salt microcrystal dispersion 1 mol Silver halide particles D 0.05 mol Binder: SBR latex (LACSTAR 3307B, manufactured by Dainippon Ink and Chemicals, Inc.) 430 g Tetrachlorophthalic acid 5 g 1,1-bis ( 2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g phthalazine 9.0 g tribromomethylphenylsulfone 12 g 4-methylphthalic acid 7 g vinyl compound 8-3 8 g hydrazine derivative H-6 5 g (surface Protective Layer Coating Solution 3) The following compositions were added to inert gelatin to prepare a surface protective layer coating solution 3.

Inert gelatin 10 g Surfactant A 0.26 g Surfactant B 0.09 g Silica fine particles (average particle size 2.5 μm) 0.1 g 1,2- (bisvinylsulfone acetamide) ethane 0.1 g Water 65 g ( Surface Protective Layer Coating Solution 4) The following compositions were added to inert gelatin to prepare Surface Protective Layer Coating Solution 4.

Inert gelatin 10 g Surfactant A 0.26 g Surfactant B 0.09 g Silica fine particles (average particle size 2.5 μm) 0.9 g Colloidal silica 0.5 g 1,2- (bisvinylsulfone acetamide) ethane 0 0.5 g of water 64 g (back surface coating solution) The following compositions were added to polyvinyl alcohol to prepare a back surface coating solution.

Polyvinyl alcohol 30 g Dye-C 5 g Water 250 g Sildex H121 (Diakai Chemical Co., Ltd., spherical silica average size 12 μm) 1.8 g

[0289]

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The coating solution for the image forming layer prepared as described above was filtered using a filter having a quasi-absolute filtration accuracy of 20 μm, and then coated on a polyethylene terephthalate support at a silver concentration of 1.6 g / m ² . . Sample 2 on it
In the case of No. 01, the coating solution 3 for the surface protective layer was applied with a quasi-absolute filtration accuracy of 20 μ
After filtration using a filter of m, in Sample 202, the coating solution 4 of the surface protective layer was coated with a coating amount of gelatin of 1.8 g / m ^2.
It was applied so that The sample 201 was dried at 55 ° C. for 1 minute, and the sample 202 was dried at 65 ° C. for 20 minutes.
After drying, apply the back surface coating solution on the surface opposite to the image forming layer for 7 minutes.
Coating was performed so that the optical density at 80 nm was 0.7, and photothermographic material samples 201 and 202 were prepared as shown in Table 2 below.
I got The Vickers hardness of the surface of the sample 202 on the image forming layer side was 110.

After coating and drying, silver halide grains in each light-sensitive material were observed with an electron microscope photograph. When the particle size of 500 organic silver salt particles was measured, sample 201 showed almost no observation of particles smaller than 0.01 μm, but sample 202 showed that the particle size of less than 0.01 μm was the total number of silver halide particles. Was 50%.

Evaluation was performed in the same manner as in Example 1. Table 2 shows the results. However, the exposure was carried out through a wedge by a semiconductor laser having a wavelength of 780 nm by laser scanning with an exposure machine having an exposure source having an angle of 80 degrees with the exposure surface of the photosensitive material.

Formula (4) Determining the relationship obtained by log (S ₀ / S ₂₁ ) The exposed sample was placed in an oven at 120 ° C. for 25 seconds and at 11 ° C.
Heat development was performed at 8 ° C. for 25 seconds. The optical density of the obtained sample was measured and the sensitivity was calculated. The sensitivity was represented by the reciprocal of the exposure amount giving a density of 2.5. The sensitivity obtained by thermal development at 120 ° C. for 25 seconds was S ₀ , and the sensitivity obtained by thermal development at 118 ° C. for 25 seconds was S ₂₁ .

Formula (5) Determining the relationship obtained by γ ₂₁ / γ _{0 The} exposed sample was placed in an oven at 120 ° C. for 25 seconds and at 11 ° C.
Heat development was performed at 8 ° C. for 25 seconds. The optical density of the obtained sample was measured and the gamma value was calculated. The gamma value was represented by the slope of a straight line connecting the densities 0.1 and 2.5 of the characteristic curve when the photothermographic material was heated and developed. The gamma value obtained by thermal development at 120 ° C. for 25 seconds was γ ₀ , and the gamma value obtained by thermal development at 118 ° C. for 25 seconds was γ ₂₁ .

Formula (6) How to determine the relationship obtained by Dmax ₂₁ / Dmax _{0 The} exposed sample was placed in an oven at 120 ° C. for 20 seconds and 2 minutes.
The heat development was performed in 5 seconds. The optical density of the obtained sample was measured and the maximum density was calculated. The maximum density obtained by thermal development at 120 ° C. for 25 seconds was Dmax ₀ , and the maximum density obtained by thermal development at 118 ° C. for 25 seconds was Dmax ₂₁ , which was calculated according to equation (6). Table 2 shows the results of the evaluation.

[0296]

[Table 2]

Table 2 shows that the sample of the present invention is superior to the comparative sample in all evaluation items.

Example 3 Sample 201 was prepared in the same manner as in Example 2 except that the subbed support and the surface protective layer of Samples 201 and 202 were changed to the following.
Samples 301 and 30 exactly as in
2 was produced. These materials were evaluated in the same manner as in Example 2. Table 3 shows the results.

<Preparation of PET Support with Back / Undercoat Layer> (1) Support Using terephthalic acid and ethylene glycol, IV = 0.66 (phenol / tetrachloroethane = 6) according to a conventional method.
/ 4 (mass ratio, measured at 25 ° C.). After pelletizing this, dried at 130 ° C. for 4 hours,
After being melted at 300 ° C., it was extruded from a T-die and then rapidly cooled to prepare an unstretched film so that the film thickness after heat setting was 120 μm. This was longitudinally stretched 3.3 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 that, it was heat-set at 240 ° C. for 20 seconds, and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends, and the film was wound up at 4.8 kg / cm ² . Thus, a roll having a width of 2.4 m, a length of 3500 m, and a thickness of 120 μm was obtained.

(2) Undercoat Layer Undercoat Layer (a) Polymer latex; styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (% by mass) 160 mg / m ² 2, 4-dichloro-6-hydroxy-s-triazine 4 mg / m ² matting agent (polystyrene, average particle size 2.4 μm) 3 mg / m ² undercoat layer (b) Alkali-treated gelatin (Ca ⁺⁺ content 30 ppm, jelly strength 230 g) ) 50 mg / m ² Compound C The coating amount at which the optical density at 780 nm is 0.7.

[0301]

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(3) Conductive layer Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 38 mg / m ² SnO ₂ / Sb (9/1 mass ratio, average particle diameter 0.25 μm) 120 mg / m ² matting agent ( Polymethyl methacrylate, average particle size 5 μm) 7 mg / m ² Melamine 13 mg / m ² (4) Protective layer Chemipearl S-120 (manufactured by Mitsui Petrochemical Co., Ltd.) 500 mg / m ² Snowtex-C (Nissan Chemical Co., Ltd.) 40 mg / m ² Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.) An undercoat layer (a) and an undercoat layer (b) were sequentially coated on both sides of a 30 mg / m ² support, and each was coated at 180 ° C. Dry for 4 minutes. Next, a conductive layer and a protective layer are sequentially applied to one surface of the coated undercoat layer (a) and the undercoat layer (b), and dried at 180 ° C. for 4 minutes to form a back / undercoat layer. The used PET support was produced. The P with back / subbing layer thus prepared
The ET support was placed in a heat treatment zone having a total length of 200 m set at 200 ° C., a tension of 3 kg / cm ² , and a transfer speed of 20 m.
/ Min. Thereafter, the film was passed through a zone at 40 ° C. for 15 seconds and wound at a winding tension of 10 kg / cm ² .

(Surface protective layer coating solution 5) 40% polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid = 59/9/26/5/1)
262 g of water was added to 500 g of a copolymer of
g, 2.5 g of cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.)
12 g of compound E, 1 g of compound F, 2 g of compound G,
7.5 g of compound H, 0.5 g of polymethyl methacrylate fine particles having an average particle size of 3 μm as a matting agent were added in order, and water was further added to make 1000 g, and the viscosity was 5 cp (2
5 ° C.) and a coating solution having a pH of 4.5 (25 ° C.).

[0304]

Embedded image

(Surface protective layer coating solution 6) 40% polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid = 59/9/26/5/1)
262 g of water was added to 500 g of a copolymer of
g, 3.6 g of cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.),
12 g of compound E, 1 g of compound F, 2 g of compound G,
7.5 g of compound H, 3.4 g of polymethyl methacrylate fine particles having an average particle diameter of 3 μm as a matting agent, and 1 g of colloidal silica are sequentially added.
g, viscosity 5cp (25 ° C), pH 3.4 (25 ° C)
Was prepared.

<Preparation of Photothermographic Material> The coating solution for the image forming layer of Example 2 was coated on the subbing layer of the PET support provided with the backing / subbing layer at a coating amount of 1.6 g / m 2. ² was applied. Further, the photothermographic materials 301 and 302 were prepared by applying the surface protective layer coating solution 5 in the sample 301 and the surface protective layer coating solution 6 in the sample 302 so that the coating amount of the polymer latex was 2.0 g / m ^2. Produced. Evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

[0307]

[Table 3]

Table 3 shows that the sample of the present invention is superior to the comparative sample in all evaluation items.

Example 4 Example 101 was carried out in the same manner as in Example 1 except that Samples 101 and 102 produced in Example 1 were processed by an automatic thermal developing machine having the structure shown in FIG. Table 4 shows the results.

FIG. 1 shows a plate heater 120 made of a flocked steel sheet, which is a heating body heated to a temperature required for processing the photosensitive material sheet A, and a sheet heater 12 made of a sheet heater.
Transfer means 126 for moving (sliding) relative to the plate heater 120 while making contact with the surface of the plate heater 120;
A pressing roller 122 is provided for pressing the back side of the contact surface of the sheet A with the plate heater 120 for transferring heat from the plate heater 120 to the sheet A. The plate heater 120 is a flat plate. The plate heater 120 is a plate-shaped heating member in which a heating element of nichrome wire is laid and accommodated in a plane, and is maintained at a developing temperature of the photosensitive material. After exposure, the photosensitive material is guided to the automatic thermal developing machine 18 via a pair of supply rollers 126 driven by a driving device. Then, the supply roller pair 126
Is passed between the pressing roller 122 made of silicone rubber and the plate heater 120 to be subjected to heat treatment. The photosensitive material that has been heat-treated is a pair of discharge rollers.
Discharged via 28. In order to avoid abrasion as much as possible, the back layer side of the photosensitive material is
Touch The pressing roller 122 is a plate heater 12
0, or at a predetermined pitch over the entire length of the plate heater 120 in the transport direction with an interval equal to or less than the thickness of the photosensitive material.
22 and the plate heater 120, the sheet conveying path 1
24 are formed. At both ends of the sheet conveying path 124,
A supply roller pair 126 and a discharge roller pair, which are means for transferring the photosensitive material, are provided.

[0311]

[Table 4]

[0312] Table 4 shows that the sample of the present invention is superior to the comparative sample in all evaluation items.

Example 5 (Preparation of Subbed PET Support) A biaxially stretched heat-fixed PET film of 125 μm thickness manufactured by Teijin Limited was subjected to the following plasma treatment 1 on both sides, and then on one side. The following undercoating coating solution a-3 was applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-3. 3 is dry film thickness 0.8μ
m and dried to form an antistatic subbing layer B
-3. Next, the following plasma treatment 2 was applied to each undercoat layer surface.

<< Plasma Processing Conditions >> Batch type atmospheric pressure plasma processing apparatus (AP-IH, manufactured by EC Chemical Co., Ltd.)
-340), the high frequency output was 4.5 kW, the frequency was 5 kHz, the processing time was 5 seconds, and the gas conditions were 90%, 5% and 5% by volume of argon, nitrogen and hydrogen, respectively. And plasma treatment 2 were performed.

<< Undercoat Coating Solution a-3 >> Butyl Acrylate (30% by Mass) T-Butyl Acrylate (20% by Mass) Styrene (25% by Mass) 2-Hydroxyethyl Acrylate (25% by Mass) Copolymer Latex Solution (Solid content 30%) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Colloidal silica (average particle size 90 μm) 0.1 g Finish to 1 liter with water << Undercoating Coating Solution b-3 >> Tin oxide (average particle diameter 36 nm doped with 0.1% indium) An amount of 0.26 g / m ² Butyl acrylate (30% by mass), styrene (20% by mass), glycidyl Acrylate (40 mass%) copolymer latex liquid (solid content 30%) 270 g hexamethylene-1,6-bis ( In subbing drying process Chiren'urea) finish to 1 liter with 0.8g water "heat treatment of the support" above subbed support, the support is heated at 140 ° C., then slowly cooled. At that time, it was transported at a tension of 1 × 10 ⁵ Pa.

(Coating of Back Layer Surface Side) A coating liquid 4 of a back layer and a coating liquid 4 of a back protective layer having the following compositions were respectively filtered using a filter having a quasi-absolute filtration accuracy of 20 μm before coating, and then prepared by an extrusion coater. A total wet film thickness of 30 was formed on the antistatically processed undercoat layer B-3 of the support.
Coating was performed simultaneously at a rate of 120 m / min to a thickness of 120 μm, followed by drying at 60 ° C. for 4 minutes.

[0317] [Coating Solution for Back Layer 4] Methyl ethyl ketone 16.4 g / m ² polyester resin (Bostic Co., Vitel PE2200B) 106mg / m ² infrared dye -C 37 mg / m ² stabilizer B-1 (manufactured by Sumitomo Chemical Co. Sumilizer BPA) 20 mg / m ² stabilizer B-2 (Yoshitomi Pharmaceutical Tomisorb 77) 20 mg / m ² cellulose acetate propylate (Eastman Chemical Company CAP504-0.2) 1.0 g / m ² cellulose acetate butyrate (Eastman Chemical Company) CAB381-20) 1.0g / m ²

[0318]

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[Back protective layer coating liquid 4] Methyl ethyl ketone 22 g / m ² polyester resin (Bostic, Vitel PE2200B) 106 mg / m ² Antistatic agent; (CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₂₀ − [CH ₃ SiO ｛CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₀ (CH ₂ CH ₂ CH ₂ O) ₁₅ CH ₃ }] ₃₀ -Si (CH ₃ ) ₃ 22 mg / m ² Fluorine surfactant Agent F-1: C ₈ F ₁₇ SO ₃ Li 10 mg / m ² Cellulose acetate propylate (CAP504-0.2 from Eastman Chemical) 1.0 g / m ² Cellulose acetate butyrate (CAB381-20 from Eastman Chemical) 0 g / m ² matting agent (Fuji Devison's Siloid 74; silica having an average particle size of 7 μm) 17 mg / m ² (Preparation of photosensitive layer) << Preparation of photosensitive silver halide emulsion E >> A1 Phenylcarbamoyl gelatin 88.3 g Compound (A) (10% methanol solution) 10 ml Potassium bromide 0.32 g Finish with water to 5429 ml B1 0.67 mol / L silver nitrate aqueous solution 2635 ml C1 Potassium bromide 51.55 g Potassium iodide 1.47 g Make up to 660 ml with water D1 Potassium bromide 154.9 g Potassium iodide 4.41 g Iridium chloride (1% solution) 93 ml E1 0.4 mol / l aqueous potassium bromide solution Silver potential control amount below F1 56% acetic acid aqueous solution 16.0 ml G1 1.72 g anhydrous sodium carbonate Finish to 151 ml with water Compound (A): HO (CH ₂ CH ₂ O) _n- [CH (C
_{H 3) CH 2 O] 17} - (CH 2 CH 2 O) m H m + n =
5-7 The solution (B1) was added to the solution (A1) using a mixing stirrer shown in JP-B-58-58288 and JP-B-58-58289.
Of the solution (C1) at 45 ° C. and pAg8.
While controlling to 09, the addition was carried out by the simultaneous mixing method in 4 minutes and 45 seconds to form nuclei.

After a lapse of 7 minutes, the remainder of the solution (B1) and the entire amount of the solution (D1) were added by a double jet method over 14 minutes and 15 seconds while controlling the temperature at 45 ° C. and the pAg at 8.09. During the mixing, the pH of the reaction solution was 5.6.

After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (F1) was added to precipitate a silver halide emulsion. The supernatant was removed, leaving 2000 ml of sedimentation,
After adding 10 L of water and stirring, the silver halide was precipitated again. The supernatant was removed, leaving 1500 ml of the sedimented portion, and 10 L of water was further added. After stirring, the silver halide was sedimented. After removing the supernatant liquid leaving 1500 ml of the sedimented portion, the solution (G1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and water was added so as to be 1161 g per mol of silver.

This emulsion had an average grain size of 0.058 μm.
m, coefficient of variation of particle size 12%, [100] face ratio 9
It was 2% monodispersed cubic silver iodobromide grains.

The obtained grains were chemically sensitized with 2 × 10 ^-4 mol of sodium thiosulfate per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added.

<< Preparation of Powder Organic Silver Salt E >> Behenic acid 130.8 g and arachidic acid 67.7 in 4720 ml of pure water.
g, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 mol sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution.
While maintaining the temperature of the above-mentioned sodium fatty acid solution at 55 ° C., 31.7 g of the above-mentioned photosensitive silver halide emulsion E and 465 ml of pure water were added, and the mixture was stirred for 5 minutes.

Then, 702.6 ml of a 1M silver nitrate solution was added to 2
And the mixture was stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and draining are repeated until the conductivity of the waste water becomes 2 μS / cm, and centrifugal dehydration is performed. Inlet hot air temperature 7
Drying was performed under a 5 ° C. operating condition until the water content became 0.1% to obtain a powdered organic silver salt E. At this time, the dry hot air used was heated air in the atmosphere with an electric heater. An infrared moisture meter was used to measure the water content of the organic silver salt composition.

<< Preparation of Preliminary Dispersion E >> Polyvinyl butyral powder (Butvar B- manufactured by Monsanto)
79) with 14.57 g of methyl ethyl ketone (hereinafter referred to as MEK).
Dissolved in 1457 g, VMA-GETZMAN
Preliminary dispersion liquid E was prepared by gradually adding 500 g of the powdered organic silver salt E while stirring with a disperser DISPERMAT CA-40M manufactured by Company N and thoroughly mixing.

<< Preparation of Photosensitive Emulsion Dispersion E >> Zirconia beads having a diameter of 0.5 mm (Toray Toraycere, manufactured by Toray Industries Co., Ltd.) were added to the preliminary dispersion E using a pump so that the residence time in the mill was 10 minutes. Media type disperser DI filled with 80%
SPERMAT SL-C12EX type (VMA-GET
ZEMNN) and dispersed at a mill peripheral speed of 13 m / s to prepare a photosensitive emulsion dispersion E.
After the dispersion, the organic silver salt particles were observed with an electron microscope photograph. Three
As a result of measuring the particle size and thickness of 00 organic silver salt particles, 2
05 were monodispersed tabular organic silver salts having an AR of 3 or more and a dispersity of 25%. Incidentally, the average particle size was 0.7 μm.
When the organic silver salt particles were similarly observed after coating and drying,
The same particles could be confirmed.

<< Preparation of Stabilizer Liquid >> 0.9 g of Stabilizer 1,
0.28 g of potassium acetate was dissolved in 10.1 g of methanol to prepare a stabilizer solution.

<< Preparation of Infrared Sensitizing Dye Liquid >> 29 mg of infrared sensitizing dye 1, 4.5 g of 2-chloro-benzoic acid, 8.4
g of Stabilizer 2 and 280 mg of 5-methyl-2-mercaptobenzimidazole were dissolved in 77.2 ml of MEK in the dark to prepare an infrared sensitizing dye solution. << Preparation of additive liquid a-1 >> 107 g of reducing agent A-4, 4.
8 g of 4-methylphthalic acid, 1 g of the compound 21 of the general formula (1) or (2) (see Chemical formula 47), and 0.74 g of infrared dye-C were dissolved in 260 g of MEK to prepare an additive solution a-1.

<< Preparation of Additive Solution b-1 >> 11.6 g of antifoggant 2 and 10 g of acid anhydride 4-11 were added to MEK126.
g) to give an additive liquid b-1.

<< Preparation of Additive Liquid c >> 21 g of an alkoxysilane compound: Ph—NH— (CH ₂ ) —Si— (OC
H ₃ ) ₃ was dissolved in 204 g of MEK to obtain an additive liquid c.

[0332]

Embedded image

<< Preparation of Photosensitive Layer Coating Solution E >> The photosensitive emulsion dispersion E (1641 g) and MEK 506 g were kept at 21 ° C. while stirring, and 10.75 g of antifoggant 1 (11.2% methanol solution) was added. The mixture was stirred for 1 hour.
Further, calcium bromide (11.2% methanol solution) 1
3.6 g was added and stirred for 20 minutes. When the silver halide therein was observed with an electron microscope, silver halide grains of less than 0.01 μm could be observed. The silver halide grains were observed with an electron microscope photograph. When the particle size of 500 organic silver salt particles was measured, the number of particles having a particle size of less than 0.01 μm was 45% of the total number of silver halide particles.

Subsequently, 11.3 g of a stabilizer solution was added to add 1
After stirring for 0 minutes, 90.5 g of an infrared sensitizing dye solution was added, followed by stirring for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While maintaining the temperature at 13 ° C, polyvinyl butyral (Monsanto Butvar)
B-79) 349.6 g was added and stirred for 30 minutes, and then 5-methyl-2-mercaptobenzimidazole 9 was added.
5 mg and 3.5 g of tetrachlorophthalic acid were added and 30
Stirred for minutes. Then 1.2 g of 5-nitroindazole, 0.4 g of 5-nitrobenzimidazole, 2.4
g of contrast agent 72-15 (vinyl compound), 1 g of contrast agent H-5-5 (hydrazine derivative) and MEK24
2 g were added. While further stirring, the additive liquid a-1
373.5 g, 148.6 g of the additional solution b-1 and 225 g of the additional solution c were sequentially added and stirred to obtain a photosensitive layer coating solution E.

<< Preparation of Photosensitive Silver Halide Emulsion F >> As in the case of the photosensitive silver halide emulsion E, pAg and pH were controlled to obtain an average grain size of 0.07 μm, a variation coefficient of grain size of 45%, and [100]. Non-monodispersed cubic silver iodobromide grains having an area ratio of 45% were obtained. Further, the obtained grains were chemically sensitized with 2 × 10 ⁻⁴ mol of sodium thiosulfate per mol of silver halide, and then 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added to obtain a photosensitive silver halide emulsion F.

<< Preparation of Powdered Organic Silver Salt F >> 130.8 g of behenic acid and 67.7 g of arachidic acid in 4720 ml of pure water.
g, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 mol sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution.
While maintaining the temperature of the above-mentioned fatty acid sodium solution at 60 ° C., 31.7 g of the above-mentioned photosensitive silver halide emulsion F and 465 ml of pure water were added and stirred for 5 minutes.

Next, 702.6 ml of a 1 mol silver nitrate solution was added over 2 minutes, and the mixture was stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and draining are repeated until the conductivity of the waste water becomes 2 μS / cm, and centrifugal dehydration is performed. Inlet hot air temperature 6
Drying was performed under a 5 ° C. operating condition until the water content became 0.3% to obtain a powdered organic silver salt F. At this time, the dry hot air used was heated air in the atmosphere with an electric heater. An infrared moisture meter was used to measure the water content of the organic silver salt composition.

<< Preparation of Preliminary Dispersion F >> Polyvinyl butyral powder (Butvar B- manufactured by Monsanto)
79) with 14.57 g of methyl ethyl ketone (hereinafter referred to as MEK).
Dissolved in 1457 g, VMA-GETZMAN
A preliminary dispersion liquid F was prepared by gradually adding 500 g of the powdered organic silver salt F while stirring with a dissolver DISPERMAT CA-40M manufactured by Company N and thoroughly mixing.

<< Preparation of Photosensitive Emulsion Dispersion F >> A 0.5 mm diameter zirconia bead (Treseram, manufactured by Toray Industries, Inc.) was added to the preliminary dispersion F using a pump so that the residence time in the mill was 2 minutes using a pump. Media type disperser DIS filled with 80%
PERMAT SL-C12EX type (VMA-GETZ
The emulsion was dispersed at a mill peripheral speed of 13 m / s to prepare a photosensitive emulsion dispersion F. After the dispersion, the organic silver salt particles were observed with an electron microscope photograph. It was a non-monodispersed organic silver salt having an average particle size of 0.7 μm and a degree of dispersion of 60%. When the organic silver salt particles were similarly observed after coating and drying, the same particles were confirmed.

<< Preparation of Stabilizer Liquid >> 0.9 g of Stabilizer 1,
0.28 g of potassium acetate was dissolved in 10.1 g of methanol to prepare a stabilizer solution.

<< Preparation of Infrared Sensitizing Dye Liquid >> 29 mg of infrared sensitizing dye 1, 4.5 g of 2-chloro-benzoic acid, 8.4
g of Stabilizer 2 and 280 mg of 5-methyl-2-mercaptobenzimidazole were dissolved in 77.2 ml of MEK in the dark to prepare an infrared sensitizing dye solution.

<< Preparation of Additive Solution a-2 >> 107 g of reducing agent A-4, 4.8 g of 4-methylphthalic acid, and 0.74 g of infrared dye-C were dissolved in 261 g of MEK to obtain an additive solution a-2. .

<< Preparation of Additive Solution b-2 >> 11.6 g of the antifoggant 2 was dissolved in 136 g of MEK to prepare an additive solution b-2.

<< Preparation of Additive Liquid c >> 21 g of an alkoxysilane compound: Ph—NH— (CH ₂ ) —Si— (OC
H ₃ ) ₃ was dissolved in 204 g of MEK to obtain an additive liquid c. << Preparation of Photosensitive Layer Coating Solution F >> The photosensitive emulsion dispersion F (1)
641 g) and 526 g of MEK at 21 ° C. while stirring.
, And 1.75 g of antifoggant 1 (11.2% methanol solution) was added, followed by stirring for 1 hour. Further, 3.6 g of calcium bromide (11.2% methanol solution) was added and stirred for 1 minute. When the silver halide therein was observed with an electron microscope, silver halide grains of less than 0.01 μm could be observed. When the silver halide was observed with an electron microscope, no silver halide grains of 0.01 μm or less were observed.

Subsequently, 11.3 g of a stabilizer liquid was added to add 1
After stirring for 0 minutes, 90.5 g of an infrared sensitizing dye solution was added, followed by stirring for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While maintaining the temperature at 13 ° C, polyvinyl butyral (Monsanto Butvar)
B-79) 349.6 g was added and stirred for 30 minutes, and then 5-methyl-2-mercaptobenzimidazole 9 was added.
5 mg and 3.5 g of tetrachlorophthalic acid were added and 30
Stirred for minutes. Then 1.2 g of 5-nitroindazole, 0.4 g of 5-nitrobenzimidazole and M
245 g of EK were added. While further stirring, 373.5 g of the additional liquid a-2 and 148.6 g of the additional liquid b-2.
g and 225 g of the additive solution c were sequentially added and stirred to obtain a photosensitive layer coating solution F.

<< Preparation of Matting Agent Dispersion 7 >> Monodisperse silica 30 having an average particle size of 6 μm was added to 1.7 g of MEK per 1 m ^2.
mg and 8000 with a dissolver-type homogenizer.
This was dispersed at 30 rpm for 30 minutes to prepare a matting agent dispersion liquid 7.

<< Preparation of Additive Solution d >> 0.17 per m ²
g of phthalazine was dissolved in MEK of 2.73 g per 1 m ^{2 to} obtain an additive liquid d.

<< Preparation of Surface Protective Layer Coating Solution 7 >> While stirring 15.9 g of MEK per 1 m ² , cellulose acetate butyrate (Eastman Chemical) was used.
CAB171-15): 1.8 g, polymethylmethacrylic acid (Rohm & Haas Company, Paraloid A-21):
85 mg, benzotriazole: 20 mg, fluorine-based surfactant F-1: 13 mg, fluorine-based surfactant F-
_{2: C 8 F 17 (CH} 2 CH 2 O) 22 C 8 F 17 50mg, silicon antistatic agent _{AS-1: (CH 3)} 3 SiO-
[(CH ₃ ) ₃ SiO] ₂₀ -[(CH ₃ SiO—CH ₂ CH
₂ CH ₂ O) (CH ₂ CH ₂ O) ₆ (CH ₂ CH ₂ CH ₂ O) _{6
CH 2 CH 2 O 20] -OSi} (CH 3) was added 320mg dissolution. Next, 1.75 g of the matting agent dispersion 7 and 2.9 g of the additive solution d were sequentially added and stirred to prepare a surface protective layer coating solution 7.

<< Preparation of Matting Agent Dispersion 8 >> 40 mg of monodispersed silica having an average particle size of 3.5 μm was added to 1.7 g of MEK per 1 m ^{2, and the} mixture was treated with a dissolver-type homogenizer.
The mixture was dispersed at 00 rpm for 30 minutes to prepare a matting agent dispersion liquid 8.

<< Preparation of Additive Solution d >> 0.17 per 1 m ²
g of phthalazine was dissolved in MEK of 2.73 g per 1 m ^{2 to} obtain an additive liquid d.

<< Preparation of Surface Protective Layer Coating Solution 8 >> While stirring 15.9 g of MEK per 1 m ² , cellulose acetate butyrate (Eastman Chemical) was used.
CAB171-15): 1.8 g, polymethylmethacrylic acid (Rohm & Haas Company, Paraloid A-21):
85 mg, 20 mg of benzotriazole and 20 mg of fluorine-based surfactant F-1 were added and dissolved. Next, 1.75 g of the matting agent dispersion liquid 8 and 2.9 g of the additive liquid d were sequentially added and stirred to prepare a surface protective layer coating liquid 8.

<< Coating on Photosensitive Layer >> The viscosity of the coating solution for the photosensitive layer and the coating solution for the surface protective layer was adjusted to 0.228 Pa · s and 0.184 Pa · s by adjusting the amount of the solvent.
Each coating solution is passed through a filter having a quasi-absolute filtration accuracy of 20 μm, filtered, discharged from a slit of an extrusion die coater, laminated, and overlaid on the undercoat layer A-3 at a speed of 90 m / min. At the same time. At that time, the coating solution for the photosensitive layer and the coating solution for the surface protective layer were applied in combinations shown in Table 5, respectively. Eight seconds later, drying was performed for 5 minutes using hot air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C., and then the temperature and humidity were 23 ° C. and 50% RH, and the tension was 196 N / m
(20 kg / m) and rolled into a roll
The following photosensitive materials were prepared. The photosensitive layer of the obtained photosensitive material had a coated silver amount of 1.5 g / m ² and the surface protective layer had a dry film thickness of 2.5 μm.

Thus, as shown in Table 5, Sample 5
01 and 502 were obtained. The amount of the remaining solvent methyl ethyl ketone (MEK) in the obtained sample was 70 mg / m ² . The Vickers hardness of the surface of the sample 501 on the image forming layer side was 100. In addition, 25 samples were obtained.
After humidity control for 24 hours in an environment of 60 ° C. and 60% RH, a film area of 46.3 cm ² was cut out under the same atmosphere.
After measuring the mass, this was finely chopped to about 5 mm, stored in a dedicated vial, sealed with a septum and an aluminum cap, and then set in a Hewlett-Packard HP7694 headspace sampler, and the headspace sampler was heated to 120 ° C. After heating for 20 minutes and evaporating water, the equilibrium water content of the sample was determined by the Karl Fischer method. The result was 6% for sample 502 and 0.7% for sample 501.

Evaluation was performed in the same manner as in Example 1. Table 5 shows the results.

[0355]

[Table 5]

Table 5 shows that the sample of the present invention is superior to the comparative sample in all evaluation items.

[0357]

According to the present invention, there is provided a photothermographic material which has excellent transportability in an automatic thermal developing machine, has no fog increase after development, and has improved stability under fluctuations in development conditions, and an image forming method thereof. Could be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view of an automatic thermal developing machine.

DESCRIPTION OF SYMBOLS A Photosensitive material sheet 120 Plate heater 122 Press roller 122a Upstream press roller 122b Downstream press roller 124 Sheet transport path 125 Heat retaining cover 126 Supply roller pair 128 Discharge roller pair

Claims (11)

[Claims] 1. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the sensitivity is represented by the following formula (1). Photosensitive material. Formula (1) log (S ₀ / S ₁₁ ) <0.7 [where S ₀ is a sensitivity obtained by thermally developing the photothermographic material at 120 ° C. for 25 seconds, and S ₁₁ is a photothermographic material. 120
This represents the sensitivity obtained by heat development at 20 ° C. for 20 seconds. The sensitivity represents the reciprocal of the exposure amount that gives a density of 2.5 when the photothermographic material is heated and developed. ] 2. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the gamma value has a relationship represented by the following formula (2). Developed photosensitive material. Formula (2) γ ₁₁ / γ ₀ > 0.8 [where γ ₀ is a gamma value obtained by thermally developing the photothermographic material at 120 ° C. for 25 seconds, and γ ₁₁ is a value obtained when the photothermographic material is obtained. It represents a gamma value obtained by heat development at 120 ° C. for 20 seconds. The gamma value is represented by the slope of a straight line connecting the densities 0.1 and 2.5 of the characteristic curve when the photothermographic material is heated and developed. ] 3. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the maximum density of the photothermographic material has a relationship represented by the following formula (3). Developed photosensitive material. Formula (3) Dmax ₁₁ / Dmax ₀ > 0.8 [In the formula, Dmax ₀ is the temperature of the photothermographic material at 120 ° C. and 25 ° C.
The maximum density obtained by thermal development in seconds, Dmax ₁₁ represents the maximum density obtained by thermally developing the photothermographic material at 120 ° C. for 20 seconds. ] 4. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the sensitivity has a relationship represented by the following formula (4). Photosensitive material. Formula (4) log (S ₀ / S ₂₁ ) <1.0 [where S ₀ is the sensitivity obtained by thermally developing the photothermographic material at 120 ° C. for 25 seconds, and S ₂₁ is the photothermographic material. 118
The sensitivity obtained by heat development at 25 ° C. for 25 seconds. The sensitivity represents the reciprocal of the exposure amount that gives a density of 2.5 when the photothermographic material is heated and developed. ] 5. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the gamma value of the photothermographic material has a relationship represented by the following formula (5). Developed photosensitive material. Formula (5) γ ₂₁ / γ ₀ > 0.7 [where γ ₀ is the gamma value obtained by thermally developing the photothermographic material at 120 ° C. for 25 seconds, and γ ₂₁ is the photothermographic material. Represents the gamma value obtained by heat development at 118 ° C. for 25 seconds. The gamma value is represented by the slope of a straight line connecting the densities 0.1 and 2.5 of the characteristic curve when the photothermographic material is heated and developed. ] 6. A photothermographic material comprising a support containing silver halide, an organic silver salt and a reducing agent, wherein the maximum density of the photothermographic material is represented by the following formula (6). Developed photosensitive material. Formula (6) Dmax ₂₁ / Dmax ₀ > 0.7 [In the formula, Dmax ₀ is the temperature of the photothermographic material at 120 ° C. and 25 ° C.
The maximum density obtained by thermal development in seconds, Dmax ₂₁ , represents the maximum density obtained by thermally developing the photothermographic material at 118 ° C. for 25 seconds. ] 7. The photothermographic material according to claim 1, wherein a hardening agent is contained in the constituent layer containing the organic silver salt. 8. The photothermographic material according to claim 1, wherein the constituent layer containing the organic silver salt contains an acid anhydride. 9. The composition according to claim 1, wherein the constituent layer containing the organic silver salt contains a compound represented by the following general formula (1) or (2). 2. The photothermographic material according to claim 1. Embedded image [Wherein, Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group, T ₁ represents a divalent linking group or a linking group comprising an aliphatic hydrocarbon group, and J ₁ represents an oxygen atom, a sulfur atom or Represents a divalent linking group or linking group containing at least one nitrogen atom. Ra, Rb, Rc, and Rd each represent a hydrogen atom, an acyl group, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group;
And Rd, Ra and Rc or Rb and Rd, and in the general formula (2), Ra and Rb, Ra and Rc or R
It can combine between b and Rc to form a nitrogen-containing heterocyclic group. M ₁ represents an ion required to neutralize the intramolecular charge. ] 10. The photothermographic material according to claim 1, wherein an equilibrium water content of the photothermographic material is within 2% by mass. 11. An image forming method comprising: exposing the photothermographic material according to claim 1 to a heat development process to form an image.