JP2000284405A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a change in photographic performances (sensitivity and Dmin) in the case of a change in development conditions (temperature and time) and preservation after processing by using a polymer latex as the binders of an image forming layer and a protective layer and incorporating a specified compound into a layer on the image forming layer side. SOLUTION: The heat developable photosensitive material has an image forming layer containing at least a nonphotosensitive organic silver salt, photosensitive silver halide, a reducing agent and a nucleus forming agent on the substrate and a protective layer on the image forming layer. A polymer latex is used as the binders of the image forming layer and the protective layer and a layer on the image forming layer side contains a compound of the formula, wherein Z1 and Z2 are each halogen, X1 is H or an electron withdrawing group, Y1 is -CO- or -SO2-, Q is arylene or a divalent heterocyclic group, L is a combining group, W is carboxyl, its salt, sulfo, its salt or the like and (n) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to an ultra-hard tone photothermographic material for an image setter used for photolithography. The present invention relates to a photothermographic material having ultra-high contrast with little fluctuation in performance with storage time.

[0002]

2. Description of the Related Art There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technique for forming an image by thermal development is a system that can simplify environmental preservation and image forming means.

In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental protection and space saving.
Therefore, there is a need for a technology relating to a photothermographic material for photoengraving, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a clear black image having high resolution and sharpness. It has been. In these photosensitive heat developing materials,
By eliminating the use of solution processing chemicals, it is possible to provide customers with a simpler and more environmentally friendly thermal development processing system.

[0004] Methods of forming an image by thermal development are described in, for example, US Patent Nos. 3,152,904 and 3,457,075, and US Pat.
Morgan and B.A. "Thermal Proces Silver System (Thermally Proces)" by Shely
sed Silver Systems) A "(Imaging Processes and M
aterials) Neblette 8th edition, Sturge, V.E.
Walworth, A .; Shepp
Edited, page 2, 1969). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

[0005] Such photothermographic materials have been put to practical use mainly in micro and medical fields.
It is a high temperature of not less than ° C., and there is a problem that the performance fluctuates and the preservability of an image is poor due to a slight fluctuation of the developing temperature or time, and improvement has been desired.

On the other hand, in the field of graphic arts, softer photothermographic materials have not been accepted because higher contrast is required.

[0007] In order to overcome this problem, a heat development technique which develops ultra-high contrast characteristics by using a nucleating agent is disclosed in US Pat.
No. 96695, No. 5556322, No. 5545515, No. 5635339, many of these photosensitive materials are toluene,
The photosensitive layer is formed by applying a coating solution using an organic solvent such as methyl ethyl ketone (MEK) or methanol as a solvent. Using an organic solvent as a solvent,
This is disadvantageous not only in the adverse effect on the human body in the manufacturing process but also in the cost due to the recovery of the solvent and the like.

On the other hand, the photothermographic material having ultra-high contrast characteristics disclosed in the above-mentioned patent documents shows good photographic performance under optimal heat development conditions, but changes in environmental temperature and humidity, development time and development time. Due to a slight change in the temperature, the maximum density (Dmax) and the dot percentage change rapidly,
There was a problem that min increased.

Therefore, a method of forming a photosensitive layer (hereinafter, also referred to as "aqueous photosensitive layer") using a coating solution of a water solvent which does not have such a concern has been considered. For example,
JP-A-49-52626 and JP-A-53-116144 describe examples using gelatin as a binder. Also Japanese Patent Laid-Open No. 50-151
No. 138 describes an example using polyvinyl alcohol as a binder.

Japanese Patent Application Laid-Open No. Sho 60-61747 describes an example in which gelatin and polyvinyl alcohol are used in combination. As another example, JP-A-58-28737 describes an example of a photosensitive layer using water-soluble polyvinyl acetal as a binder.

Certainly, when such a binder is used, the photosensitive layer can be formed by using a coating solution of an aqueous solvent, and there are great environmental and cost advantages.

However, when a polymer such as gelatin, polyvinyl alcohol, or water-soluble polyacetal is used as a main binder, the compatibility with an organic silver salt is poor, and not only a coated material which can be practically used due to the coated surface quality cannot be obtained, but also Only those having a markedly impaired commercial value, such as a low blackening density in exposed areas and a high density in unexposed areas, were obtained.

[0013] A technology for producing a water-based photosensitive material excellent in environment and cost, having good coating surface quality and exhibiting ultra-high contrast characteristics,
JP-A-10-10669, Japanese Patent Application No. 8-316985
No., Japanese Patent Application No. 9-171750, Japanese Patent Application No. 10-2500
3, Japanese Patent Application No. 10-34184, Japanese Patent Application No. 10-413
01, Japanese Patent Application No. 10-41304, Japanese Patent Application No. 10-79
994 and Japanese Patent Application No. 10-112721. Although the coating surface quality and photographic performance have been remarkably improved by these techniques, further improvement in performance is desired from the viewpoint of quality stability in the market.

Color photoengraving includes Y, M, C
It is good to perform the exposure and heat development of these four plates at the same time, but it is often the case that the exposure / heat development is performed with a time lag. In such a case, since the elapsed time after the heat development processing of each film is different, the dimensions of each film do not match, which often causes a color shift.

To solve this problem, a technique of applying a support having an undercoat layer containing a vinylidene chloride copolymer to a photothermographic material is disclosed in Japanese Patent Application No. 10-221039.
And Japanese Patent Application No. 10-355429. These techniques have a remarkable effect on dimensional changes, but new problems such as an increase in fog (Dmin) due to storage or light irradiation of the processed film, and a change in the exposure time to the PS plate. There has occurred.

[0016]

Accordingly, an object of the present invention is to solve the problem of photographic performance (sensitivity, D) with respect to fluctuations in development temperature conditions (temperature, time) and storage time after processing.
The present invention is to provide a photothermographic material in which the fluctuation of the photothermographic material is improved, and more specifically, to provide a photothermographic material which exhibits ultra-high contrast characteristics more stably for photolithography. Another object of the present invention is to provide a photothermographic material having excellent dimensional stability.

[0017]

These objects are achieved by the present invention described below. (1) On a support, an image forming layer containing at least (a) a non-photosensitive organic silver salt, (b) a photosensitive silver halide, (c) a reducing agent and (d) a nucleating agent, and this image A protective layer on the forming layer, wherein a polymer latex is used as a binder for the image forming layer and the protective layer, and the layer on the image forming layer side contains a compound represented by the formula (1). Photothermographic material.

[0018]

Embedded image

[In the formula (1), Z ¹ and Z ² each represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, and Y ¹ represents a —CO— group or a —SO ₂ — group. ,
Q represents an arylene group or a divalent heterocyclic group; L represents a linking group; W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphate group, a hydroxyl group, a quaternary ammonium group or a polyethyleneoxy group. Represent. n represents 0 or 1. (2) a substituted alkene derivative represented by the following formula (2):
The photothermographic material according to the above (1), comprising a substituted isoxazole derivative represented by the following formula (3) and at least one nucleating agent selected from a specific acetal compound represented by the following formula (4).

[0020]

Embedded image

[In the formula (2), R ¹ , R ² and R
³ independently represent a hydrogen atom or a substituent;
Represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. formula
In (3), R ⁴ represents a substituent. In equation (4),
X and Y each independently represent a hydrogen atom or a substituent; A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic group; Represents a thio group or a heterocyclic amino group. In the formula (4), X and Y, and A and B may be bonded to each other to form a cyclic structure. (3) The support has a thickness of 0.3 μm or more (total thickness per one side) containing a vinylidene chloride copolymer containing at least 70% by weight of a repeating unit of vinylidene chloride monomer on both surfaces thereof. The photothermographic material according to the above (1) or (2), having an undercoat layer.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The photothermographic material of the present invention comprises at least (a) a non-photosensitive organic silver salt, (b) a photosensitive silver halide,
(C) an image forming layer containing a reducing agent and (d) a nucleating agent (that is, a photosensitive layer), and a protective layer on the image forming layer.
Polymer latex is used as a binder for these image forming layers and protective layers. In such a photothermographic material, at least one of the layers on the image forming layer side (that is, the image forming layer and its adjacent layer, or the protective layer)
By containing the compound represented by the formula (1),
A change in photographic performance due to a temperature change during thermal development can be suppressed, and an increase in Dmin due to storage time after processing is small. This effect is remarkable in a system containing a nucleating agent as a plate making film or a support having an undercoat surface containing a vinylidene chloride copolymer.

The organic silver salt that can be used in the present invention includes:
Relatively stable to light, but forms a silver image when heated to 80 ° C or higher in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids,
Particularly, a silver salt of a long-chain fatty carboxylic acid (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) is preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor is preferably present in about 5-7 of the imaging layer.
0% by weight can be constituted. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate,
Silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, it is preferable to use silver behenate having a silver behenate content of 85 mol% or more, more preferably 95 mol% or more, of the above-mentioned organic silver salts or a mixture of the organic silver salts. . Here, the content of silver behenate indicates the molar fraction of silver behenate with respect to the organic acid silver used. As the organic acid silver other than silver behenate contained in the organic acid silver used in the present invention, those mentioned above can be preferably used.

The organic acid silver which is preferably used in the present invention is
Alkali metal salts of organic acids shown above (Na salt, K salt,
It is prepared by reacting silver nitrate with a solution or suspension. The alkali metal salt of an organic acid of the present invention is obtained by treating the above organic acid with an alkali. The silver salt of an organic acid of the present invention can be carried out batchwise or continuously in any suitable vessel. The stirring in the reaction vessel can be performed by any stirring method depending on the required characteristics of the particles. Examples of the method for preparing silver organic acid include a method in which an aqueous silver nitrate solution is gradually or rapidly added to a reaction vessel containing an organic acid alkali metal salt solution or suspension, and a method in which an organic acid prepared in advance in a reaction vessel containing a silver nitrate aqueous solution is used. Preferably, a method of gradually or rapidly adding an alkali metal salt solution or suspension, and a method of simultaneously adding a previously prepared aqueous solution of silver nitrate and an organic acid alkali metal salt solution or suspension into a reaction vessel are preferably used. Can be.

The silver nitrate aqueous solution and the organic acid alkali metal salt solution or suspension may be of any concentration for controlling the particle size of the prepared organic acid silver, and may be added at any addition rate. Can be. The silver nitrate aqueous solution and the organic acid alkali metal salt solution or suspension can be added by a method of adding at a constant addition rate, an accelerated addition method by an arbitrary time function, or a deceleration addition method. Further, it may be added to the surface of the reaction solution or may be added to the reaction solution. In the case of a method in which a previously prepared aqueous silver nitrate solution and an organic acid alkali metal salt solution or suspension are simultaneously added to the reaction vessel, either the silver nitrate aqueous solution or the organic acid alkali metal salt solution or suspension is preceded. Although it can be added, it is preferable to add the silver nitrate aqueous solution in advance. The degree of precedence is preferably 0 to 50 vol% of the total amount added, and 0 to 2 vol%.
5 vol% is particularly preferred. As described in JP-A-9-127643, a method of adding while controlling the pH or silver potential of the reaction solution during the reaction can also be preferably used.

The pH of the silver nitrate aqueous solution or organic acid alkali metal salt solution or suspension to be added can be adjusted according to the required characteristics of the particles. An optional acid or alkali can be added for pH adjustment. In addition, depending on the required characteristics of the particles, for example, the temperature in the reaction vessel can be set arbitrarily for controlling the particle size of the prepared organic acid silver salt. Alternatively, the suspension can also be adjusted to any temperature. The organic acid alkali metal salt solution or suspension is preferably heated and kept at 50 ° C. or higher in order to ensure fluidity of the solution.

The silver salt of an organic acid used in the present invention is preferably prepared in the presence of a tertiary alcohol. Preferably, the tertiary alcohol is one having a total carbon number of 15 or less,
Particularly preferred is 10 or less. Preferred examples of the tertiary alcohol include tert-butanol, but the present invention is not limited thereto.

The tertiary alcohol used in the present invention may be added at any timing during the preparation of the organic acid silver salt. However, the tertiary alcohol may be added during the preparation of the organic acid alkali metal salt to dissolve the organic acid alkali metal salt. Is preferred. The amount of the tertiary alcohol used in the present invention can be arbitrarily used in a weight ratio of 0.01 to 10 with respect to H ₂ O as a solvent at the time of preparing the silver salt of an organic acid. Is preferred.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but needle crystals having a short axis and a long axis are preferred. In the present invention, the minor axis is 0.01 μm or more and 0.2 μm or more.
0 μm or less, major axis of 0.10 μm or more and 5.0 μm or less, minor axis of 0.01 μm or more and 0.15 μm or less, and major axis of 0.10 μm or more and 4.0 μm or less are more preferred. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by each minor axis, major axis is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of determining the standard deviation of the volume-weighted average diameter of the organic silver salt, the percentage of the value divided by the volume-weighted average diameter (coefficient of variation) is preferably 100% or less, more Preferably 80% or less,
More preferably, it is 50% or less. As a measuring method, for example, the particle size (volume weighted average diameter) obtained by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained. Can be.

The organic silver salt which can be used in the present invention is
Preferably, desalting can be performed. The method for desalting is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, and floc-forming water washing by a coagulation method can be preferably used.

In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size and no aggregation, an organic silver salt which is an image forming medium and a photosensitive silver salt are substantially contained. It is preferable to use a dispersion method in which a water dispersion liquid which is not included in the liquid is converted into a high-speed flow and then the pressure is reduced.

After passing through such steps, the mixture is mixed with an aqueous solution of a photosensitive silver salt to prepare a coating solution for a photosensitive image forming medium. When a photothermographic material is prepared using such a coating solution, a haze is low, and a low-fogging, high-sensitivity photothermographic material can be obtained. On the other hand, when the photosensitive silver salt is coexistent when the light is converted into a high-pressure, high-speed flow and dispersed, the fog increases and the sensitivity is remarkably lowered. When an organic solvent is used instead of water as a dispersion medium, haze increases, fog increases, and sensitivity tends to decrease. On the other hand, when a conversion method for converting a part of the organic silver salt in the dispersion to the photosensitive silver salt is used instead of the method of mixing the aqueous solution of the photosensitive silver salt, the sensitivity is reduced.

In the above, the aqueous dispersion converted and dispersed under high pressure and high speed contains substantially no photosensitive silver salt, and its water content is relative to that of the non-photosensitive organic silver salt. 0.
The content is 1 mol% or less, and the photosensitive silver salt is not positively added.

In the present invention, the solid dispersion apparatus and the technique used for carrying out the dispersion method as described above are described in, for example, "Dispersion Rheology and Dispersion Technology" (Toshio Kajiuchi, Hiroki Usui, 1991, Shinzansha Publishing Co., Ltd., p357
-P403), "The 24th Progress of Chemical Engineering", edited by The Society of Chemical Engineers, Tokai Branch, 1990, Maki Shoten, p184-p185),
Although detailed in the dispersing method of the present invention, the aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and sent into a pipe, and then passed through a narrow slit provided in the pipe, Thereafter, the dispersion is finely dispersed by causing an abrupt pressure drop in the dispersion.

The high-pressure homogenizer to which the present invention relates is generally composed of (a) a "shear force" generated when the dispersoid passes through a narrow gap at a high pressure and a high speed, and (b) a dispersoid is generated under a high pressure and a normal pressure. It is considered that the particles are dispersed into fine particles by a dispersing force such as "cavitation force" generated when the particles are released. As an example of this type of dispersing apparatus, a Gaulin homogenizer is mentioned in the past.In this apparatus, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on a cylindrical surface, and the force is applied to the surrounding wall by the force. The particles collide and are emulsified and dispersed by the impact force. Working pressure is generally 10
0~600kg / cm ^2, the flow rate is in the range of a few M～30m / sec, be devised that the high flow rate portion was devised such increasing the number collisions in the saw-toothed in order to increase the dispersion efficiency I have. On the other hand, in recent years, apparatuses capable of dispersing at higher pressure and higher flow rate have been developed, and typical examples thereof include a microfluidizer (Microfluidex International Corporation) and a nanomizer (specialized machine). Industrial Co., Ltd.).

As a dispersion apparatus suitable for the present invention, a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation is used.
(G ¹ 0Z with interaction chamber), M-
110Y (with H10Z interaction ^{chamber), M-140K (G 1} 0Z with interaction chamber), HC-5000 (L30Z or H23
With 0Z interaction chamber), HC-80
00 (with an E230Z or L30Z interaction chamber) and the like.

Using these devices, an aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and fed into a pipe, and then passed through a narrow slit provided in the pipe to obtain a desired pressure. Is applied, and thereafter, the pressure in the pipe is rapidly returned to the atmospheric pressure, or the like, and a sudden pressure drop is caused in the dispersion to obtain an organic silver salt dispersion optimal for the present invention. .

Prior to the dispersion operation, it is preferable to predisperse the raw material liquid. As means for preliminary dispersion, known dispersion means (e.g., high-speed mixer, homogenizer, high-speed impact mill, Banbury mixer, homomixer, kneader, ball mill, vibration ball mill, planetary ball mill, attritor, sand mill, bead mill, colloid mill,
Jet mill, roller mill, tron mill, high-speed stone mill) can be used. In addition to mechanical dispersion, the particles may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersing aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after completion of the fine particle formation.

In the organic silver salt dispersion of the present invention, the flow rate,
It is possible to disperse to the desired particle size by adjusting the pressure difference during pressure drop and the number of treatments.However, from the viewpoint of photographic characteristics and particle size, the flow rate is 200 m / sec to 600 m / sec, is preferably in the range pressure is 900~3000kg / cm ^2, flow rate 300
m / sec ～600M / sec, the pressure difference at the pressure drop 1500~3000kg / cm ²
More preferably, it is within the range. The number of times of distributed processing can be selected as needed, but usually 1 to 10 times of processing is selected. From the viewpoint of productivity, the number of treatments is selected about once to three times. It is not preferable to raise the temperature of such an aqueous dispersion under high pressure from the viewpoint of dispersibility and photographic characteristics.At a temperature higher than 90 ° C., the particle size tends to increase, and the fog tends to increase. is there. Therefore, in the present invention, the step before the conversion to the high pressure and high flow rate, the step after the pressure is reduced, or both of these steps include a cooling step, and the temperature of such water dispersion is reduced by the cooling step. It is preferably kept in the range of ~ 90 ° C,
More preferably, the temperature is maintained in the range of 5 to 80C, particularly preferably in the range of 5 to 65C. In particular, it is effective to provide the above cooling step at the time of high-pressure dispersion in the range of 1500 to 3000 kg / cm ² . The cooler, depending on its required heat exchange,
Double tube or double tube using static mixer,
A multi-tube heat exchanger, a coiled tube heat exchanger, and the like can be appropriately selected. Further, in order to increase the efficiency of heat exchange, it is sufficient to select a suitable one such as a pipe thickness, a wall thickness and a material in consideration of a working pressure. Refrigerant used for the cooler, from the amount of heat exchange,
Well water at 20 ° C., cold water at 5 to 10 ° C. treated with a refrigerator, and a refrigerant such as ethylene glycol / water at -30 ° C. can be used if necessary.

In the dispersion operation of the present invention, it is preferable to disperse the organic silver salt in the presence of an aqueous solvent-soluble dispersant (dispersion aid). Examples of the dispersing agent include polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, a maleic acid monoester copolymer, a synthetic anionic polymer such as an acrylomethylpropanesulfonic acid copolymer, and carboxymethyl. Starch, semi-synthetic anionic polymers such as carboxymethyl cellulose, alginic acid, anionic polymers such as pectic acid, the compounds described in JP-A-7-350753, or known anionic, nonionic, cationic surfactants and other polyvinyl Known polymers such as alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, and naturally occurring polymer compounds such as gelatin can be appropriately selected and used. Lumpur acids, particularly preferred water-soluble cellulose derivatives.

It is a general method to mix a dispersion aid with an organic silver salt powder or an organic silver salt in a wet cake state before dispersion and to send the mixture to a dispersion machine as a slurry. Heat treatment or treatment with a solvent may be performed in the combined state to obtain an organic silver salt powder or a wet cake. The pH may be controlled by a suitable pH adjuster before, during or after dispersion.

Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing agent. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after completion of the fine particle formation.

The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of the fine particles during storage, or stored in a highly viscous state (for example, in a jelly state using gelatin) with a hydrophilic colloid. You can also do.
Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

The particle size (volume-weighted average diameter) of the organic silver salt solid fine particle dispersion of the present invention is determined, for example, by irradiating a solid fine particle dispersion dispersed in a liquid with a laser beam and changing the fluctuation of the scattered light with time. It can be obtained from the particle size (volume weighted average diameter) obtained by obtaining the autocorrelation function. A solid fine particle dispersion having an average particle size of 0.05 μm or more and 10.0 μm or less is preferable. The average particle size is more preferably 0.1 μm or more and 5.0 μm or less, and still more preferably the average particle size is 0.1 μm or more and 2.0 μm or less.

The particle size distribution of the organic silver salt is preferably monodispersed. Specifically, the percentage of the standard deviation of the volume-weighted average diameter divided by the volume-weighted average diameter (coefficient of variation)
Is 80% or less, more preferably 50% or less, even more preferably 30%
% Or less.

The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion.

The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio of the organic silver salt to water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by weight, and more preferably 10 to 30% by weight.
Although it is preferable to use the above-mentioned dispersing aid, it is preferable to use the dispersing aid in the minimum amount within a range suitable for minimizing the particle size, and 1 to 30% by weight, especially 3 to 15% by weight based on the organic silver salt.
A range of weight% is preferred.

In the present invention, it is possible to produce a photosensitive material by mixing an aqueous dispersion of an organic silver salt and an aqueous dispersion of a photosensitive silver salt. The mixing ratio of the organic silver salt to the photosensitive silver salt depends on the purpose. The ratio of the photosensitive silver salt to the organic silver salt is 1 to 3
It is preferably in the range of 0 mol%, more preferably 3 to 20 mol%, especially 5
It is preferably in the range of ~ 15 mol%. Mixing two or more aqueous dispersions of organic silver salts with two or more aqueous dispersions of photosensitive silver salts during mixing is a method preferably used for adjusting photographic characteristics.

Although the organic silver salt of the present invention can be used in a desired amount, it is expressed as a coating amount per 1 m ² of the light-sensitive material, and the silver amount is 0.1%.
55 g / m ² is preferred, and more preferably 1-3 g / m ² .

In the present invention, it is preferable to add a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt. Regarding the addition of a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt,
It is preferably added in the form of a water-soluble metal salt that is not a halide, and specifically, it is preferably added in the form of a nitrate or a sulfate. The addition of a halide is not preferred because it deteriorates the image storability of the processed photosensitive material due to light (such as room light or sunlight), that is, the so-called printout property. For this reason, in the present invention, it is preferable to add in the form of a water-soluble metal salt which is not the above-mentioned halide.

Ca, Mg, Zn preferably used in the present invention
And the addition time of the metal ion selected from Ag is, after the formation of the non-photosensitive organic silver salt particles, immediately after the particle formation,
Any time before the application, such as before the dispersion, after the dispersion, and before and after the preparation of the coating liquid, may be at any time, and preferably after the dispersion and before and after the preparation of the coating liquid.

In the present invention, Ca, Mg, Zn and A
g is preferably from 10 ^-3 to 10 ^-1 mol per mol of non-photosensitive organic silver, particularly 5 ×
10 ^{-3 to} 5 × 10 ^-2 mol is preferred.

The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. . The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously.
Further, silver halide grains having a core / shell structure can be preferably used. The structure is preferably 2
Core / shell particles having a ５5-fold structure, more preferably a 2- to 4-fold structure, can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods for forming photosensitive silver halide are well known in the art, for example, Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458.
Can be used.Specifically, a photosensitive silver halide is prepared by adding a silver-supplying compound and a halogen-supplying compound to a gelatin or other polymer solution, and then the organic silver halide is added. A method of mixing with a silver salt is used. The grain size of the photosensitive silver halide is
It is preferably small for the purpose of suppressing white turbidity after image formation, specifically, 0.20 μm or less, more preferably
0.01 μm or more and 0.15 μm or less, more preferably 0.02 μm or more
0.12 μm or less is preferred. The grain size as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited, but the spectral sensitizing efficiency when a spectral sensitizing dye is adsorbed is high.
The proportion occupied by the [100] plane is preferably high. The ratio is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. The Miller index [100] plane ratio was determined by T. Tani; J. Imaging Sci., 29, 165 (1985), which utilizes the adsorption dependence of [111] and [100] planes on the adsorption of sensitizing dyes. It can be determined by the method described.

The light-sensitive silver halide grains of the present invention can be formed by using Group VII or VIII (Groups 7 to 10) of the periodic table.
Of a metal or metal complex. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is 1 × 10
The range is preferably from ^-9 mol to 1 × 10 ^-3 mol.
More preferably, the range is from ^-8 mol to 1 x 10 ^-4 mol. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III)
Complex salts, pentachloroacolodium (III) complex salts, tetrachlorodiachodium (III) complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trioxalathrodium (III) complex salts are exemplified. These rhodium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used for stabilizing a solution of the rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl, NaCl, KBr, NaBr
Etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The amount of these rhodium compounds added is
1 × 10 per mole of silver halide^-8Mol to 5 × 10^-FourMole of
The range is preferably, particularly preferably 5 × 10^-8Mol ~ 1x
10 ^-FiveIs a mole.

These compounds can be appropriately added at the time of the production of silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042, JP-A-1-285941,
It is added in the form of a water-soluble complex salt described in JP-A Nos. 2-20852 and 2-20855. Particularly preferred are hexacoordinate complexes represented by the following formula. [ML ₆ ] ⁿ -where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4.

In this case, the counter ion is not important, and an ammonium or alkali metal ion is used.

Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands and the like.
Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^- [RuCl ₅ (H ₂ O)] ^2- [RuCl ₅ (NO)] ^2- [RuBr ₅ ( ^{NS)] 2- [Ru (CO} ) 3 Cl 3] 2- [Ru (CO) Cl 5] 2- [Ru (CO) Br 5] 2- [OsCl 6] 3- [OsCl 5 (NO)] 2 ^- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (O) ₂ (CN) ₄ ] ^4-

The amount of these compounds added was 1
It is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁴ mol per mol, particularly preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol.

These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains.

In order to add these compounds into silver halide grains by adding them during silver halide grain formation, a metal complex powder or an aqueous solution dissolved together with NaCl and KCl is added to the aqueous solution during grain formation. A method in which silver halide grains are added to a salt or a water-soluble halide solution, or are added as a third solution when a silver salt and a halide solution are simultaneously mixed, and silver halide grains are prepared by a three-solution simultaneous mixing method; Alternatively, there is a method in which a required amount of an aqueous solution of a metal complex is charged into a reaction vessel during particle formation. Especially powder or NaCl, KCl
Is preferable to add an aqueous solution dissolved together with the above to a water-soluble halide solution.

For the addition to the particle surface, a required amount of an aqueous solution of a metal complex can be added to the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

Various compounds can be used as the iridium compound used in the present invention, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, and pentachloronitrosyliridium. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used for stabilizing a solution of the iridium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) is used. Etc.) or a method of adding an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain doped with iridium in advance during the preparation of silver halide.

The silver halide grains used in the present invention may further include cobalt, iron, nickel, chromium, palladium,
It may contain metal atoms such as platinum, gold, thallium, copper and lead. For compounds of cobalt, iron, chromium and ruthenium, hexacyano metal complexes can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion,
Examples include, but are not limited to, hexacyanochromate ions and hexacyanoruthenate ions. The metal complex in the silver halide may be contained uniformly, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration, and there is no particular limitation.

The above metal is 1 × per mole of silver halide.
It is preferably from 10 ^-9 to 1 × 10 ^-4 mol. Further, in order to contain the above-mentioned metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added at the time of preparing particles.

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

The gold sensitizer used for sensitizing the silver halide emulsion of the present invention to gold may have a gold oxidation number of +1 or +3, and is usually used as a gold sensitizer. Gold compounds can be used. Representative examples include chloroauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

The amount of the gold sensitizer to be added varies depending on various conditions. As a guide, the amount is from 10 ⁻⁷ mol to 10 ⁻³ mol, more preferably from 10 ⁻⁶ mol to 5 × 10 ⁻ mol per mol of silver halide. Not more than ⁴ moles.

The silver halide emulsion of the present invention is preferably used in combination with gold sensitization and another chemical sensitization. As other chemical sensitization methods, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used. When used in combination with the gold sensitization method,
For example, sulfur sensitization and gold sensitization, selenium sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization Preferred methods include sulfur sensitization, selenium sensitization, tellurium sensitization, and gold sensitization.

The sulfur sensitization preferably used in the present invention is
Usually, a sulfur sensitizer is added and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is,
Usually, an unstable type and / or a non-unstable type selenium compound is added, and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, JP-A-4-25832, JP-A-4-10
Compounds described in Nos. 9240 and 4-324855 can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in JP-A-5-3132.
It can be tested by the method described in No. 84. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals,
Tellurosulfonates, compounds having a P-Te bond, containing T
e Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, UK Patent 235,211 and 1,121,496,
No. 1,295,462, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-204640, JP-A-3-53693, JP-A-3-31598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibid 6
45 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.
Trans.) 1,2191 (1980), edited by S. Patai, The Chemistry of Organ, Selenium and Tellurium Campounds
ic Serenium and Tellunium Compounds), Vol. 1 (1986),
The compounds described in Vol. 2 (1987) can be used.
Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physical ripening.

In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, 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 can be used. . Also, when the pH of the emulsion is 7 or more or p
Reduction sensitization can be achieved by aging while keeping Ag at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in EP 293,917.

The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example,
Those with different average grain sizes, different halogen compositions, different crystal habits, different chemical sensitization conditions)
You may use together.

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, and more preferably 0.03 to 0.3 mol, per mol of the organic silver salt. It is particularly preferably at least 0.25 mol and not more than 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, and a homogenizer. Etc., or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, or the like.
There is no particular limitation as long as the effects of the present invention are sufficiently exhibited.

Next, the compound of the formula (1) used in the present invention will be described in detail. In the formula (1), Z ¹ and Z ² are each independently a halogen atom (fluorine, chlorine,
Most preferably, Z ¹ and Z ² are both bromine atoms.

In the formula (1), X ¹ is a hydrogen atom or an electron-withdrawing group. The electron-withdrawing group referred to herein is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group,
It represents a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a halogen atom, an acyl group, a heterocyclic group or the like. In the formula (1), X ¹ is preferably a hydrogen atom or a halogen atom, and most preferably a bromine atom.

In the formula (1), Y ¹ is —CO— or —SO ₂ —
, And the preferably -SO ₂ - it is. In the formula (1), Q represents an arylene group or a divalent heterocyclic group.

The arylene group represented by Q in the formula (1) is preferably a monocyclic or condensed arylene group having 6 to 30 carbon atoms, more preferably a monocyclic or condensed arylene group having 6 to 20 carbon atoms. And phenylene, naphthylene and the like, and particularly preferably a phenylene group.
The arylene group represented by Q may have a substituent, and any substituent may be used as long as it does not adversely affect photographic performance. Examples of the substituent include a halogen atom (a fluorine atom, Atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (N-substituted nitrogen-containing heterocyclic group) Substituted with a quaternary nitrogen-containing heterocyclic group (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, or an N atom Imino group, thiocarbonyl group, carbazoyl group,
Cyano group, thiocarbamoyl group, alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy Group, sulfonyloxy group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary An ammonium group, an (alkyl or aryl) sulfonyluureido group, a nitro group, an (alkyl, aryl or heterocycle) thio group, an acylthio group, an (alkyl or aryl) sulfonyl group, an (alkyl or Aryl) sulfinyl group,
Examples thereof include a sulfo group or a salt thereof, a sulfamoyl group, a phosphoryl group, a group having a phosphate amide or phosphate structure, and a silyl group. These substituents may be further substituted with these substituents. Particularly preferably, the substituent of the arylene group represented by Q in the formula (1) is an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, a carboxyl group or a salt thereof,
It is a salt of a sulfo group or a phosphate group.

In the formula (1), the heterocyclic ring in the divalent heterocyclic group represented by Q is a 5- to 7-membered saturated or unsaturated heterocyclic ring containing at least one N, O or S atom. Yes, these may be a single ring or may form a condensed ring with another ring. Examples of the heterocycle in the divalent heterocyclic group represented by Q include pyridine, pyrazine, pyrimidine, benzothiazole, benzimidazole, thiadiazole, quinoline, isoquinoline, triazole, triazine and the like. These may have a substituent, and examples thereof include the same groups as the substituents of the arylene group represented by Q.

Q in the formula (1) is preferably an arylene group, particularly preferably a phenylene group.

L in the formula (1) represents a linking group, for example, an alkylene group (including an alkylidene group and a cyclo-form. Preferably, it has 1 to 30 carbon atoms, more preferably 1 carbon atom.
-20, and particularly preferably 1-10 carbon atoms. ), An arylene group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 10 carbon atoms), and an alkenylene group (preferably having 2 to 30 carbon atoms). Yes, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms), alkynylene group (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, Particularly preferably, it has 2 to 10 carbon atoms.) And a heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms). , -O- group, -NR- group, -CO- group, -COO
-Group, -OCOO- group, -NRCO- group, -NRCON
R- group, -OCONR- group, -S- group, -SO- group,-
Examples include an SO ₂ — group, a —SO ₂ NR— group, a group containing a phosphorus atom, and a group formed by combining these (here, the group represented by R has a hydrogen atom or a substituent Is an alkyl group or an aryl group which may have a substituent).

The linking group represented by L in the formula (1) may have a substituent, and examples thereof include the same substituents as those of the arylene group represented by Q.

The linking group represented by L in the formula (1) is preferably an alkylene group, an arylene group, an —O— group, an —NRC
O- group, a group formed by combining -SO ₂ NR- group, and their. When possible, it may be partially cyclized. n is 0 or 1.

In formula (1), W represents a carboxyl group or a salt thereof (Na, K, ammonium salt, etc.), a sulfo group or a salt thereof (Na, K, ammonium salt, etc.), a phosphate group or a salt thereof (Na, K, , An ammonium salt, etc.), a hydroxyl group, a quaternary ammonium group (eg, tetrabutylammonium, trimethylbenzylammonium, etc.) and a polyethyleneoxy group. W is preferably a carboxyl group or a salt thereof, a salt of a sulfo group, or a hydroxyl group.

Next, specific examples of the compound of the present invention will be shown, but the present invention is not limited thereto.

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The compounds of the present invention can be easily synthesized by ordinary organic synthesis reactions. A typical synthesis example is shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (P-60) (1) Synthesis of Intermediate (B) 93 g of a commercially available compound (A), 43 g of sodium hydroxide, 123 g of sodium chloroacetate and 10 g of potassium iodide were dissolved in 300 ml of water. Stirred at 80 ° C. for 2 hours. After lowering the internal temperature to 30 ° C, concentrated hydrochloric acid 50m
l was added and stirred for a while to precipitate crystals. The crystals were subjected to suction filtration and dried, and as a result, 80 g of an intermediate (B) was obtained. White crystals.

(2) Synthesis of Exemplified Compound (P-60) Bromine 33 was added to a solution of 57 g of NaOH and 500 ml of water at room temperature.
ml, then 24 g of intermediate (B), NaOH
An aqueous solution of 8 g and 100 ml of water was added dropwise at room temperature. The precipitated crystals were filtered, and the obtained crystals were added to dilute hydrochloric acid and filtered. As a result of sufficiently washing with water and drying, the exemplified compound (P-
60) was obtained in an amount of 30 g. White crystals.

Synthesis Example 2 Synthesis of Exemplified Compound (P-7) (1) Synthesis of Intermediate (C) 30 g of Exemplified Compound (P-60) and 1 ml of DMF (dimethylformamide) were dissolved in 100 ml of thionyl chloride and stirred at 70 ° C for 30 minutes. Thereafter, excess thionyl chloride was distilled off under reduced pressure to obtain 31 g of an intermediate (C). White crystals.

(2) Synthesis of Exemplified Compound (P-7) A solution of 4.7 g of diethanolamine and 50 ml of methanol was cooled on ice, and 4.1 g of the intermediate (C) was added. After stirring for 5 minutes, 50 ml of water was added, and white crystals precipitated. This was filtered, dissolved in a small amount of DMAc (dimethylacetamide), and crystals were precipitated by adding methanol little by little. As a result of filtering and drying, 4.0 g of Exemplified Compound (P-7) was obtained. White crystals.

Synthesis Example 3 Synthesis of Exemplified Compound (P-6) 15 g of glycine, 17 g of NaHCO ₃ , 100 ml of water,
20 g of the intermediate (C) was added to a solution of 100 ml of THF (tetrahydrofuran), and the mixture was stirred at room temperature for 5 minutes. After diluting hydrochloric acid to neutralize the reaction solution, 200 ml of water was added and the precipitated crystals were filtered. The obtained crude crystals are mixed with a small amount of DMA
c) and methanol was added until crystals precipitated. As a result of filtering and drying the crystals, exemplary compound (P-6) was obtained.
Was obtained. White crystals.

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The compound represented by the formula (1) of the present invention is
Dissolve in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be. Further, the compound to which the acidic group is bonded may be neutralized with an equivalent amount of alkali and added as a salt.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsified dispersion can be prepared and used. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method.

The compound represented by the formula (1) of the present invention is
It may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side, but is preferably added to the image forming layer or a layer adjacent thereto. The amount of the compound of the formula (1) used in the present invention may be a desired amount in accordance with the performance such as sensitivity and fog, but is preferably from 10 ^-4 to 1 mol per 1 mol of the non-photosensitive silver salt in the image forming layer. And more preferably 10 ^{-3 to} 5 × 10 ^-1 mol.

When the photothermographic material of the present invention is used for graphic arts, γ after the heat development step (a straight line connecting density 0.2 and density 2.5 when the logarithm of the amount of exposure is represented on the horizontal axis). Is preferably 5 or more and 20 or less, more preferably 10 or more and 18 or less. One way to achieve this is to include a nucleating agent in the photosensitive layer or other adjacent layers.

As the nucleating agent used in the present invention, a substituted alkene derivative, a substituted isoxazole derivative, and a specific acetal compound are preferably used.

The substituted alkene derivative represented by the formula (2), the substituted isoxazole derivative represented by the formula (3), and the specific acetal compound represented by the formula (4) which are preferably used in the present invention will be described. .

In the formula (2), R¹, R^Two, R^ThreeEach
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing property.
Represents a group or a silyl group. In the formula (2), R¹And Z, R^Two
And R ^Three, R¹And R^TwoOr R^ThreeAnd Z are joined together
An annular structure may be formed. In the formula (3), R
^FourRepresents a substituent. In equation (4), X and Y are respectively
A and B each independently represent a hydrogen atom or a substituent.
Independently, an alkoxy group, an alkylthio group, an alkylamido
Group, aryloxy group, arylthio group, anilino
Group, heterocyclic oxy group, heterocyclic thio group, or hetero
Represents a ring amino group. In equation (4), X and Y or A
And B may combine with each other to form a cyclic structure
No.

The compound represented by the formula (2) will be described in detail.
I will tell. In the formula (2), R¹, R^Two, R^ThreeIs German
Represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group.
Or a silyl group. In the formula (2), R¹And Z, R^TwoAnd R
^Three, R¹And R^TwoOr R^ThreeAnd Z are linked together to form a ring
A structure may be formed.

When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group and a cycloalkyl group). An alkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including an N-substituted nitrogen-containing heterocyclic group), and a heterocyclic group containing a quaternized nitrogen atom ( For example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfonylcarbamoyl group, an acylcarbamoyl group, Famoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, A droxy group (or a salt thereof), an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, and carbamoyl Oxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfa Moylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group , A nitro group, a mercapto group, an (alkyl, aryl, or heterocyclic) thio group, an acylthio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group,
Examples thereof include an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphoryl group, a group having a phosphoric acid amide or a phosphoric ester structure, a silyl group, and a stannyl group. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the formula (2) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with an N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom,
Perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group (or salt thereof), sulfo group (or salt thereof), heterocyclic group, alkenyl group, alkynyl group, Examples include an acyloxy group, an acylthio group, a sulfonyloxy group, and an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is a saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group,
Examples thereof include a pyrazinyl group, a quinoxalinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, a hydantoin-1-yl group, a succinimide group, and a phthalimido group.

The electron-withdrawing group represented by Z in the formula (2) may further have a substituent, and the substituent includes R ¹ , R ² and R ^{3 in the} formula (2). The same substituents as the substituents that may be present when representing the substituents are exemplified.

In the formula (2), R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. The cyclic structure is
It is a non-aromatic carbon ring or a non-aromatic hetero ring.

Next, the preferred range of the compound represented by the formula (2) will be described. The silyl group represented by Z in the formula (2) is preferably a trimethylsilyl group, t
-Butyldimethylsilyl group, phenyldimethylsilyl group, triethylsilyl group, triisopropylsilyl group,
And a trimethylsilyldimethylsilyl group.

The electron-withdrawing group represented by Z in the formula (2) is preferably a group having a total number of carbon atoms of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carbonyl group,
Imino group, imino group substituted with N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acyloxy group, acylthio group, or any electron withdrawing And a phenyl group substituted with a functional group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group,
An alkylsulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group, and particularly preferably a cyano group, a formyl group, an acyl group. , An alkoxycarbonyl group, an imino group or a carbamoyl group.

In the formula (2), the group represented by Z is more preferably an electron-withdrawing group. In the formula (2), the substituent represented by R ¹ , R ² and R ³ is preferably a total of 0 carbon atoms.
To 30 groups, specifically the same groups as the electron-withdrawing group represented by Z in the above formula (2), and alkyl groups, hydroxy groups (or salts thereof), and mercapto groups (or salts thereof) An alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, an acylamino group, a sulfonamide group, Or a substituted or unsubstituted aryl group.

Further, in the formula (2), R ¹ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom, or a silyl group.

When R ¹ represents an electron-withdrawing group, the following groups having preferably 0 to 30 carbon atoms in total, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), Or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, a carboxy group (or a salt thereof) Or a saturated or unsaturated heterocyclic group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a saturated or unsaturated heterocyclic group.

When R ¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms in total, and examples of the substituent include arbitrary substituents.
Among them, an electron-withdrawing substituent is preferable.

In the formula (2), R ¹ is more preferably
It is time to represent an electron withdrawing group or an aryl group. Equation (2)
In the formula (2), the substituents represented by R ² and R ³ are preferably the same as the electron-withdrawing group represented by Z in the above formula (2), an alkyl group, a hydroxy group (or a salt thereof). ), A mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group,
Examples include an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group.

In the formula (2), R ² and R ³ are more preferably when one of them is a hydrogen atom and the other is a substituent. The substituent is preferably an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group. Group, alkylamino group, anilino group,
Heterocyclic amino group, acylamino group (particularly perfluoroalkaneamide group), sulfonamide group, substituted or unsubstituted phenyl group, or a heterocyclic group, more preferably a hydroxy group (or a salt thereof), a mercapto group ( Or a salt thereof), an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
A heterocyclic thio group or a heterocyclic group, particularly preferably a hydroxy group (or a salt thereof), an alkoxy group, or a heterocyclic group.

In the formula (2), Z and R ¹ , or R ²
It is also preferred that and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number including a substituent of 1 to 7. 4
0, more preferably 3 to 30.

[0147] Among the compounds represented by formula (2), more One of preferred, Z is a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group,, R ¹ is Represents an electron-withdrawing group or an aryl group, and one of R ^{2 and} R ³ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, The compound represents a ring oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group. Furthermore, one of the particularly preferable compounds represented by the formula (2) is that Z and R ^{1 form a} non-aromatic 5- to 7-membered cyclic structure, and R ² or R ³ Is one of a hydrogen atom, the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, Or a compound representing a heterocyclic group. At this time, Z which forms a non-aromatic cyclic structure together with R ¹ is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group and the like, and R ¹ is an acyl group, a carbamoyl group , An oxycarbonyl group, a thiocarbonyl group, a sulfonyl group,
Preferred are an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like.

Next, the compound represented by the formula (3) will be described. In the formula (3), R ⁴ represents a substituent. As the substituent represented by R ⁴ , the same substituents as described for the substituents R ^{1 to} R ³ in formula (2) can be mentioned.

The substituent represented by R ⁴ is preferably an electron-withdrawing group or an aryl group. When R ⁴ represents an electron-withdrawing group, preferably the following groups having a total carbon number of 0 to 30,
That is, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group,
A phosphoryl group, an imino group, or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic group. preferable. Particularly preferably, a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group,
It is a carbamoyl group or a heterocyclic group.

When R ⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 6 to 30 carbon atoms, and the substituent is represented by R ¹ , R ² , R ³ of the formula (1). When represents a substituent, the same as those described as the substituent can be mentioned.

R ⁴ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group or a substituted or unsubstituted phenyl group, and most preferably a cyano group, a heterocyclic group or an alkoxycarbonyl group. is there.

Next, the compound represented by the formula (4) will be described in detail. In the formula (4), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent:
Represents an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group. X and Y or A and B may be bonded to each other to form a cyclic structure.

As the substituents represented by X and Y in the formula (4), the same substituents as described for the substituents R ^{1 to} R ^{3 in} the formula (2) can be mentioned. Specifically, alkyl groups (including perfluoroalkyl groups, trichloromethyl groups, etc.), aryl groups, heterocyclic groups, halogen atoms, cyano groups, nitro groups, alkenyl groups, alkynyl groups, acyl groups, formyl groups, alkoxy groups Carbonyl group, aryloxycarbonyl group, imino group, imino group substituted with an N atom, carbamoyl group, thiocarbonyl group, acyloxy group, acylthio group, acylamino group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphoryl group, carboxy Group (or its salt), sulfo group (or its salt), hydroxy group (or its salt), mercapto group (or its salt), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero group Ring thio group, amino group, alkylami Group, anilino group, heterocyclic amino group, a silyl group, and the like.

These groups may further have a substituent. X and Y may be bonded to each other to form a cyclic structure, and the cyclic structure formed in this case may be a non-aromatic carbon ring or a non-aromatic hetero ring. .

The substituents represented by X and Y in the formula (4) are preferably groups having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and include a cyano group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group , An acylamino group, an acyloxy group, an acylthio group, a heterocyclic group, an alkylthio group, an alkoxy group, or an aryl group.

In the formula (4), X and Y are more preferably cyano, nitro, alkoxycarbonyl, carbamoyl, acyl, formyl, acylthio, acylamino, thiocarbonyl, sulfamoyl, alkylsulfonyl. Group, an arylsulfonyl group, an imino group, an imino group substituted with an N atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group Group, alkylsulfonyl group,
An arylsulfonyl group, an acyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, or a phenyl group substituted with any electron-withdrawing group; is there.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the cyclic structure to be formed is preferably a 5- to 7-membered ring, and has a total carbon number of 1 to 40, more preferably 3 to 7 members.
30 is preferred. X and Y forming a cyclic structure include an acyl group, a carbamoyl group, an oxycarbonyl group,
Preferred are a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like.

In the formula (4), A and B are each independently:
Represents an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group, which are bonded to each other to form a cyclic structure. You may. In the formula (4), the groups represented by A and B preferably have a total carbon number of 1 to 40, more preferably a total carbon number of 1 to 40.
To 30 and may further have a substituent.

In the formula (4), A and B more preferably combine with each other to form a cyclic structure.
The cyclic structure formed at this time is preferably a 5- to 7-membered non-aromatic hetero ring, and preferably has a total carbon number of 1 to 40, and more preferably 3 to 30. In this case, A, by way of example in which B is linked (-A-B-), for example _{-O- (CH 2) 2 -O -} , - O-
(CH ₂ ) ₃ -O-, -S- (CH ₂ ) ₂ -S-, -S- (CH ₂ ) ₃ -S-, -S-ph-S-,-
N (CH ₃ )-(CH ₂ ) ₂ -O-, -N (CH ₃ )-(CH ₂ ) ₂ -S-, -O- (CH ₂ ) ₂ -S
-,, -O- (CH ₂ ) ₃ -S-, -N (CH ₃ ) -ph-O-, -N (CH ₃ ) -ph-S-,-
N (ph)-(CH ₂ ) ₂ -S- and the like.

The compounds represented by the formulas (2) to (4) of the present invention may have incorporated therein an adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio, arylthio, thiourea, thioamide,
U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045 and JP-A-59-201045, such as mercapto heterocyclic groups and triazole groups. 201046, 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

The compounds represented by the formulas (2) to (4) of the present invention may be those having a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. Good. Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. As the polymer, for example, JP-A-1-100
No. 530.

The compounds represented by the formulas (2) to (4) of the present invention contain a cationic group (specifically, a group containing a quaternary ammonium group or a quaternized nitrogen). A nitrogen-containing heterocyclic group containing an atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy group, Sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.)
May be included. Particularly, a group containing a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group or a group containing an (alkyl, aryl, or heterocyclic) thio group is one of preferred examples of the present invention. Specific examples of these groups include, for example, JP-A-7-2344.
No. 71, JP-A-5-333466, JP-A-6-190
No. 32, JP-A-6-19031, JP-A-5-4576
No. 1, U.S. Pat. No. 4,994,365, U.S. Pat.
04, JP-A-3-259240, JP-A-7-561
0, JP-A-7-244348, German Patent 40060
No. 32 and the like.

Next, specific examples of the compounds represented by formulas (2) to (4) of the present invention are shown below. However, the present invention is not limited to the following compounds.

[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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The compounds represented by the formulas (2) to (4) of the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol) and ketones (acetone, methyl ethyl ketone). ),
It can be used by dissolving in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like.

Further, by a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve mechanically. An emulsified dispersion can be prepared and used. Alternatively, the compound powder can be dispersed and used in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic wave by a method known as a solid dispersion method.

The compounds represented by the formulas (2) to (4) of the present invention may be added to the image forming layer or added to a layer other than the image forming layer to be diffused into the image forming layer.

The addition amount of the compounds represented by the formulas (2) to (4) of the present invention is preferably 1 × 10 ⁻⁶ to 1 mol per 1 mol of silver, and 1 × 10 ^{−5 to} 5 × 10 5 ^-1 mol is more preferred, and 2
X10 ^{-5 to} 2 × 10 ^-1 mol is most preferred.

The compounds represented by the formulas (2) to (4) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515, US Pat. No. 5,635,339,
U.S. Pat. No. 5,654,130, International Patent WO-97 / 34
196 or Japanese Patent Application Nos. 9-309813 and 9
The compound can be synthesized with reference to the method described in -272002.

The compounds represented by formulas (2) to (4) of the present invention may be used alone or in combination of two or more. In addition to the above, U.S. Pat. No. 5,545,515, U.S. Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, International Patent WO-97 / 34196, U.S. Pat.
No. 28, or Japanese Patent Application No. 8-2799.
No. 62, Japanese Patent Application No. 9-228881, Japanese Patent Application No. 9-273
No. 935, Japanese Patent Application No. 9-309813, Japanese Patent Application No. 9-29
No. 6174, Japanese Patent Application No. 9-282564, Japanese Patent Application No. 9-2
No. 72002, Japanese Patent Application No. 9-272003, Japanese Patent Application No. 9-272003
You may use together the compound described in 332388.

In the present invention, a hydrazine derivative can be used in combination as a nucleating agent, and a compound represented by the following formula (H) is preferable.

[0180]

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In the formula, R ²⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a block group, and G ¹ represents —CO—, —COCO—, —C (= S)
_{-, - SO 2, -SO -} , - PO (R 30) - group (. R ³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10), or an iminomethylene Represents a group.
A ¹ and A ² are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group,
Represents an arylsulfonyl group or an acyl group. m ¹ is 0 or 1, and when m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group.

Examples of hydrazine derivatives include, for example, JP-A-63-29751 and US Pat. No. 4,385,108.
No. 4459347, JP-A-59-195233.
Nos. 59-200231 and 59-201045
Nos. 59-201046 and 59-201047
Nos. 59-201048 and 59-201049
And JP-A-61-170733 and 61-27074.
Nos. 4, 62-948, 63-234244, 63-234245, 63-234246, JP-A-2-285344, JP-A-1-100530, JP-A-64-86134, and JP-A-64-86134 No. 4-16938, JP-A-5- 197091, WO95-32452, W
O95-32453, JP-A-9-235264, JP-A-9-235265, JP-A-9-235266, JP-A-9-235267, JP-A-9-179229,
JP-A-7-234471, JP-A-5-333466
JP-A-6-19032, JP-A-6-19031
No. JP-A-5-45761, U.S. Pat.
5, U.S. Pat. No. 4,988,604, JP-A-3-259
No. 240, JP-A-7-5610, JP-A-7-2443
No. 48, German Patent No. 4006032 and the like.

The hydrazine derivative of the present invention may be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve, etc. Can be dissolved and used.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution, and An emulsified dispersion can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The hydrazine derivative of the present invention may be added to the image forming layer or may be added to a layer other than the image forming layer and diffused into the image forming layer.

The amount of the hydrazine derivative of the present invention was 1
It is preferably 1 × 10 ^-6 to 1 mol with respect to the mol, and 1 × 10 ^-6
-5 × 10 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10
^-1 mole is most preferred.

Further, the present invention provides a method for forming a super-high contrast image.
A high contrast accelerator can be used in combination with the nucleating agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically, AM-1 to AM-5, and hydroxamic acids described in 5,545,507, specifically, HA-1 to HA-1
1, acrylonitriles described in 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in 5,558,983, specifically CA-1 to CA-6, Japanese Patent Application No. 8-132836
Salt, specifically A-1 to A-42,
B-1 to B-27, C-1 to C-14 and the like can be used.

The synthesis method, addition method, addition amount and the like of these high contrast enhancement agents can be carried out as described in each of the cited patents.

In the present invention, an acid or a salt thereof formed by hydration of diphosphorus pentoxide is preferably used in combination with a nucleating agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline Acids (salts); Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt),
Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate,
Examples include ammonium hexametaphosphate.

The acid or a salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto in that a desired effect is exhibited in a small amount. .

The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide used in the present invention (the coating amount per 1 m ^{2 of the} light-sensitive material) may be a desired amount in accordance with the performance such as sensitivity and fog. However, 0.1 to 500 mg / m ² is preferable, and 0.5 to 100
mg / m ² is more preferred.

The photothermographic material of the present invention contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The reducing agent may be added to the image forming layer or may be added to a layer other than the image forming layer and diffused into the image forming layer. When added to layers other than the image forming layer, 10
It is preferable to use a relatively large amount of 5050 mol%. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In photothermographic materials using organic silver salts, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
47-33621, 49-46427, 49-115540, 50-14
No. 334, No. 50-36110, No. 50-147711, No. 51-32632,
No. 51-1023721, No. 51-32324, No. 51-51933, No. 52-8
4727, 55-108654, 56-146133, 57-82828
No. 57-82829, JP-A-6-3793, U.S. Pat.
No. 6, 3,751,252, 3,751,255, 3,761,270,
3,782,949, 3,839,048, 3,928,686, 5,4
64,738, German Patent 2321328, European Patent 692732 and the like. For example, phenylamide oxime,
Amidoximes such as 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2′-bis (hydroxymethyl) propionyl-β-
A combination of an aliphatic carboxylic acid aryl hydrazide such as a combination of phenylhydrazine and ascorbic acid with ascorbic acid; a combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis (ethoxyethyl) hydroxyl Amines, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; azine and sulfonamide phenol (E.g., phenothiazine and 2,6-dichloro-4-
Benzenesulfonamidophenol); ethyl-α-
Α-cyanophenylacetic acid derivatives such as cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′- Dihydroxy-1,1'-binaphthyl and bis (2
Bis-β-naphthol as exemplified by -hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxy Acetophenone); 5-pyrazolone, such as 3-methyl-1-phenyl-5-pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone. Reductones as exemplified; sulfonamide phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2- Chromanes such as dimethyl-7-t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydrogen 1,4-dihydropyridines such as lopyridine; bisphenols (eg, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4 , 4-Ethylidene-bis (2-t-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2 -Bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and Certain indane-1,3-diones; chromanol (such as tocopherol).
Particularly preferred reducing agents are bisphenol and chromanol.

The reducing agent of the present invention may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

When an additive known as a "toning agent" for improving an image is contained, the optical density may be increased. Toning agents may also be advantageous in forming black silver images. The toning agent is preferably contained in an amount of 0.1 to 50% (mol) per mol of silver on the surface having the image forming layer,
More preferably, the content is 0.5 to 20% (mole). Also,
The toning agent may be a so-called precursor that is derivatized so as to have a function effectively only during development.

In a photothermographic material utilizing an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077 and JP-A-47-10282.
Nos. 49-5019, 49-5020, 49-91215, 49-9
No. 1215, No. 50-2524, No. 50-32927, No. 50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-279
No. 23, No. 52-14788, No. 52-99813, No. 53-1020, No. 5
3-76020, 54-156524, 54-156525, 61-1836
No. 42, JP-A-4-56848, JP-B-49-10727, 54-2033
No. 3, U.S. Pat.Nos. 3,080,254, 3,446,648, 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent 138079
No. 5, Belgian Patent No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimides (eg, N
-Hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-
Mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole Illustrative mercaptans; N- (aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl)-
Naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N′-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1 , 8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl-5 [(3-ethyl-2-benzothia) Zolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7- Derivatives such as dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic acid) Combination of anhydride such as phthalic acid); phthalazine, phthalazine derivatives (e.g., 4- (1-naphthyl) phthalazine, 6
-Chlorophthalazine, 5,7-dimethoxyphthalazine, iso-
Propylphthalazine, 6-iso-butylphthalazine, 6-tert
-Butylphthalazine, 5,7-dimethylphthalazine, and
Derivatives such as 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives
(Eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; silver halide in situ as well as color tone modifier Rhodium complex that also functions as a source of halide ions for formation, such as hexachlororhodium
(III) ammonium, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine- 2,4-
Benzoxazine-2,4-diones such as dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric -Triazines (e.g., 2,4-dihydroxypyrimidine,
2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (e.g., 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6
-Dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).

The color-toning agent of the present invention may be added by any method such as a solution, a powder and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

As the sensitizing dye in the present invention, any dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17
Item 643IV-A (p.23, December 1978), Item 1831X (August 1979)
p.437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate making cameras can be advantageously selected.

Examples of spectral sensitization to red light include He-Ne
For a so-called red light source such as a laser, a red semiconductor laser or an LED, a compound of I-1 to I-38 described in JP-A-54-18726, and a compound of I-1 described in JP-A-6-75322. I-3
5 and the compounds I-1 to I- described in JP-A-7-287338.
34 compounds, dyes 1 to 20 described in JP-B-55-39818,
The compounds I-1 to I-37 described in JP-A-62-284343 and the compounds I-1 to I-34 described in JP-A-7-287338 are advantageously selected.

For a semiconductor laser light source in the wavelength range of 750 to 1400 nm, cyanine, merocyanine, styryl,
A variety of known dyes, including hemicyanine, oxonol, hemioxonol and xanthene dyes, can be spectrally sensitized favorably. Useful cyanine dyes are, for example, cyanine dyes having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Pat.
3,719,495, 3,877,943, UK Patent 1,466,201,
No. 1,469,117, No. 1,422,057, No. 3-10391, No. 6
-52387, JP-A-5-341432, JP-A-6-94781, JP-A-6-3011
The dye may be appropriately selected from known dyes as described in No. 41.

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
No. 72661, No. 6-222491, No. 2-230506, No. 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-301
No. 141, dyes described in U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524, JP-A-51-127719,
No. 52-80829, No. 54-61517, No. 59-214846, No. 60-67
No. 50, 63-159841, JP-A-6-35109, 6-59381
No., 77-146537, 77-146537, Tokuyohei 55-50111,
Dyes described in British Patent 1,467,638 and US Patent 5,281,515).

Further, as a dye forming a J-band, a dye described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887,
JP-A-2-96131 and JP-A-59-48753 are disclosed and can be preferably used in the present invention.

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. In particular, combinations of sensitizing dyes are frequently used 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
Research Disclosure Volume 176, 17643 (December 1978) No. 23
Section IV of Page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2, 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy
It may be added to the emulsion by dissolving it in a solvent such as 1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, alone or in a mixed solvent.

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, this solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. Method of adding to Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, the dye is dissolved in an acid and this solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or base. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in U.S. Pat. JP-A-51-746, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion as disclosed in JP-A-58-105141.
As disclosed in No. 24, a method of dissolving a dye using a compound that causes red shift and adding this solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Patents 2,735,766 and 3,628,960,
4,183,756, 4,225,666, JP-A-58-184142,
As disclosed in the specification of JP-A-60-196749 and the like, the timing before silver halide grain forming step and / or desalting, during and / or after desalting and before the start of chemical ripening. As disclosed in the specification such as JP-A-58-113920, any time immediately before chemical ripening or during the process, after chemical ripening, and before coating the emulsion before coating It may be added at the time and in the process.
Also, as disclosed in the specification of U.S. Pat. The compound may be added separately during or after chemical ripening, or before or after chemical ripening, or may be added separately. May be added.

The amount of the sensitizing dye used in the present invention may be a desired amount according to the performance such as sensitivity and fog.
10 per mole of silver halide in the image forming layer (photosensitive layer)
^-6 to 1 mol is preferable, and 10 ^-4 to 10 ^-1 mol is more preferable.

The silver halide emulsion according to the present invention or /
And the organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and can be stabilized against reduced sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716, U.S. Pat. Azaindene, U.S. Pat.
8,663 mercury salt, U.S. Pat.No. 3,287,135 urazole, U.S. Pat.No. 3,235,652 sulfocatechol, British Patent 623,448 oxime,
Nitron, nitroindazole, U.S. Patent No. 2,839,405
No. 3,220,839, thiuronium salts, and U.S. Pat.Nos. 2,566,263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.Nos. 4,108,665 and 4,442,202 No. 4,128,557
Nos. 4,137,079 and 4,138,365 and 4,
No. 4,59,350 and U.S. Pat.
And the phosphorus compounds described in 1,985.

As the antifoggant preferably used in the present invention, an organic halide other than the compound of the formula (1) can be used in combination. For example, JP-A-50-119624, 50-120328,
No. 51-121332, No. 54-58022, No. 56-70543, No. 56-99
No. 335, No. 59-90842, No. 61-129642, No. 62-129845
No., JP-A-6-208191, No. 7-5621, No. 7-2781, No. 8-
No. 15809, Japanese Patent Application No. 10-292863, U.S. Pat.No. 5,340,712
Nos. 5,369,000 and 5,464,737.

These antifoggants may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The compounds which are preferably used as the antifoggant in the present invention are compounds of the formula (S) described in Japanese Patent Application No. 11-23995.

[0212] These cyclic compounds are known in the art as an inhibitor of photographic performance deterioration due to formaldehyde gas. It is extremely interesting and difficult to predict that such compounds have shown remarkable effects on fog prevention and sensitivity fluctuation during storage in photothermographic materials, especially those using a nucleating agent described below. Met. Specific examples of this series of compounds are described in JP-A-61-73.
No. 150, No. 58-10738, No. 50-87028
And the like.

Although not required to practice the present invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the emulsion layer (image forming layer). Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The addition amount of mercury used in the present invention is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol per mol of coated silver. Range of moles.

The photothermographic material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acids of the present invention may be any benzoic acid derivative, but examples of preferred structures include those described in U.S. Pat.
No. 9, No. 4, 152, 160, Japanese Patent Application No. 8-151242, No. 8-151241
And the compounds described in JP-A-8-98051 and the like. The benzoic acids of the present invention may be added to any part of the light-sensitive material. However, the added layer is preferably added to a layer having a light-sensitive layer, more preferably to an organic silver salt-containing layer. . The benzoic acid of the present invention may be added at any time during the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be added at any time from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable after salt preparation and immediately before application. The benzoic acid of the present invention may be added by any method such as powder, solution, and fine particle dispersion. 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. The addition amount of the benzoic acids of the present invention may be any amount, but is preferably 1 × 10 ⁻⁶ mol or more and 2 mol or less per mol of silver, and 1 × 10 ⁻³ mol.
More preferably, the molar ratio is from 0.5 mol to 0.5 mol.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure, but may be any of Ar-SM, Ar-SSA
Those represented by r are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic rings in these groups are benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, carbazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, Tetrazole, triazine, pyrimidine,
Pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is, for example,
Halogen (e.g., Br and Cl), hydroxy, amino,
Carboxy, alkyl (e.g., having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy
(E.g., those having one or more carbon atoms, preferably those having 1 to 4 carbon atoms) and aryl (which may have a substituent) selected from the group consisting of substituents Is also good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
Mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis- (benzothiazole, 3-mercapto-1,2,4-triazole,
4,5-diphenyl-2-imidazole thiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine,
2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine Monohydrate, 2-amino-5-mercapto-1,
3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydrokilos-2-mercaptopyrimidine, 2
-Mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole , 3- (5-mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N '-[3- (5-mercaptotetrazolyl) phenyl] urea, 2-mercapto-4-phenyloxazole,
Examples include N- [3- (mercaptoacetylamino) propyl] carbazole, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is 0.0001 to 1.0 per mol of silver in the emulsion layer (image forming layer).
A molar range is preferred, more preferably an amount of 0.001 to 0.3 mole per mole of silver.

In the image forming layer (photosensitive layer) in the present invention, a polyhydric alcohol (for example, glycerin and diol of the type described in US Pat. No. 2,960,404) as a plasticizer and a lubricant, and US Pat. No. 2,588,765 are used. And fatty acids or esters described in US Pat. No. 3,121,060 and silicone resins described in British Patent No. 955,061.

In the image forming layer or the protective layer of the image forming layer in the invention, US Pat. Nos. 3,253,921 and 2,27
Light absorbing substances and filter dyes as described in 4,782, 2,527,583 and 2,956,879 can be used. Also, for example, U.S. Pat.
The dye can be mordanted as described in US Pat. As the amount of filter dye used, the absorbance at the exposure wavelength is 0.
1-3 are preferable, and 0.2-1.5 are particularly preferable.

Various dyes and pigments can be used in the photosensitive layer, which is the image forming layer of the present invention, from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer of the present invention may be any, for example, pigments and dyes described in the Color Index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, Examples thereof include carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments including phthalocyanine, and inorganic pigments. Preferred dyes used in the present invention include anthraquinone dyes (e.g., compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), azomethine Dye (compound 17 described in JP-A-5-341441)
To 47 etc.), indoaniline dyes (e.g. JP-A-5-289227)
Nos. 11 to 19 and compounds described in JP-A-5-341441
47, compounds 2-10 to 11 described in JP-A-5-165147) and azo dyes (compounds 10 to 16 described in JP-A-5-341441). As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds used is determined by the desired absorption, but generally 1 m ²
It is preferably used in a range of 1 × 10 ⁻⁶ g or more and 1 g or less.

The photothermographic material of the invention has a photosensitive layer as an image forming layer containing at least one silver halide emulsion on one side of a support, and a back layer on the other side. It is preferably a so-called one-sided photosensitive material.

In the present invention, the back layer preferably has a maximum absorption in a desired range of about 0.3 to 2.0.
750-360nm if the desired range is 750-1400nm
Is preferably 0.005 or more and less than 0.5, more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3. When the desired range is 750 nm or less, the halation is such that the maximum absorption in the desired range before image formation is 0.3 or more and 2.0 or less, and the optical density at 360-750 nm after image formation is 0.005 or more and less than 0.3. Preferably, it is a prevention layer. The method for lowering the optical density after image formation to the above range is not particularly limited. For example, as described in Belgian Patent No. 733,706, a method in which the density of a dye is reduced by decolorization by heating, And a method of decreasing the density by decoloring by light irradiation described in JP-A-17833.

When an antihalation dye is used in the present invention, such a dye has a desired absorption in a desired range, has a sufficiently low absorption in the visible region after treatment, and has a preferable absorbance spectrum shape of the back layer. Any compound may be used as long as is obtained. For example, the following are disclosed, but the present invention is not limited thereto.
As a single dye, JP-A-59-56458, JP-A-2-216140
No. 7-13295, No. 7-11432, U.S. Pat.No.5,380,635, JP-A-2-688539, page 13, lower left column, line 1
On page 9, lower left column, line 9, there are compounds described in JP-A-3-24539 from page 14, lower left column to page 16, lower right column. 53-132334, 56-501
480, 57-16060, 57-68831, 57-101835,
No. 59-182436, JP-A-7-36145, JP-A-7-199409, JP-B-48-33692, JP-B50-16648, JP-B-2-41734, U.S. Pat. No.
There is 5,187,049.

In the present invention, suitable binders for the back layer are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, and 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 (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal))
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

The heat-developable photographic emulsion used in the present invention comprises one or more layers on a support. One layer must contain additional optional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is that the first emulsion layer (usually the layer adjacent to the support) contains an organic silver salt and silver halide, and the second layer or both layers do not contain some other components. No. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, or may include all components in a single layer as described in U.S. Pat.No.4,708,928. Is also good. In the case of a multi-dye, multi-color photothermographic material, each emulsion layer generally has a functional or non-functional layer between the emulsion layers (photosensitive layers), as described in U.S. Pat. No. 4,460,681. Are kept distinct from each other by using the barrier layer.

US Pat. Nos. 4,460,681 and 4,374,9
Backside resistive heating layer as shown in No. 21
stive heating layer) can also be used in a photosensitive heat developed photographic image system.

A hardener may be used in each layer such as the photosensitive layer, the protective layer, and the back layer of the present invention. Examples of hardeners include:
U.S. Pat.No. 4,281,060, polyisocyanates described in JP-A-6-208193 and the like, epoxy compounds described in U.S. Pat.
Vinyl sulfone compounds described in No. 48 and the like are used.

The polymer latex used in the binder of the present invention 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. For the polymer latex of the present invention, `` Synthetic resin emulsion (Hei 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)), `` Chemistry of Synthetic Latex (Souichi Muroi, published by the Society of Polymer Publishing (197)
0)) "and JP-A-64-538. The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably 5 to 100.
A range of about 0 nm is preferable. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

As the polymer latex of the present invention, other than a polymer latex having a normal uniform structure, a so-called core / polymer latex may be 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.

The glass transition temperature (Tg) of the polymer of the polymer latex used in the binder of the present invention is as follows:
The preferred temperature range differs between the back layer and the image forming layer. The protective layer and the back layer have a glass transition temperature of 25 ° C. to 100 ° C. from the viewpoint of film strength and prevention of adhesion failure in order to come into contact with various devices, and the image forming layer promotes the diffusion of photographic useful materials during thermal development. In order to obtain good photographic properties such as high Dmax and low fog, a glass transition temperature of -30C to 40C is preferable, and a glass transition temperature of 0C to 4C is particularly preferable.
0 ° C. The gel fraction of the polymer in the polymer latex used in the image forming layer is 30 wt% or less for the same reason.
Preferably it is 90% by weight. The gel fraction in this case was determined by using a polymer latex at a drying temperature of 70 ° C. to form a membrane sample at 25 ° C. in tetrahydrofuran (TH).
F) was immersed for 24 hours, and the amount of insoluble matter was quantified and determined according to the following formula. Gel fraction (wt%) = [weight of insoluble matter (g) / weight of membrane using polymer latex (g)] × 100

Examples of the polymer used in the polymer latex of the present invention include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. There is. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. 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 1,000, in terms of weight average molecular weight.
About 0-100,000 is preferable. If the molecular weight is too small, the mechanical strength as a binder is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the photothermographic material of the present invention include the following. Methyl methacrylate / ethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer,
Styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer and the like. Such polymers are also commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,85
7, 857x2 (Nippon Zeon Co., Ltd.), VONCORT R3340, R
3360, R3370, 4280, 2830, 2210 (all manufactured by Dainippon Ink and Chemicals, Inc.), Julimer ET-410, 530, SEK101-SEK30
1, FC30, FC35 (all manufactured by Nippon Pure Chemical Co., Ltd.), Polysol F
Polyester resins such as 410, AM200, and AP50 (all manufactured by Showa Polymer Co., Ltd.) include FINETEX ES650, 611, 675, and 8
HYDRAN AP10, 20, 30, 40, VONDIC 1320NS (Dai Nippon Ink Chemical Co., Ltd.) L) as rubber-based resin
ACSTAR 7310K, 3307B, 4700H, 7132C, LQ-618-1 (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 410, 430, 43
5, 2507 (Nippon Zeon Co., Ltd.) and other vinyl chloride resins such as Nipol G351 and G576 (Nippon Zeon Co., Ltd.)
For example, vinylidene chloride resins such as L502 and L513 (manufactured by Asahi Kasei Kogyo Co., Ltd.) and Aron D7020, D5040, D5071 (manufactured by Toa Gosei Co., Ltd.). And the like). These polymers may be used alone, or may be used by blending two or more kinds as necessary.

Among these polymer latexes, acrylic, styrene, acrylic / styrene, vinyl chloride, and vinylidene chloride polymer latexes are preferably used as the binder for the protective layer. Specifically, acrylic resin-based VONCORT R3370, 4280, Nipol Lx857, methyl methacrylate / 2-ethylhexyl acrylate /
Hydroxyethyl methacrylate / styrene / acrylic acid copolymer, vinyl chloride resin Nipol G576, and vinylidene chloride resin Aron D5071 are preferably used.

As the binder for the image forming layer, a styrene / butadiene polymer latex is preferably used. Specifically, rubber-based resins such as LACSTAR3307B and Nipo
l Lx430, 435 are preferably used.

As the binder for the back layer, an acrylic, olefin, or vinylidene chloride-based polymer latex is used. Specifically, an olefin such as an acrylic resin-based julimer ET-410, Sebian A-4635, or Polysol F410 is used. Resin-based Chemipearl S120, vinylidene chloride-based
L502 and Aron D7020 are preferred.

The photographic constituent layer of the present invention is preferably prepared by applying an aqueous coating solution and then drying. However, the term “aqueous” as used herein means that 60% by weight or more of the solvent (dispersion medium) of the coating liquid is water. Components other than water of the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol,
Water-miscible organic solvents such as furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, and oxyethyl phenyl ether can be used.

The total amount of the binder for the protective layer of the present invention is 0.1.
^{2 to} 6.0 g / m ² , more preferably 0.5 to 4.0 g / m ²
Is preferable.

The total amount of the binder for the image forming layer of the present invention is 0.2 to 30 g / m ² , more preferably 1.0 to 15 g / m ^2.
Is preferable.

The total amount of the binder for the back layer of the present invention is 0.01 to 3 g / m ² , more preferably 0.05 to 1.5 g.
/ M ² is preferred.

A cross-linking agent for cross-linking and a surfactant for improving coating properties may be added to each layer.

Each of these layers may be provided in two or more layers. When there are two or more image forming layers, it is preferable to use a polymer latex as a binder for all the layers. Further, the protective layer is a layer provided on the image forming layer and may be present in two or more layers.
Preferably, a polymer latex is used for the layer, especially the outermost protective layer. The back layer is a layer provided on the undercoat layer on the back surface of the support, and there may be two or more layers. However, it is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.

The minimum film forming temperature (MFT) of the polymer latex of the present invention is -30 ° C to 90 ° C, more preferably 0 ° C to 7 ° C.
About 0 ° C. is preferable. A film-forming aid may be added to control the minimum film-forming temperature. The film-forming auxiliary is also called a temporary plasticizer and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex.For example, the aforementioned `` Synthetic Latex Chemistry (Souichi Muroi, published by Polymer Publishing Association (19
70))). Preferred film-forming aids are the following compounds, but the present invention is not limited to the following compounds.

Z-1: benzyl alcohol Z-2: 2,2,4-trimethylpentanediol-
1,3-monoisobutyrate Z-3: 2-dimethylaminoethanol Z-4: diethylene glycol

In particular, when forming the protective layer, it is preferable to add a film-forming auxiliary, and the amount of addition is 1 to 30% by weight based on the solid content of the polymer latex in the coating solution for the protective layer. And more preferably 5 to 20% by weight.

The image forming layer and the protective layer of the invention preferably contain a hydrophilic polymer as a dispersion stabilizer. As specific examples, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and the like are preferably used. Particularly preferred is polyvinyl alcohol.

Specific examples of the hydrophilic polymer used in the image forming layer and the protective layer of the invention are shown below, but the invention is not limited to the following compounds.

[0247]

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The addition amount of these hydrophilic polymers is 1 to 30% by weight, preferably 5 to 20% by weight, of the polymer latex binder derived from the polymer latex of the image forming layer. Further, the amount of the hydrophilic polymer added to the protective layer is preferably 0.2 to 20% by weight of the polymer latex binder derived from the polymer latex of the protective layer, and more preferably 0.5 to 10 watts.
t% is preferred.

An undercoat layer containing a vinylidene chloride copolymer is provided on both sides of the support of the present invention. The vinylidene chloride copolymer at this time is a repeating unit of a vinylidene chloride monomer (hereinafter, also referred to as “vinylidene chloride monomer”).
At least 70% by weight. When the amount of the vinylidene chloride monomer is less than 70% by weight, sufficient moisture-proof properties cannot be obtained, and the dimensional change over time after thermal development becomes large. Further, the vinylidene chloride copolymer may include a repeating unit of a carboxyl group-containing vinyl monomer (hereinafter, also referred to as “carboxyl group-containing vinyl monomer”) as another structural repeating unit of the vinylidene chloride monomer. preferable. The inclusion of such a constitutional repeating unit is because the polymer (polymer) is crystallized by using only the vinyl chloride monomer, so that it is difficult to form a uniform film when the moisture-proof layer is applied, and This is because a carboxyl group-containing vinyl monomer is indispensable for stabilizing the (polymer).

The vinylidene chloride copolymer of the present invention contains 70%
〜99.9% by weight, more preferably 85-99% by weight of vinylidene chloride monomer and 0.1-5% by weight, more preferably 0.2-3% by weight of a carboxyl group-containing vinyl monomer. Is a copolymer.

The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer of the present invention is a vinyl monomer having one or more carboxyl groups in the molecule, and specific examples thereof include acrylic acid, methacrylic acid and itacone. Acids, citraconic acid, and the like.

The vinylidene chloride copolymer of the present invention may contain, in addition to the vinylidene chloride monomer and the carboxyl group-containing monomer, a repeating unit of a monomer copolymerizable therewith.

Specific examples of these monomers include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, styrene and the like.

These monomers may be used alone or in combination of two or more.

The vinylidene chloride copolymer of the present invention has a weight average molecular weight of 45,000 or less, more preferably 10,000 to 45.
000 or less is preferred. When the molecular weight increases, the adhesion between the vinylidene chloride copolymer layer and the support layer such as polyester deteriorates.

The vinylidene chloride copolymer of the present invention may be in the form dissolved in an organic solvent or in the form of an aqueous dispersion of latex, but the form of an aqueous dispersion of latex is preferred.

In this case, a latex of polymer particles having a uniform structure or a latex of polymer particles having a so-called core-shell structure having different compositions in the core portion and the shell portion may be used.

The particle size and the like of the polymer particles in the latex are the same as those used for the binder of the image forming layer and the protective layer described later.

The arrangement of the monomer units of the vinylidene chloride copolymer is not limited, and may be any of periodic, random, block and the like.

Specific examples of the vinylidene chloride copolymer of the present invention include the following. However, ()
The numbers in the parentheses represent weight ratios. The average molecular weight represents a weight average molecular weight.

V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1) (average molecular weight)
42000) V-2 Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (87:
Latex of 4: 4: 4: 1) (average molecular weight of 40,000) V-3 Latex of vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90: 6: 2: 2) (average molecular weight of 38000) V-4 Vinylidene chloride : Ethyl methacrylate: 2-hydroxyethyl methacrylate: acrylic acid (90: 8:
1.5: 0.5) latex (average molecular weight 44000) V-5 Core-shell type latex (core 90% by weight, shell 10% by weight) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (93:
3: 3: 0.9: 0.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (8
8: 3: 3: 3: 3) (Average molecular weight 38000) V-6 Core-shell type latex (70% by weight core, 30% by weight shell) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (9
2.5: 3: 3: 1: 0.5) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (average molecular weight 20,000)

The vinylidene chloride copolymer may be used alone or in combination of two or more.

The content of the vinylidene chloride copolymer of the present invention is at least 0.3 μm, preferably at least 0.3 μm and at most 4 μm, as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer. Range.

The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support. Usually, one layer is provided on each side. May be provided in two or more layers.
When a multi-layer structure of two or more layers is used, the total amount of the vinylidene chloride copolymer may be within the range of the present invention.

As described above, since the vinylidene chloride copolymer layer is usually formed as a single layer, the thickness thereof is preferably 0.3 μm or more and 4 μm or less in order to obtain a good coated surface. More preferably, it is in the range of 0.6 μm or more and 3 μm or less, and still more preferably in the range of 1.0 μm or more and 2 μm or less.

Such a layer may contain a crosslinking agent, a matting agent and the like in addition to the vinylidene chloride copolymer.

Various supports can be used for the photothermographic material of the present invention. Typical supports include polyesters such as polyethylene terephthalate, polyethylene naphthalate, etc., cellulose nitrate, cellulose esters, polyvinyl acetal, polycarbonate and the like. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferred in terms of strength, dimensional stability, chemical resistance and the like. The thickness of the support is preferably 90 to 180 μm as a base thickness excluding the undercoat layer.

The support used in the photothermographic material of the present invention may be used in order to alleviate the internal strain remaining in the film at the time of biaxial stretching and eliminate the heat shrinkage distortion generated during the heat development.
Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of 30 to 185 ° C is preferably used. Such a thermal relaxation treatment may be performed at a constant temperature within the temperature range, or may be performed while increasing the temperature.

The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. In the case where the transfer is carried out in the form of a web, the transfer tension of the support during the heat treatment is preferably relatively low, and specifically, 7 kg /
cm ² or less, particularly preferably to 4.2 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is about 0.5 kg / cm ² .

Such heat treatment is preferably carried out after a treatment for improving the adhesion of the image forming layer and the back layer to the support, an undercoating layer containing a vinylidene chloride copolymer, and the like are applied. .

The support 12 after such heat treatment was used.
The heat shrinkage by heating at 0 ° C for 30 seconds is-
0.03% to + 0.01%, lateral direction (TD) is 0 to 0.
Preferably, it is 04%.

The support may be coated with an undercoat layer using SBR, polyester, gelatin or the like as a binder, if necessary, in addition to the vinylidene chloride copolymer layer. These undercoat layers may have a multilayer structure or may be provided on one side or both sides of the support. At least one of these undercoat layers can be a conductive layer. The general thickness (per layer) of the undercoat layer may be from 0.01 to 5 μm, more preferably from 0.05 to 1 μm, and the thickness as a conductive layer is from 0.01 to 1 μm, more preferably from 0.1 to 1 μm. 03-
0.8 μm.

The back layer or undercoat layer adjacent to the support of the photothermographic material of the present invention preferably contains a metal oxide in order to reduce adhesion of dust. It is preferable that at least one of the layers (provided on both surfaces of the support) be a conductive layer. However, the conductive layer is preferably not the outermost back layer.

Here, the metal oxide used is disclosed in
Particularly preferred are those described in JP-A-20033 and JP-A-56-82504.

The amount of the conductive metal oxide of the present invention to be used is preferably 0.05 to ²⁰ g, more preferably 0.1 to 10 g per 1 m ² of the light-sensitive material. The surface resistivity of the metal oxide-containing layer is 10 ¹² Ω or less in an atmosphere of 25 ° C. and 25% RH,
Preferably, it is 10 ¹¹ Ω or less. Thereby, good antistatic properties can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually about 10 ⁷ Ω.

In the present invention, a better antistatic property can be obtained by using a fluorine-containing surfactant in addition to the above metal oxide.

The preferred fluorinated surfactant used in the present invention has a fluoroalkyl group, a fluoroalkenyl group or a fluoroaryl group having 4 or more (usually 15 or less) carbon atoms, and an anionic group ( Sulfonic acid (salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cationic group (amine salt, ammonium salt,
Aromatic amine salts, sulfonium salts, phosphonium salts),
Surfactants having a betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue) No.

These fluorinated surfactants are disclosed in
0722, UK Patent 1,330,356, US Patent 4,335,201
No. 4,347,308, British Patent No. 1,417,915, JP-A-55
-149938, 58-196544 and British Patent No. 1,439,402. Some of these specific examples are described below.

[0279]

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The layer to which the fluorine-containing surfactant of the present invention is added is not particularly limited as long as it is at least one layer of the photothermographic material. For example, a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer,
A back layer can be used. Among them, a preferable addition site is the surface protective layer, and either one of the image forming layer side and the back layer side may be used. However, it is more preferable that the compound is added to at least the image forming layer side surface protective layer.

When the surface protective layer is composed of two or more layers, any one of them may be used, and the surface protective layer may be further overcoated on the surface protective layer.

The amount of the fluorinated surfactant used in the present invention may be 0.0001 to 1 g per m ² of the light-sensitive material, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003. ０．１0.1 g.

The fluorinated surfactant of the present invention comprises 2
Species or more may be mixed.

In the present invention, the Beck smoothness is determined by the Japanese Industrial Standard (JIS) P8119 “Smoothness test method of paper and paperboard using Beck tester” and TAPPI standard method T4.
79 can be easily obtained.

The Bekk smoothness of at least one of the surface having the image forming layer of the photothermographic material of the invention and the outermost layer surface opposite to the image forming layer, preferably both, is 2,000 seconds or less, more preferably 10 seconds or less. 2000 seconds.

The Beck smoothness of the surface of the outermost layer having the image forming layer of the photothermographic material and the surface of the outermost layer opposite to the surface are determined by the average particle diameter of fine particles called a matting agent contained in the layers on both sides. And it can be controlled by changing the addition amount in various ways. The matting agent is preferably contained in the protective layer which is the outermost layer farthest from the support on the surface having the image forming layer, and is preferably contained in the back layer which is not the outermost layer on the opposite side.

The preferred average particle size of the matting agent in the present invention is in the range of 1 to 10 μm.

In the present invention, a preferable addition amount of the matting agent is in the range of 5 to 400 mg / m ² , particularly 10 to 200 mg / m ² .

The matting agent used in the present invention may be any solid particles which do not adversely affect various photographic characteristics. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, and silicates of calcium and aluminum. Examples include matting agents for organic polymers such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof.

In the present invention, the porous matting agent described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, JP-A-4-127142, page 3 upper right column A matting agent surface-modified with an alkali described in line 7 to page 5, lower right column, line 4, an organic polymer matting agent described in paragraphs [0005] to [0026] of JP-A-6-118542. It is more preferable to use

Also, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an amorphous matting agent and a spherical matting agent, mats having different average particle sizes. (For example, a matting agent having an average particle diameter of 1.5 μm or more and a matting agent having an average particle diameter of 1 μm or less described in JP-A-6-118542).

In the present invention, it is preferable that a slip agent is contained in the surface having the image forming layer and / or the outermost surface layer opposite to the surface.

The lubricant in the present invention is not particularly limited, and may be any compound as long as it is present on the surface of an object and reduces the coefficient of friction on the surface of the object as compared to the case where it is not present.

Representative examples of the slip agent used in the present invention include, for example, US Pat. No. 3,042,522 and British Patent No. 95
No. 5,061, U.S. Pat.Nos. 3,080,317, 4,004,927,
No. 4,047,958, No. 3,489,567, British Patent No. 1,143,
No. 118, etc., silicone-based slip agent, U.S. Pat.
No. 4,043, No. 2,732,305, No. 2,976,148, No. 3,2
No. 06,311, German Patent No. 1,284,295, higher fatty acid type, alcohol type, acid amide type slip agent described in No. 1,284,294, etc., British Patent No. 1,263,722, U.S. Patent No. 3,933,516 No. Patent No. 2,588,765, No. 3,1
No. 21,060, UK Patent No. 1,198,387, etc., ester-based and ether-based slip agents, U.S. Pat.
There is a taurine-based slip agent described in 3,042,222.

Specific examples of preferably used slip agents include Cellolsol 524 (main component carnauba wax), Polylon A, 393, H-481 (main component polyethylene wax), and Himicron G-110 (main component ethylene bisstearic acid). Amide), High Micron G-270
(Main component stearic acid amide) (all manufactured by Chukyo Yushi Co., Ltd.).

The amount of the slip agent used is 0.1 to 50% by weight, preferably 0.5 to 30% by weight, based on the amount of the binder in the added layer.

A method for obtaining a color image using the photothermographic material of the present invention is described in JP-A-7-13295, page 10, left column 4
There is a method described from the third line to the 11th left column, 40th line. Also, as a stabilizer for color dye images, UK Patent No. 1,326,889
No. 3,432,300, U.S. Pat.No. 3,698,909, U.S. Pat.
Nos. 574,627, 3,573,050, 3,764,337 and 4,042,394.

The photothermographic emulsion of the present invention can be coated by various coating operations including dip coating, air knife coating, flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

In the photothermographic material of the present invention, additional layers such as a dye-receiving layer for receiving a moving dye image, an opaque layer when reflective printing is desired, a protective topcoat layer and photothermographic techniques It may include a known primer layer and the like. The light-sensitive material of the present invention is preferably capable of forming an image with only one light-sensitive material, and it is preferable that a functional layer required for image formation such as an image receiving layer does not become another light-sensitive material.

The exposure apparatus used for the imagewise exposure according to the present invention may be any apparatus capable of performing exposure with an exposure time of less than 10 ^-7 seconds, but is generally an LD (Laser Diode) or an LED.
An exposure apparatus using (Light Emitting Diode) as a light source is preferably used. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

The exposure of the present invention is performed by overlapping the light beams of the light source with each other, and the overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap means, for example, that the beam diameter is equal to the full width at half maximum of the beam intensity (FWHM).
Can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient).

In the present invention, this overlap coefficient is 0.2
0.5 or less, and a lower value is more desirable from the viewpoint of high productivity.

The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. Also,
The channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface type, a multi-channel is preferably used.

The photothermographic material of the present invention has a low haze at the time of exposure and tends to cause interference fringes. Examples of the interference fringe prevention technology include a technology disclosed in Japanese Patent Application Laid-Open No. HEI 5-113548 and the like, in which a laser beam is obliquely incident on a photosensitive material, and a technology disclosed in International Patent WO95 / 31754 and the like. Methods using a mode laser are known, and it is preferable to use these techniques.

The heat development step of forming an image on the photothermographic material of the present invention may be performed by any method and may be performed by any method. Usually, the temperature of the photosensitive material exposed imagewise is increased. Is developed. As a preferred embodiment of the thermal developing machine to be used, as a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum, Japanese Patent Publication No. 5-56499, Patent Publication No. 684453, Japanese Patent Application Laid-Open No. 9-292695, Kaihei 9-297385 and International Patent WO95
/ 30934, as a non-contact type, JP-A-7-13294, International Patent WO 97/28489, 97/28488
And JP-A-97 / 28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C, more preferably 100 to 140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

As a method for preventing processing unevenness due to a dimensional change during thermal development of the photothermographic material of the present invention, a temperature of 80.degree.
A method of forming an image by heating at a temperature of less than 5 ° C. (preferably 113 ° C. or less) for 5 seconds or more so as not to produce an image, and then thermally developing the image at 110 ° C. or more and 140 ° C. or less (so-called multi-step heating method) It is valid.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine of FIG. 1 flattens the photothermographic material 10 after carrying out the heat development by correcting the photothermographic material 10 into a planar shape and carrying it into the heating section while carrying out preheating. It has a carry-out roller pair 12 that carries out the heat from the heating unit while correcting the shape. The photothermographic material 10 is thermally developed while being transported from the carry-in roller pair 11 to the carry-out roller pair 12. In the conveying means for conveying the photothermographic material 10 during the heat development, a plurality of rollers 13 are provided on the side where the surface having the image forming layer contacts, and the non-woven fabric (for example, A smooth surface 14 on which aromatic polyamide or Teflon) is attached is provided. The back surface of the photothermographic material 10 is conveyed by sliding a back surface on a smooth surface 14 by driving a plurality of rollers 13 in contact with the surface having the image forming layer. Heating means roller 1
3 and the photothermographic material 10
The heater 15 is installed so as to be heated from both sides. As a heating means in this case, a plate heater or the like can be used. Although the clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, it is appropriately adjusted to a clearance that can transport the photothermographic material 10. Preferably it is 0 to 1 mm.

Material and smooth surface 1 of the surface of the roller 13
The member 4 is durable at high temperature and may be anything as long as it does not hinder the conveyance of the photothermographic material 10, but the material of the roller surface is made of silicone rubber, and the member of the smooth surface is made of aromatic polyamide or Teflon (PTFE). Non-woven fabrics are preferred. It is preferable that a plurality of heaters be used as the heating means, and that the heating temperature be set freely.

The heating section comprises a preliminary heating section A having a carry-in roller pair 11 and a heat development processing section B provided with a heater 15. The preliminary heating section A upstream of the heat development processing section B is provided. Is lower than the heat development temperature (for example, 10 to 50).
It is preferable that the temperature is set to be higher than the glass transition temperature (Tg) of the support of the photothermographic material 10 so that development unevenness does not occur.

Further, a guide plate 16 is provided downstream of the thermal development processing section B, and a slow cooling section C having a pair of unloading rollers 12 and the guide plate 16 is provided. The guide plate 16 is preferably made of a material having low thermal conductivity, and is preferably cooled gradually.

The above description has been made with reference to the illustrated examples. However, the present invention is not limited to this. For example, JP-A-7-13294, Japanese Patent Application No. 10-177610,
The thermal developing machine used in the present invention, such as that described in Japanese Patent Application No. 10-249940, may have various configurations. In the case of the multi-stage heating method preferably used in the present invention, two or more heat sources having different heating temperatures may be provided, and heating may be performed continuously at different temperatures.

[0312]

EXAMPLES The effects of the present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of Support (Base) Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6) according to a conventional method. / 4 (measured at 25 ° C. in a weight ratio). This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled.
An unstretched film having a thickness of 120 μm after heat setting was prepared.

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. 3. After slitting the chuck portion of the tenter, knurling is performed on both ends.
The film was wound at 8 kg / cm ² . In this way, the width 2.4 m,
A roll having a length of 3500 m and a thickness of 120 μm was obtained.

(2) Undercoat layer (a-1) Polymer latex V-5 A core-shell type latex comprising 90% by weight of a core and 10% by weight of a shell, the core comprising vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93/3/3 / 0.9 / 0.1 (% by weight) Shell part Vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 8
8/3/3/3/3 (% by weight) Weight average molecular weight 38000 Solid content 3.0 g / m ² 2,4-Dichloro-6-hydroxy-s-triazine 23 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ² undercoat layer (a-2) polymer latex styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (% by weight) Solid content 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 ²⁺ content 30 ppm, jelly Strength 230g) 50mg / m ²

(3) Conductive layer Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 42 mg / m ² deionized gelatin (Ca ^{2 +} content 0.6 ppm) 8 mg / m ² compound A 0.2 mg / m ² polyoxyethylene phenyl ether 10 mg / m ² Sumitex resin M-3 (water-soluble melamine compound, Sumitomo chemical Co., Ltd.) 18 mg / m ² dye A Amount of coating at which optical density of 783 nm becomes 1.0 SnO ₂ / Sb (9/1 weight ratio, needle-shaped fine particles, major axis / minor axis = 20 to 30, manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² matting agent ( Polymethyl methacrylate, average particle size 5μm) 7mg / m ²

[0317]

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(4) Protective layer Polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer)) 1000 mg / m ² polystyrenesulfonate (molecular weight of 1000-5000) 2.6 mg / m ² Cellosol 524 (Chukyo Yushi Co.) 25 mg / m ² Sumitex resin M-3 (water-soluble melamine compound, Sumitomo chemical Co., Ltd.) 218 mg / m ²

(5) Preparation of Support I An undercoat layer (a-1) and an undercoat layer (b) were sequentially applied to both sides of the support (base) and dried at 180 ° C. for 4 minutes. Next, the undercoat layer (a-1) and the undercoat layer (b) are applied, and a conductive layer and a protective layer are sequentially applied to one side of the undercoat layer,
Each was dried at 180 ° C. for 4 minutes to prepare a PET support I having a back layer / undercoat layer. Undercoat layer (a-
The dry thickness (one side) of 1) was 2.0 μm.

(6) Preparation of Support II Similarly, an undercoat layer (a-
2) and the undercoat layer (b) are sequentially applied, and
After drying at 4 ° C. for 4 minutes, a conductive layer and a protective layer were sequentially applied to one side and dried at 180 ° C. for 4 minutes, respectively, to prepare a PET support II having a back layer / undercoat layer. The dry thickness (one side) of the undercoat layer (a-2) was 2.0 μm.

(7) Heat treatment for transport (7-1) Heat treatment PET supports I and II having a back layer / undercoat layer
It was placed in a heat treatment zone with a total length of 200 m set at 0 ° C. and transported at a tension of 3 kg / cm ² and a transport speed of 20 m / min. (7-2) Post-heat treatment After the heat treatment, post-heat treatment was performed by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time was 10 kg / cm ² .

<< Preparation of Silver Halide Emulsion >> (Emulsion A) 11 g of phthalated gelatin and potassium bromide in 700 ml of water
30 mg of lithium, 10 mg of sodium benzenethiosulfonate
After dissolving and adjusting the pH to 5.0 at a temperature of 40 ° C, silver nitrate 18.
1 mol / l of 159 ml of aqueous solution containing 6 g and potassium bromide
(NH_Four)_TwoRhCl_Five(H _TwoO) 5 × 10^-6Mol / l
Turtle and K_ThreeIrCl₆2 × 10^-FiveIn moles / liter
Control aqueous solution while maintaining the aqueous solution at pAg 7.7.
It was added over 6 minutes and 30 seconds by the wet method. Then, silver nitrate 5
1 mol / l of 476 ml of an aqueous solution containing 5.5 g and potassium bromide
And K_ThreeIrCl₆2 × 10^-FiveInclude in moles / liter
While maintaining the halogen salt aqueous solution at pAg 7.7,
It was added over a period of 28 minutes and 30 seconds by the Bulljet method. Then pH
And then subjected to coagulation and sedimentation for desalting.
g, low molecular weight gelatin having an average molecular weight of 15,000 (calcium
23.7 g, pH 5.9, pAg 8.0
Was adjusted. The resulting particles have an average particle size of 0.08 μm,
Cubic particles with a projected area variation coefficient of 9% and a (100) face ratio of 90%
Was.

The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver. After 3 minutes, 154 μm of sodium thiosulfate was added.
Mol, and the mixture was aged for 100 minutes.
Methyl-1,3,3a, 7-tetrazaindene is 5 × 10
After adding ^-4 mol, the temperature was lowered to 40 ° C.

Thereafter, the temperature was maintained at 40 ° C.
12.8 × 10 ^-4 mole of the following sensitizing dye A per mole, 6.4 ×
10 ^-3 mol of compound B are added with stirring, and after 20 minutes 30
The mixture was rapidly cooled to ° C. to complete the preparation of silver halide emulsion A.

[0325]

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<< Preparation of Silver Organic Acid Dispersion >><Organic Acid Silver A> 6.1 g of arachiic acid, 37.6 g of behenic acid, 700 ml of distilled water, 70 ml of tert-butanol, and 123 ml of a 1N aqueous solution of NaOH were mixed at 75 ° C. The mixture was stirred for an hour to react, and the temperature was lowered to 65 ° C. Next, 112.5 ml of an aqueous solution of 22 g of silver nitrate was added over 45 seconds, and the mixture was left as it was for 5 minutes, and the temperature was lowered to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid content thus obtained is treated as a wet cake without drying,
To a wet cake having a dry solid content of 100 g, 7.5 g of polyvinyl alcohol (trade name: PVA-217) and water were added to make the total amount 500 g, and the mixture was preliminarily dispersed with a homomixer.

Next, the pre-dispersed stock solution is dispersed in a disperser (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain an organic acid silver dispersion A. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.04 μm and an average major axis of 0.8 μm.
m, needle-like particles having a variation coefficient of 30%. The measurement of the particle size was performed by MasterSizerX manufactured by Malvern Instruments Ltd. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. Thus, organic acid silver A having a silver behenate content of 85 mol% was prepared.

<< Preparation of Solid Fine Particle Dispersion of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane >> 1,1-bis (2-hydroxy-3, 5-dimethylphenyl) -3,5,5-trimethylhexane 20 g for Kuraray Co., Ltd.
3.0 g of MP-203 made of MP polymer and 77 ml of water were added, and the mixture was thoroughly stirred and left as a slurry for 3 hours. Then 0.5
360 g of zirconia beads having a diameter of 360 mm were prepared and placed in a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 3 hours to prepare a dispersion of solid fine particles of a reducing agent. The particle size is 80% by weight of the particles
It was 0.3 μm or more and 1.0 μm or less.

<< Preparation of solid fine particle dispersion A of polyhalogen compound >> Kuraray Co., Ltd.
4 g of MP-203 made of MP polymer, 0.25 g of compound C, and 66 g of water
Was added and stirred well, and then 200 g of 0.5 mm zirconia beads were prepared and placed in a vessel together with the slurry. A dispersing machine (1 / 16G sand grinder mill: IMEX)
For 5 hours to prepare a solid fine particle dispersion. The particle diameter was such that 80% by weight of the particles were 0.3 μm or more and 1.0 μm or less.

[0330]

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<< Preparation of Emulsion Layer Coating Solution >> The following binder, material and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Thus, an emulsion layer coating solution was obtained.

Binder; Luckstar 3307B 406 g as solid content (manufactured by Dainippon Ink and Chemicals, Inc .; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl)- 3,5,5-trimethylhexane 119 g as solids Compound of formula (1) of the present invention (Table 1) Tribromomethylphenylsulfone 11.6 g as solids Solid fine particle dispersion A of polyhalogen compound 0.1 mol When adding the compound of (1), this dispersion A was reduced and adjusted to a total of 0.1 mol.) Sodium benzenethiosulfonate 0.44 g benzotriazole 1.25 g polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.) 10.0 g iso-propylphthalazine 0.10 mol sodium dihydrogen orthophosphate 0.13 g development inhibitor A 9.38 g nucleating agent (compound C-62 of the present invention) 0.03 mol dye A 783 Coating amount at which nm optical density becomes 0.3 Silver halide emulsion A 0.05 mol as Ag amount

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<< Preparation of Coating Solution for Protective Layer Under Emulsion Surface >> Polymer latex solution of methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) (copolymer a glass transition temperature of 57 ° C. in, 21.5wt%, 15wt% containing compound D with respect to the solid content of the latex as coalescent as solid concentration) of H ₂ O was added to 956G, compound E 1.62 g , 2.3 g of compound G, 1.98 g of matting agent (polystyrene particles, average particle size 7 μm) and 23.6 g of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.), and further H ₂ O
Was added to prepare a coating solution (pH 5.6).

<< Preparation of Coating Solution for Emulsion Upper Protective Layer >> Polymer latex solution of methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) (copolymer a glass transition temperature of 54 ° C. in, 21.5wt%, 15wt% containing compound D with respect to the solid content of the latex as coalescent as solid concentration) of H ₂ O was added to 630 g, carnauba wax ( Chukyo Yushi Co., Ltd., Cellsol 524) 3
6.30 g of 0 wt% solution, 0.72 g of compound E, 7.95 g of compound F,
Compound G 0.7 g, matting agent (polystyrene particles, average particle size 7 μm) 1.18 g and polyvinyl alcohol (Kuraray
8.30 g of PVA-235), and then H ₂ O.
A coating solution was prepared (pH 2.8).

[0335]

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<< Preparation of Photothermographic Material >> Undercoat Layer
The above emulsion layer coating solution was applied onto the undercoat layer of the PET support on the side coated with (a) and the undercoat layer (b) so that the coating amount of silver was 1.7 g / m ² . Furthermore, the coating liquid for the solid content of the polymer latex was 1.31 g / m ^2.
At the same time as the emulsion coating solution. Thereafter, the coating solution for the upper protective layer on the emulsion surface was applied thereon so that the coating amount of the solid content of the polymer latex was 3.02 g / m ² , to produce a photothermographic material. The film surface pH on the image forming layer side of the obtained photothermographic material was 4.9, and the Bekk smoothness was 660.
Second, the pH of the opposite membrane surface is 5.9, and the Beck smoothness is 560.
Seconds.

<< Evaluation of Photographic Performance >> (Exposure Processing) The obtained photothermographic material was
After adjusting the humidity to ℃ and 45% RH, the beam diameter (FWHM of 1/2 of beam intensity) 12.56μm, laser output 50mW, output wavelength 783
using a laser exposure apparatus of single channel cylindrical inner surface type provided with a semiconductor laser of nm, the exposure time by changing the rotational speed of the mirror, adjusting dose by changing the output value, 2 × 10 ^-8 Exposure in seconds. At this time, the overlap coefficient (FWHM / pitch width of sub-scan) is 0.5
It is.

(Thermal Development Processing) The exposed photothermographic material was heated using the thermal developing machine shown in FIG. 1 and the roller surface material of the thermal development processing section was made of silicone rubber, and the smooth surface was made of Teflon nonwoven fabric. A heat development process was performed at 100 ° C. for 5 seconds and a heat development processing unit at 120 ° C. for 20 seconds. The temperature accuracy in the width direction is ± 1
° C.

(Evaluation of Photographic Performance) The obtained images were evaluated with a Macbeth TD904 densitometer (visible density). The measurement results were Dmin, sensitivity (represented by the relative value of the reciprocal of the ratio of the amount of exposure that gives a density higher than Dmin by 1.0), and γ (contrast).
Was evaluated. γ is the density of 0.2 with the logarithm of the exposure amount as the horizontal axis.
It was expressed by the slope of a straight line connecting points 2.5 and 2.5. Sensitivity is sample No.1
It was expressed as a relative value when the sensitivity of (photographic characteristic 1) was set to 100. )

(Development Temperature Latitude) After exposure in the same manner as described above, development was performed under conditions of 119 ° C. for 20 seconds and 122 ° C. for 20 seconds, and evaluated. The evaluation was expressed by a sensitivity difference (Δlog E) giving a density of 1.0 and a Dmin difference (ΔDmin).

(Evaluation of Image Preservation Property)
After performing a thermal development process (120 ° C., 20 seconds) in the same manner as described above, 10,000 lux Xe at 25 ° C. and 50% RH.
After irradiation with a light source, UV light (λ = 365 nm)
Evaluation was made based on the increase in Dmin.

The results are shown in Table 1. As is evident from Table 1, the configuration of the present invention has a small performance variation with temperature change, and has good image storability without depending on the base undercoat.

[0343]

[Table 1]

(Example 2) Sample Nos. 4 and 11 of Example 1
Was subjected to exposure and development to a density of 4.0 by the method of Example 1, and the dimensional change rate due to the heat development treatment and the dimensional change rate over time after the treatment were measured.

(Measurement method of dimensional change rate due to thermal development processing)
Two holes having a diameter of 8 mm were formed in the untreated sample (size 5 cm × 25 cm) having the entire surface exposed, with an interval of 200 mm.
The distance between the two holes was accurately measured using a pin gauge with a precision of / 1000 mm. The dimension at this time is defined as X (unit: mm). Then, using the heat developing machine shown in FIG.
After the heat development processing under the developing condition of second, the dimensions 120 minutes later were measured with a pin gauge. The dimension at this time is Y (unit: m
m). The dimensional change rate (%) = [(Y−X) / 200] × 100.

(Measurement method of dimensional change rate over time after thermal development processing) A sample (size 5 cm × 2
5 mm), two holes each having a diameter of 8 mm were formed at a distance of 200 mm, and then, at a temperature of 120 ° C. and 30 ° C. using the heat developing machine shown in FIG.
After 3 minutes of heat development, the size after 3 minutes is reduced to 1/1000
It measured using the pin gauge of mm precision. The dimension at this time is defined as X ₁ (unit: mm). Then, the size Y ₁ (unit: mm) after a lapse of 240 minutes was measured.

This series of measurements was performed under an atmosphere of 25 ° C. and 75% RH and an atmosphere of 25 ° C. and 20% RH, respectively. The dimensional change rate (%) = [(Y ₁ −X ₁ ) / 200] × 100.

The results are shown in Table 2. As is clear from Table 2, it can be seen that in Sample No. 4 using the support I, the dimensional change due to the heat development treatment, particularly the dimensional change due to the aging after the treatment, was extremely small.

[0349]

[Table 2]

[0350]

According to the present invention, the performance as a high-contrast photographic material is excellent, and fluctuations in development conditions and photographic performance due to storage can be prevented.

[Brief description of the drawings]

FIG. 1 is a side view showing an example of the configuration of a heat developing machine used for a heat development process of a photothermographic material according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 heat-developable photosensitive material 11 carry-in roller pair 12 carry-out roller pair 13 roller 14 smooth surface 15 heating heater 16 guide plate A preheating section B heat development processing section C slow cooling section

Claims (3)

[Claims] An image forming layer comprising at least (a) a non-photosensitive organic silver salt, (b) a photosensitive silver halide, (c) a reducing agent and (d) a nucleating agent on a support, A protective layer is provided on the image forming layer, a polymer latex is used as a binder for the image forming layer and the protective layer, and the layer on the image forming layer side contains a compound represented by the formula (1). Characteristic photothermographic material. Embedded image [In the formula (1), Z ¹ and Z ² each represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, and Y ¹
Represents a —CO— group or a —SO ₂ — group, Q represents an arylene group or a divalent heterocyclic group, L represents a linking group, W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, phosphorus Represents an acid group, a hydroxyl group, a quaternary ammonium group or a polyethyleneoxy group. n represents 0 or 1. ] 2. At least one selected from a substituted alkene derivative represented by the following formula (2), a substituted isoxazole derivative represented by the following formula (3), and a specific acetal compound represented by the following formula (4): 2. The photothermographic material according to claim 1, comprising a nucleating agent. Embedded image [In the formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z, R ² and R
³ , R ¹ and R ² , and R ³ and Z may be bonded to each other to form a cyclic structure. In the formula (3), R ⁴
Represents a substituent. In the formula (4), X and Y each independently represent a hydrogen atom or a substituent;
Each independently represents an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group. In the formula (4), X and Y, and A and B may be bonded to each other to form a cyclic structure. ] 3. A thickness of 0.3 μm or more (total thickness per one side) in which a support contains a vinylidene chloride copolymer containing at least 70% by weight of vinylidene chloride monomer repeating units on both surfaces. 2. An undercoat layer according to claim 1.
Or 2 photothermographic materials.