JP2000284399A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure ultrahigh contrast, to suppress fog and to prevent the occurrence of black spots by incorporating a nucleating agent on the side of a substrate having photosensitive silver halide and specifying the content of formic acid or its salt to be a specific value or less. SOLUTION: The heat developable photosensitive material contains a nucleating agent on the side of the substrate having photosensitive silver halide and has <=5 mmol content of formic acid or its salt based on 1 mol silver. The nucleating agent preferably contains at least one compound selected from compounds of formulae I-III and a hydrazine derivative. In the formulae, R11-R13 are each H or a substituent, Z is an electron withdrawing group or silyl, R14 is a substituent, X and Y are each H or a substituent and A and B are each alkoxy, alkylthio, alkylamino, aryloxy, arylthio, anilino, heterocyclic oxy, heterocyclic thio or heterocyclic amino.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, particularly to a photothermographic material suitable for photolithography, such as a scanner and an image setter, and a method for producing the same. More specifically, the present invention makes it possible to obtain an image which is super-high contrast, hardly fogged, does not generate black spots, and has a Dmax (maximum density) and a good halftone dot quality, which is optimal for photolithography. The present invention relates to a photothermographic material for photoengraving and a method for producing the same.

[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, environmental preservation in the photoengraving field,
From the viewpoint of space saving, it is strongly desired to reduce the amount of processing waste liquid. There, you can use a laser scanner or a laser imagesetter to make the exposure more efficient,
There is a need for a technique relating to a photothermographic material for photolithography capable of forming a sharp black image having high resolution and sharpness. In these photothermographic 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.

[0003] A method of forming an image by thermal development is described in, for example, US Patent Nos. 3,152,904 and 3,457,075, and
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 image formed 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.

Although the photothermographic materials have been conventionally known, most of these materials form a photosensitive layer by applying a coating solution using an organic solvent such as toluene, methyl ethyl ketone (MEK) or methanol as a solvent. are doing.
The use of an organic solvent as a solvent is disadvantageous not only in adverse effects on the human body in the manufacturing process but also in cost due to recovery of the solvent and the like.

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. Japanese Patent Application Laid-Open No. 50-151138 discloses an example using polyvinyl alcohol as a binder. Further, JP-A-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, if such a binder is used, the photosensitive layer can be formed using a coating solution of a water solvent, and environmentally friendly,
The cost advantage is great. However, when a polymer such as gelatin, polyvinyl alcohol, or water-soluble polyacetal is used as a binder, the compatibility with an organic silver salt is poor, and not only a coated material that can be practically used on a coated surface cannot be obtained, but also the silver color of a developed portion Only those having a markedly impaired commercial value, such as brown or yellow whose tone is far from black which is originally preferable, and a low blackening density of an exposed portion and a high density of an unexposed portion were obtained.

EP-A-762,196 and JP-A-9-90550 disclose that a photosensitive silver halide grain used for a photothermographic material contains a group VII or VIII metal ion or a metal complex ion. It is disclosed that high contrast photographic characteristics can be obtained by incorporating a hydrazine derivative into a material. However, when a nucleating agent such as hydrazine is used in combination with the binder used in the above-mentioned aqueous solvent coating solution, a high-contrast image can be obtained. When used, there is a problem that sand-like fog frequently occurs in unexposed areas called black spots which occur specifically.
Furthermore, the dot quality was not satisfactory.

[0007] EP 809141 discloses that a non-photosensitive reducible silver source (for example, organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide) and a silver reducing agent are dispersed in an organic binder. It describes that a small amount of formic acid is fogged in the photothermographic material obtained by coating to promote the generation of black spots. However, since this photographic material does not contain a nucleating agent, it is impossible to obtain a photothermographic material having a high Dmax (highest density) and a high halftone dot quality, which is optimal for photolithography. Further, since this light-sensitive material contained iodide, black spots were easily generated, and the dot quality was very poor. Therefore, the super hard tone, low fog, no black spots, and environmental
Cost-effective photothermographic material, and Dmax
There has been a demand for a technique for providing a photothermographic material having a high (highest density) and a good halftone dot quality, which is most suitable for photolithography.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems of the prior art. That is,
INDUSTRIAL APPLICABILITY The present invention is particularly suitable for photolithography, particularly for scanners and imagesetters, for ultra-high contrast, less fogging, no black spots, high Dmax (maximum density) and good halftone dot quality. One of the problems to be solved is to provide a photothermographic material capable of obtaining an optimum image. Another object of the present invention is to provide a photothermographic material which can be applied in an aqueous system and is advantageous in terms of environment and cost.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have incorporated a nucleating agent on the support having a photosensitive silver halide,
At the same time, the formic acid or formate content should be 5
It has been found that by setting the amount to be less than mmol, an excellent photothermographic material having desired effects can be provided, and the present invention has been provided. That is, according to one aspect of the present invention, in a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, the photothermographic material is formed on the support having a photosensitive silver halide. A photothermographic material comprising a nucleating agent and a content of formic acid or formate of 5 mmol or less per mole of silver is provided.

In the present invention, the nucleating agent is preferably a compound represented by the following formula (1), (2) or (3):
And at least one compound selected from hydrazine derivatives.

Embedded image [In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹¹ and Z, R ¹² and R ¹³ ,
R ¹¹ and R ¹² , and R ¹³ and Z may combine with each other to form a cyclic structure. In the formula (2), R ¹⁴ represents a substituent. In the formula (3), X and Y each independently represent a hydrogen atom or a substituent, and 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 thio group or a heterocyclic amino group. In the formula (3), X and Y, and A and B may be bonded to each other to form a cyclic structure. The nucleating agent particularly preferably contains at least one compound selected from the compounds represented by the following formula (A) or (B).

Embedded image [In the formula (A) or the formula (B), Z ¹ and Z ² each represent a nonmetallic atomic group that can form a 5- to 7-membered ring structure, and Y ¹ and Y ² each represent- Represents a C (＝ O) — group or a —SO ₂ — group, and X ¹ and X ² are each a hydroxy group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, a mercapto group (or a salt thereof) ), An alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group,
Represents a heterocyclic amino group, an acylamino group, a sulfonamide group, or a heterocyclic group. Y ³ represents a hydrogen atom or a substituent. ]

In the present invention, the content of formic acid or formate on the side of the photothermographic material having the image forming layer containing the photosensitive silver halide is preferably 1 mmol or less per mole of silver. The photothermographic material of the present invention preferably does not contain iodide.

According to another aspect of the present invention, the nucleating agent is added using a nucleating agent solution or a nucleating agent dispersion having a formic acid or formate concentration of 10 mol% or less based on the nucleating agent. The method for producing a photothermographic material of the present invention, comprising:

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the following, embodiments and methods of the photothermographic material of the present invention will be described in detail. The photothermographic material of the present invention has, on at least one surface of a support, an image forming layer (that is, a photosensitive layer) containing an organic silver salt as a non-photosensitive silver salt, a photosensitive silver halide and a binder. And a nucleating agent is contained in the layer on the image forming layer side, and the content of formic acid or formate is 5 mmol or less per 1 mol of silver. By the combination of these features, a photothermographic material having a high contrast, high Dmax, low fogging, and good halftone dot quality with little black spots can be obtained.

The type of the nucleating agent used in the present invention is not particularly limited, but from the viewpoint of high contrast, Dmax, fogging, black spots and halftone dot quality, the formulas (1) to (1) described in the present specification are used. The compound represented by the formula (3) is preferable, and the compound represented by the formula (A) or (B) described in the present specification is most preferably used.

In the present invention, the content of formic acid is 5 mmol or less per 1 mol of silver, but is particularly preferably 1 mol / mol of silver from the viewpoint of fog, black spots and halftone dot quality.
Mmol or less. It is preferable that iodide is not contained because it deteriorates black spots and halftone dot quality.

The photothermographic material of the present invention has a non-photosensitive silver salt. The organic silver salt that can be used in the present invention is relatively stable to light, but can be used in the presence of an exposed photocatalyst (such as a photosensitive silver halide image) and a reducing agent.
It is a silver salt that forms a silver image when heated to at least ℃. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, in particular silver salts of long-chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Also preferred are organic or inorganic silver salt complexes in which the ligand has a complex stability constant in the range of 4.0 to 10.0.
The silver donor material can preferably comprise about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. These examples are
Including, but not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, and 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 organic acid having a silver behenate content of 75 mol% or more, more preferably 85 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 silver salt 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 used in the present invention can be obtained by treating the above organic acid with an alkali. The organic silver salt used in 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. The silver salt of an organic acid can be prepared by adding a silver nitrate aqueous solution gradually or rapidly to a reaction vessel containing an alkali metal salt solution or suspension of an organic acid, or by preparing an organic acid prepared beforehand in a reaction vessel containing a silver nitrate aqueous solution. 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 a solution or suspension of an organic acid alkali metal salt 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 organic acid silver 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 time during the preparation of the organic acid silver salt, but it is preferable to add the tertiary alcohol during the preparation of the organic acid alkali metal salt and dissolve the organic acid alkali metal salt before use. . The amount of the third alcohol can be used freely between 0.01 and 10 by weight ratio to of H ₂ O as a solvent at the time of organic acid silver preparation, the range of 0.03 to 1 is preferred.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle-like crystal having a short axis and a long axis is preferable. 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 is the standard deviation of the lengths of the minor and major axes divided by the minor and major axes, respectively.
0 fraction is preferably 80% or less, more preferably 50% or less,
It is more preferably at most 30%. 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 obtaining 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 80% or less, more Preferably 50% or less,
It is more preferably at most 30%. 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. A solid fine particle dispersion having an average particle size of 0.05 μm or more and 10.0 μm or less in this measurement method is preferable. More preferably an average particle size of 0.1 μm or more and 5.0 μm or less, more preferably an average particle size of 0.1 μm
Not less than 2.0 μm.

The organic silver salt that can be used in the present invention includes:
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 stream and then the pressure is reduced. After passing through such a process, the mixture is mixed with a photosensitive silver salt aqueous solution to produce a photosensitive image forming medium coating solution. 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 which is dispersed by being converted to high pressure and high speed is substantially free of a photosensitive silver salt, and has a water content relative to that of a 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 and 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 "shearing 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 dispersing apparatus suitable for the present invention, a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation is used.
(With G10Z interaction chamber), M-
110Y (with H10Z interaction chamber), M-140K (with G10Z 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,
After the aqueous dispersion containing at least the organic silver salt is pressurized by a high-pressure pump or the like and sent into the pipe, a desired pressure is applied by passing through a narrow slit provided in the pipe, and thereafter, the inside of the pipe is It is possible to obtain an optimal organic silver salt dispersion for the present invention by causing a rapid pressure drop in the dispersion by, for example, rapidly returning the pressure to the atmospheric pressure.

Prior to the dispersion operation, it is preferable to pre-disperse 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 dispersion of an organic silver salt, it is possible to disperse the particles in a desired particle size by adjusting the flow rate, the differential pressure at the time of pressure drop, and the number of treatments. / Sec to 600m / sec, the differential pressure during pressure drop
Is preferably in the range of 900~3000kg / cm ^2, the flow rate is 300 meters / sec to 60
More preferably, the pressure difference at the time of 0 m / sec and the pressure drop is in the range of 1500 to 3000 kg / cm ² . The number of times of dispersion processing can be selected as needed, but usually 1 to 10 times is selected, but from the viewpoint of productivity, about 1 to 3 times is selected. Elevating such an aqueous dispersion under high pressure is
At a high temperature exceeding 90 ° C., the particle size tends to increase and fog tends to increase. 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.
The temperature is preferably maintained in the range of 90 to 90 ° C, more preferably in the range of 5 to 80 ° C, particularly preferably in the range of 5 to 65 ° C. 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 . As the cooler, a double tube, a double tube using a static mixer, a multi-tube heat exchanger, a coiled tube heat exchanger, or the like can be appropriately selected according to the required heat exchange amount. 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. The refrigerant used for the cooler should be 20 ° C well water, 5-10 ° C cold water treated by a refrigerator, and, if necessary, -30 ° C ethylene glycol / water refrigerant, etc. You can also.

In the dispersion operation, 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 compound described in JP-A-7-350753,
Alternatively, known anionic, nonionic, cationic surfactants and other known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, or naturally occurring polymer compounds such as gelatin Can be appropriately selected and used, but polyvinyl alcohols and water-soluble cellulose derivatives are particularly preferred.

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 as a slurry to a dispersing machine. 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. In addition to mechanical dispersion, pH
By performing control, the particles may be roughly dispersed in a solvent, and then the pH may be changed in the presence of a dispersing agent to form fine particles. 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 fine particles during storage, or stored in a highly viscous state by a hydrophilic colloid (for example, in a jelly state using gelatin). You can also. Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

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.
It is preferable to use the above-mentioned dispersing aid, but it is preferable to use the dispersing aid in a minimum amount within a range suitable for minimizing the particle size.
A range of 5% by weight is preferred. In the present invention, it is possible to produce a photosensitive material by mixing the organic silver salt aqueous dispersion and the photosensitive silver salt aqueous dispersion, the mixing ratio of the organic silver salt and the photosensitive silver salt can be selected according to the purpose, The ratio of the photosensitive silver salt to the organic silver salt is preferably in the range of 1 to 30 mol%, more preferably 3 to 20 mol%, particularly preferably 5 to 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. Organic silver salts can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably from 1 to 3 g / m ^2.

In the present invention, iodides, especially NaI, K
It is preferable that the light-sensitive material does not contain a metal iodide represented by I. This is because iodide has a sensitizing effect, but also has an effect of accelerating the generation of black spots and deteriorating dot quality.

The photothermographic material of the present invention includes Ca, M
It is preferable to add a metal ion selected from g, 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 preferable to add it in the form of a water-soluble metal salt which is not a halide. It is preferably added in the form of a salt or the like. 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. When a metal ion selected from Ca, Mg, Zn and Ag is added, the timing of addition is as follows: after the particles of the non-photosensitive organic silver salt are formed, immediately after the particles are formed, before the dispersion, after the dispersion and before and after the preparation of the coating solution. It may be at any time as long as immediately before application, preferably after dispersion,
Before and after preparation of the coating solution. Ca, Mg, Z in the present invention
As the addition amount of the metal ion selected from n and Ag,
It is preferably from 10 ^-3 to 10 ^-1 mol, particularly preferably from 5 × 10 ^{-3 to} 5 × 10 ^-2 mol, per 1 mol of non-photosensitive organic silver.

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 change stepwise, or may change continuously. Further, silver halide grains having a core / shell structure can be preferably used. The structure is preferably 2-
Core / shell particles having a quintuple structure, more preferably a quaternary 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. However, silver iodobromide and silver iodochlorobromide are not preferred in terms of black spots and halftone dot quality.

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 thereafter, an organic compound is prepared. A method of mixing with a silver salt is used. The grain size of the photosensitive silver halide 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 less.
μm or more and 0.15 μm or less, more preferably 0.02 μm or more and 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. Also,
When 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-like 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 photosensitive silver halide grains used in the present invention contain a metal or a metal complex of Group VII or VIII of the periodic table. Group VII or VII of the periodic table
Rhodium, rhenium, ruthenium, osnium and iridium are preferred as the group I metal or the central metal of the metal complex. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is from 1 × 10 ⁻⁹ mol to 1 × per mol of silver.
The range of 10 ⁻³ mol is preferred, and 1 × 10 ⁻⁸ mol to 1 ×
A range of 10 ^-4 mole is more preferred. 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 (II)
I) Complex salts, pentachloroacolodium (III) complex salts, tetrachlorodiachodium (III) complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, trioxalathrodium (III) complex salts, and the like. Can be These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the rhodium compound is generally used, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaC
l, KBr, NaBr, etc.). 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 addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-4 mol, and particularly preferably in the range of 5 × 10 ^-8 mol to 1 × 1 mol per mol of silver halide.
0 ^-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, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. . Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852.
And 2-20855 in the form of a water-soluble complex salt. 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 ammonium or alkali metal ions are 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 addition amount of these compounds is 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FourMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-FiveMole
It is. The addition of these compounds was
Suitable during the manufacture of the emulsion and at each stage before the application of the emulsion.
However, it may be added at the time of forming an emulsion,
It is preferably incorporated into silver gemide grains.

In order to add these compounds during silver halide grain formation and incorporate them into silver halide grains, a powder of a metal complex 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 as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-solution simultaneous mixing method is used, 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 charged into the reaction vessel immediately after the formation of the particles, during or at the end of 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 an appropriate solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) is used. Etc.) or alkali halides excluding iodide (eg, KCl, NaCl, KBr, NaBr
Etc.) can be used. 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.

Further, the silver halide grains used in the present invention may contain 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 phase containing the metal complex in the silver halide may be uniform, may be contained in the core at a high concentration, or may be contained in the shell at a high concentration, and there is no particular limitation. The metal is 1 × 10 ^-9 to 1 × 10 per mol of silver halide.
^-4 mol is preferred. In addition, in order to incorporate the 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 a method known in the art, such as a noodle method or flocculation method, but in the present invention, it may or may not be desalted.

As a gold sensitizer used for sensitizing a silver halide emulsion with gold, an oxidation number of gold of +1 or +
It may be trivalent, and a gold compound usually used as a gold sensitizer can be used. Typical examples are chloroauric acid,
Examples include potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, and pyridyl trichlorogold. Although the amount of the gold sensitizer to be added varies depending on various conditions, it is generally about 10 ^-7 mol to 10 ^-3 mol, more preferably 10 ^-6 mol, per mol of silver halide.
The molar ratio is not less than 5 × 10 ⁻⁴ . The silver halide emulsion is preferably used in combination with gold sensitization and another chemical sensitization. Other chemical sensitization methods include sulfur sensitization, selenium sensitization,
Known methods such as tellurium sensitization and noble metal sensitization can be used. When used in combination with gold sensitization, for example, sulfur sensitization and gold sensitization, selenium sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization,
Sulfur sensitization, tellurium sensitization, and gold sensitization, and sulfur sensitization, selenium sensitization, tellurium sensitization, and gold sensitization are preferable.

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 addition amount of the sulfur sensitizer, pH during the chemical ripening, the temperature, but varies depending on various conditions such as the size of the silver halide grains, 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, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, JP-A-4-25832,
The compounds described in JP-A Nos. 4-109240, 3-21798 and the like 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 which 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 the silver halide emulsion can be tested by the method described in JP-A-5-313284. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te A compound having a bond,
Tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te-containing heterocycles, Tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, U.S. Patent Nos. 4-20464
No. 0, No. 3-53693, No. 3-31598, No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (198
0), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S.
The Chemistry of Organic Serenium and Telluniu, edited by S. Patai
m Compounds), Vol 1 (1986) and Vol. 2 (1987). 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, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, 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 be coexistent during the formation of silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Specific compounds of the reduction sensitization method include, as well as ascorbic acid, thiourea dioxide, for example, stannous chloride,
Aminoiminomethanesulfinic acid, hydrazine derivatives,
Borane compounds, silane compounds, polyamine compounds and the like can be used. Also, adjust the pH of the emulsion to 7 or more or pAg.
Reduction sensitization can be achieved by ripening while keeping the temperature 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 used in the present invention by the method described in European Patent Publication No. 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 is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, more preferably 0.03 to 0.25 mol, per mol of the organic silver salt. preferable. Regarding the mixing method and 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, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. And the like, 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. There is no particular limitation as long as it appears in.

Next, the nucleating agent used in the present invention will be described. Although the type of the nucleating agent used in the present invention is not particularly limited, examples of preferred nucleating agents include those represented by formulas (1) to (1).
The substituted alkene derivative, the substituted isoxazole derivative and the specific acetal compound represented by (3), and the hydrazine derivative are mentioned. More preferred examples of the compounds represented by the formulas (1) to (3) include a cyclic compound represented by the formula (A) or the formula (B). Also,
A plurality of these nucleating agents may be used in combination.

First, the hydrazine derivative that can be used in the present invention will be described. The type of the hydrazine derivative that can be used in the present invention is not particularly limited, but a hydrazine derivative represented by the following formula (H) is preferably used.

[0055]

Embedded image

In the formula (H), R ₂ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁ represents a hydrogen atom or a block group, and G 1 represents —CO—, —COCO—, —.
_{C = S -, - SO 2} -, - SO -, - PO (R 3) - group (R
₃ is selected from the same range as the groups defined in R _1, may be different from R _1. ) Or iminomethylene group. A ₁ and A _{2 each} represent a hydrogen atom, or an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, one of which is a hydrogen atom and the other is substituted or unsubstituted. m
₁ is 0 or 1, and when m ₁ is 0, R ₁ is an aliphatic group,
Represents an aromatic group or a heterocyclic group.

The hydrazine derivative represented by the formula (H) will be described in detail. In formula (H), the aliphatic group represented by R ₂ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl, alkenyl, or alkynyl group having 1 to 30 carbon atoms. The aromatic group represented by R ₂ in the formula (H) is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring,
Examples include an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring, a triazine ring, a morpholine ring, a piperidine ring, and a piperazine ring. R
₂ may be substituted with any substituent. R ₂ in the formula (H) is preferably an aryl group, an alkyl group, or an aromatic heterocyclic group, and more preferably a substituted or unsubstituted phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an aromatic group. Group heterocyclic group.

When R ₂ in the formula (H) represents a substituted alkyl group having 1 to 3 carbon atoms, R ₂ is more preferably a substituted methyl group, and further preferably a di- or tri-substituted methyl group. When R ₂ in the formula (H) represents a substituted methyl group, preferred specific examples include a t-butyl group,
Dicyanomethyl group, dicyanophenylmethyl group, triphenylmethyl group (trityl group), diphenylmethyl group, methoxycarbonyldiphenylmethyl group, cyanodiphenylmethyl group, methylthiodiphenylmethyl group, cyclopropyldiphenylmethyl group, and the like. Trityl groups are most preferred. When R ₂ in the formula (H) represents an aromatic heterocyclic group, preferred hetero rings include a pyridine ring, a quinoline ring, a pyrimidine ring, a triazine ring, a benzothiazole ring, a benzimidazole ring, a thiophene ring and the like. . In the formula (H), R ₂ is most preferably a substituted or unsubstituted phenyl group.

In the formula (H), R ₁ represents a hydrogen atom or a blocking group, and the blocking group is specifically an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group (a single group). Ring or fused ring aryl group),
Represents a heterocyclic group, an alkoxy group, an aryloxy group, a substituted or unsubstituted amino group or a hydrazino group. R ₁ in the formula (H) is preferably an alkyl group (a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoro group). Ethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, hydroxymethyl group, benzenesulfonamidomethyl group, trifluoroacetylmethyl group, dimethylaminomethyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group, methoxymethyl Group, phenoxymethyl group, 4-ethylphenoxymethyl group, phenylthiomethyl group, t-butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, methoxycarbonyldiphenylmethyl group, cyanodiphenylmethyl , A methylthiodiphenylmethyl group), an alkenyl group (an alkenyl group having 1 to 10 carbon atoms, for example, a vinyl group, a 2-ethoxycarbonylvinyl group, a 2-trifluoro-2-methoxycarbonylvinyl group, a 2,2-dicyanovinyl) Group, 2-cyano-2-methoxycarbonylvinyl group, etc.) and aryl group (monocyclic or condensed-ring aryl group containing a benzene ring, particularly preferred are, for example, phenyl group, perfluorophenyl group, 3,5 -Dichlorophenyl group, 2-methanesulfonamidophenyl group, 2-carbamoylphenyl group, 4,
5-dicyanophenyl group, 2-hydroxymethylphenyl group, 2,6-dichloro-4-cyanophenyl group, 2-
A chloro-5-octylsulfamoylphenyl group), a heterocyclic group (a 5- to 6-membered, saturated or unsaturated, monocyclic or condensed heterocyclic group containing at least one nitrogen, oxygen, and sulfur atom) For example, morpholino group, piperidino group (N-substituted), imidazolyl group, indazolyl group, pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group, pyridyl group, pyridinio group, quinolinio group, quinolyl group, hydantoyl group, imidazolidinyl group and the like) An alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, a 2-hydroxyethoxy group, a benzyloxy group, a t-butoxy group, etc.), an amino group (an unsubstituted amino group, and a 1 to 10 carbon atoms). An alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino (Including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom), for example, a 2,2,6,6-tetramethylpiperidin-4-ylamino group, a propylamino group, a 2-hydroxyethylamino group , Anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.). The group represented by R ₁ may be substituted with any substituent.

Among the groups represented by R ₁ in the formula (H), preferred are those wherein when R ₂ represents a phenyl group or an aromatic heterocyclic group and G 1 is a —CO— group, a hydrogen atom, It is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and most preferably a hydrogen atom or an alkyl group. When R ₁ represents an alkyl group, the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, a sulfonamide group, an amino group, an acylamino group, or a carboxy group. . When R ₂ in the formula (H) represents a substituted methyl group and G 1 is a —CO— group, R ₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group ( Unsubstituted amino group, alkylamino group, arylamino group, heterocyclic amino group), more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylamino group, an arylamino group, a heterocyclic group. It is an amino group. In the case of G1 is -COCO- group, regardless of R _2, R ₁ is an alkoxy group in formula (H), an aryloxy group, an amino group preferably, a substituted amino group, specifically an alkylamino group, an arylamino Groups or saturated or unsaturated heterocyclic amino groups are preferred. G1 is -SO ₂ also - group, regardless of R _2, R ₁ in formula (H) is an alkyl group, an aryl group or a substituted amino group.

In the formula (H), G1 is preferably -CO
Or a -COCO- group, particularly preferably -C
O- group. In the formula (H), A ₁ and A ₂ are hydrogen atoms,
An alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more), an acyl group having 20 or less carbon atoms (Preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more,
Alternatively, it is a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group. A ₁ and A ₂ are most preferably hydrogen atoms.

[0062] represents a m1 is 1 or 0 In the formula (H), when m1 is 0, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group. When m1 is 0, R ₁ is particularly preferably a phenyl group, a substituted alkyl group or alkenyl group, having 1 to 3 carbon atoms, for a phenyl group and a substituted alkyl group having 1 to 3 carbon atoms among these, the The preferred range is the same as the preferred range of R ₂ described above.
When R ₁ in the formula (H) is an alkenyl group, preferably R ₁ is a vinyl group, and the following substituents: a cyano group, an acyl group, an alkoxycarbonyl group, a nitro group, a trifluoromethyl group, a carbamoyl group A vinyl group having one or two substituents selected from the above is particularly preferred. Specifically, a 2,2-dicyanovinyl group, a 2-cyano-2-methoxycarbonylvinyl group, a 2-acetyl-
And a 2-ethoxycarbonylvinyl group. m1
Is preferably 1.

In the formula (H), R₁Is G1-R₁Part of
Split from the remaining molecules, -G1-R ₁Including partial atoms
It is a kind of cyclization reaction that produces a cyclic structure
Hydrazine derivative represented by the formula (H)
The body contains a group of adsorptive groups that adsorb to silver halide.
It may be embedded. R of formula (H)₁Or R_TwoNisso
Is commonly used in immobile photographic additives such as couplers
Embedded ballast groups or polymers
And R of formula (H)₁Or R_TwoReplace
It may contain a plurality of hydrazino groups as a group.
The compound represented by the formula (H) has a hydrazino group
Represents a multimer. Further, R of the formula (H)₁Or R_TwoIs
A cationic group (specifically, a quaternary ammonium group)
Or a nitrogen-containing group containing a quaternized nitrogen atom.
Terrorist ring), ethyleneoxy or propylene
A group containing a repeating unit of an xyl group, (alkyl, aryl
Or heterocycle) dissociated by thio group or base
Possible dissociable groups (carboxy, sulfo, acylsul
Famoyl group, carbamoylsulfamoyl group, etc.)
It may be rare. Examples of these include, for example,
No. 63-29751, U.S. Pat. No. 4,385,108
No. 4,459,347, JP-A-59-19523.
No. 3, No. 59-200231, No. 59-201045
Nos. 59-201046 and 59-201047
Nos. 59-201048 and 59-201049
And JP-A-61-170733 and 61-27074.
No. 4, No. 62-948, No. 63-234244, No.
63-234245, 63-234246, JP
JP-A-2-285344, JP-A-1-100530,
Kaikai 64-86134, JP-A-4-16938, JP-A-5-197091
No., WO95 / 32452, WO95 / 32453
No., JP-A-9-235264, JP-A-9-235265, JP-A-9-23
No. 5266, JP-A-9-235267, JP-A-9-179229, JP-A
7-234471, JP-A-5-333466, JP-A-5-333466
JP-A-6-19032, JP-A-6-19031, JP-A-6-19031
5-45761, U.S. Pat. No. 4,994,365, U.S.A.
Japanese Patent No. 4,988,604, JP-A-73-25924
No. 0, JP-A-7-5610, JP-A-7-244348
And compounds described in German Patent No. 4006032 and the like.
It is.

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

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

The hydrazine derivative used in the present invention is 2
More than one species may be used in combination. In addition to the above, the following hydrazine derivatives can be used (in some cases, they can be used in combination). The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following patents. That is,
JP-A-10-10672, JP-A-10-161270
JP-A-10-62898, JP-A-9-30487
0, JP-A-9-304872, JP-A-9-3048
No. 71, JP-A-10-31282, U.S. Pat.
695, all hydrazine derivatives described in EP 714320A.

The hydrazine derivative can be prepared by using water or a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. In addition, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved by a well-known emulsification dispersion method. Then, an emulsified dispersion can be prepared and used mechanically. Alternatively, the hydrazine derivative powder can be dispersed in a suitable solvent such as water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. The hydrazine derivative may be added to the image recording layer or any other layer on the image recording layer side with respect to the support, but is preferably added to the image recording layer or a layer adjacent thereto. The amount of the hydrazine derivative to be added is preferably 1 × 10 ^-6 to 1 mol per 1 mol of silver, and 1 × 10 ^{-5 to} 5 ×.
10 ^-1 mol is more preferable, and 2 x 10 ^-5 to 2 x 10 ^-1 mol is most preferable.

In the present invention, a substituted alkene derivative represented by the formula (1), a substituted isoxazole derivative represented by the formula (2), and a specific acetal represented by the formula (3) are preferably used as a nucleating agent. The compound will be described.

[0072]

Embedded image

In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹¹ and Z,
R ¹² and R ¹³ , R ¹¹ and R ¹² , or R ¹³ and Z may be bonded to each other to form a cyclic structure. In the formula (2), R ¹⁴ represents a substituent. In the formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, Represents a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In equation (3), X and Y or A
And B may combine with each other to form a cyclic structure.

The compound represented by the formula (1) will be described in detail. In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹¹ and Z, R ¹²
And R ¹³ , R ¹¹ and R ¹² , or R ¹³ and Z may be bonded to each other to form a cyclic structure. When R ¹¹ , R ¹² and R ¹³ represent a substituent, examples of the substituent include, for example, a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, Active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (including N-substituted nitrogen-containing heterocyclic group), heterocyclic group containing quaternized nitrogen atom (eg, pyridinio group) ), Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, imino group, imino group substituted with N atom, thiocarbonyl group, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl Group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy Or a salt thereof, an alkoxy group (including a group containing repeating ethyleneoxy group or propyleneoxy group units),
Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino 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 ammonium group, oxamoylamino group, (alkyl Or aryl) sulfonyluureido, acylureido, acylsulfamoylamino, nitro, mercapto, (alkyl, aryl or heterocycle) thio, acylthio, (alkyl or aryl) s A honyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphoryl group, a group containing a phosphoric acid amide or a phosphate ester structure, Examples thereof include 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 (1) is a substituent whose Hammett's substituent constant σ _p can take a positive value. Carbonyl 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 (1) may further have a substituent, and as the substituent, R ¹¹ , R ¹² , and R ^{13 in} the formula (1) represent a substituent. The same substituents as the substituents which may be present at the time of expression are exemplified. In the formula (1), R ¹¹ and Z, R ¹² and R ¹³ , R
¹¹ and R ¹² , or R ¹³ and Z may be bonded to each other to form a cyclic structure. The cyclic structure formed at this time is a non-aromatic carbon ring or a non-aromatic hetero ring. It is.

Next, the preferred range of the compound represented by the formula (1) will be described. The silyl group represented by Z in the formula (1) 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 (1) 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, a thiocarbonyl group, Imino group, imino group substituted by 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 A phenyl group substituted with a functional group, and more preferably,
Cyano group, alkoxycarbonyl group, carbamoyl group,
Imino group, sulfamoyl group, 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. The group represented by Z in the formula (1) is more preferably an electron-withdrawing group.

The substituent represented by R ¹¹ , R ¹² and R ¹³ in the formula (1) is preferably a group having a total carbon number of 0 to 30, specifically, Z in the above formula (1). A group having the same meaning as the electron-withdrawing group represented, and 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, Heterocyclic thio group, amino group,
Alkylamino group, arylamino group, heterocyclic amino group, ureido group, acylamino group, sulfonamide group,
Or a substituted or unsubstituted aryl group.

Further, in the formula (1), R ¹¹ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, or an acylamino group, a hydrogen atom, or a silyl group. When R ¹¹ 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, 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 ¹¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms, and the substituent may be any substituent.
Among them, an electron-withdrawing substituent is preferable. In formula (1), R ¹¹ more preferably represents an electron-withdrawing group or an aryl group. In the formula (1), the substituents represented by R ¹² and R ¹³ are preferably, specifically,
(1) a group having the same meaning as the electron-withdrawing group represented by Z, 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; Group, arylthio group, heterocyclic thio group, amino group, alkylamino group, anilino group,
Examples include a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group.

In formula (1), R ¹² and R ¹³ are more preferably when one of them is a hydrogen atom and the other is a substituent. Preferably as the substituent, 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, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly a perfluoroalkaneamide group), a sulfonamide group, a 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, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group, Preferably a hydroxy group (or a salt thereof), an alkoxy group,
Or a heterocyclic group. In the formula (1), it is also preferable that Z and R ¹¹ , or R ¹² and R ¹³ 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 40, more preferably 3 to 30.

Among the compounds represented by the formula (1), more preferred
One of the most desirable is that Z is a cyano group, a formyl group, an acyl group.
Group, alkoxycarbonyl group, imino group, or carb
Represents a moyl group;¹¹Is an electron-withdrawing group or an aryl group
And R¹²Or R¹³One of them is a hydrogen atom,
The other is a hydroxy group (or a salt thereof), a mercapto group (or
Or its salt), an alkoxy group, an aryloxy group,
Ring oxy, alkylthio, arylthio, hete
It is a compound that represents a rocyclic thio group or a heterocyclic group. Sa
Further, among the compounds represented by the general formula (1), they are particularly preferred.
One of the things is Z and R¹¹Is a non-aromatic 5- to 7-member
Forming a ring structure,¹²Or R ¹³Either one
Is a hydrogen atom, the other is a hydroxy group (or a salt thereof),
Mercapto group (or salt thereof), alkoxy group, aryl
Oxy group, heterocyclic oxy group, alkylthio group, aryl
A compound representing a luthio group, a heterocyclic thio group, or a heterocyclic group
It is a compound. At this time, R¹¹Together with a non-aromatic cyclic structure
As Z to be formed, an acyl group, a carbamoyl group,
A cyclocarbonyl group, a thiocarbonyl group, a sulfonyl group, etc.
Preferred and R¹¹Represents an acyl group, carbamoyl
Group, oxycarbonyl group, thiocarbonyl group, sulfoni
Group, imino group, imino group substituted by N atom, acyl group
A mino group and a carbonylthio group are preferred.

Next, the compound represented by the formula (2) will be described. In the formula (2), R ¹⁴ represents a substituent. Examples of the substituent represented by R ¹⁴ include the same as those described for the substituents of R ^{11 to} R ^{13 in} the formula (1). The substituent represented by R ¹⁴ is preferably an electron-withdrawing group or an aryl group. When R ¹⁴ represents an electron withdrawing group, preferably
The following groups having a total carbon number of 0 to 30, namely, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, alkylsulfonyl group,
Arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group, phosphoryl group, imino group, or a saturated or unsaturated heterocyclic group, further cyano group, acyl group, formyl group, alkoxycarbonyl group, carbamoyl group, Sulfamoyl, alkylsulfonyl, arylsulfonyl, and heterocyclic groups are preferred. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a heterocyclic group.

When R ¹⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and the substituent is represented by R ¹¹ , R ¹² , R ¹³ of the formula (1). When represents a substituent, the same as those described as the substituent can be mentioned. R ¹⁴ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group,
Or a substituted or unsubstituted phenyl group, most preferably a cyano group, a heterocyclic group, or an alkoxycarbonyl group.

Next, the compound represented by the formula (3) will be described in detail. In the formula (3), 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 (3), the same substituents as described for the substituents of R ^{11 to} R ^{13 in} the formula (1) 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, arylsulfonyl, sulfamoyl, phosphoryl, carboxy (or salt thereof), sulfo (or salt thereof), hydroxy (or salt thereof), mercapto (or salt thereof), alkoxy, aryl Oxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group,
Examples thereof include an alkylamino group, an anilino group, a heterocyclic amino group, and a silyl group. 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 (3) 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 (3), X and Y are more preferably cyano group, nitro group, alkoxycarbonyl group, carbamoyl group, acyl group, formyl group, acylthio group, acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, aryl Sulfonyl group, imino group,
An imino group, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group substituted with an N atom, particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group , Acyl group, acylthio group, acylamino group, thiocarbonyl group, formyl group, imino group, N
Examples include an imino group substituted with an atom, a heterocyclic group, and a phenyl group substituted with an arbitrary electron-withdrawing group.

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 (3), A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group, which may be bonded to each other to form a cyclic structure. In the formula (3), the groups represented by A and B are preferably groups having a total carbon number of 1 to 40, more preferably groups having a total number of carbon atoms of 1 to 30, and may further have a substituent. Good.

In the formula (3), 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.

In the present invention, cyclic compounds represented by the following formulas (A) and (B) are most preferably used as nucleating agents.

[0089]

Embedded image

In the formula (A), Z ¹ is -Y ¹ -C (= C
Represents a nonmetallic atomic group capable of forming a 5- to 7-membered ring structure together with H—X ¹ ) —C (＝ O) —. Z ¹ is preferably an atomic group selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hydrogen atom, and several atoms selected from these are connected to each other by a single bond or a double bond. And -Y ¹ -C (= CH-X ¹ ) -C (= O)-
Form a 7-membered ring structure. Z ¹ may have a substituent, and Z ¹ itself may be a part of an aromatic or non-aromatic carbocycle or an aromatic or non-aromatic hetero ring. , Z ¹ is -Y ¹ -C (= CH-
The 5- to 7-membered ring structure formed together with X ¹ ) —C (＝ O) — forms a fused ring structure. Z ² in the formula (B) represents ^{-Y 2 -C (= CH-X} 2) -C (Y 3) = non-metallic atomic group capable to form a 5-membered to 7-membered ring structure with N-.
Z ² is preferably an atomic group selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hydrogen atom, and several atoms selected from these are connected to each other by a single bond or a double bond. And -Y ² -C (= CH-X ² )
-C (Y ³⁾ = to form a 5- to 7-membered ring structure with N-. Z ² may have a substituent, and Z ² itself is
It may be part of an aromatic or non-aromatic carbocycle or part of an aromatic or non-aromatic heterocycle, in which case Z ² is —Y ² —C (＝ CH—X ² ) —C ( ring structure of Y ³⁾ = 5-membered to 7-membered formed together with N- will form a condensed ring structure.

When Z ¹ and Z ² have a substituent, examples of the substituent are selected from the following. That is, typical substituents include, for example, a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), an alkyl group (aralkyl group, cycloalkyl group,
Active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group Carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group or Propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, Or heterocyclic) amino group, N-substituted nitrogen-containing heterocyclic 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 ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group,
Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group,
Including (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphate ester structure Group, silyl group, stannyl group and the like. These substituents may be further substituted with these substituents.

Next, Y ^{3 in the} formula (B) will be described. In the formula (B), Y ³ represents a hydrogen atom or a substituent,
When Y ³ represents a substituent, examples of the substituent include the following groups. That is, alkyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide Group, ureido group, thioureido group, imide group, alkoxy group,
An aryloxy group, an (alkyl, aryl, or heterocyclic) thio group. These substituents may be substituted with any substituents, and specific examples include the substituents that Z ¹ or Z ² may have.

In the formula (A) or (B), X ¹ and X ² represent a hydroxy group (or a salt thereof), an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group,
Isopropoxy group, octyloxy group, dodecyloxy group, cetyloxy group, t-butoxy group, etc., aryloxy group (eg, phenoxy group, pt-octylphenoxy group, etc.), heterocyclic oxy group (eg, benzotriazolyl) -5-oxy group, pyridinyl-3-oxy group, etc.),
Mercapto group (or salt thereof), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, dodecylthio group, etc.), arylthio group (eg, phenylthio group, p-dodecylphenylthio group, etc.), heterocyclic thio group (eg, 1- Phenyltetrazoyl-5-thio group, mercaptothiadiazolylthio group, etc.), amino group, alkylamino group (for example, methylamino group, propylamino group,
Octylamino group, dimethylamino group, etc.), arylamino group (eg, anilino group, naphthylamino group, etc.), heterocyclic amino group (eg, pyridylamino group, benzotriazol-5-ylamino group, etc.), acylamino group (eg, acetamido group, Octanoylamino group, benzoylamino group, trifluoroacetylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, dodecylsulfonamide group, etc.),
Or a heterocyclic group.

Here, the heterocyclic group is a nitrogen-containing heterocyclic group linked by a nitrogen atom, and is a substituted or unsubstituted aromatic or non-aromatic, saturated or unsaturated, monocyclic or condensed ring. A nitrogen heterocyclic group such as N-methylhydantoyl group, succinimide group, phthalimide group, N,
N′-dimethylurazolyl group, imidazolyl group, benzotriazolyl group, indazolyl group, morpholino group, 4,
4-dimethyl-2,5-dioxo-oxazolyl group and the like. Here, the salt means a salt of an alkali metal (sodium, potassium, lithium) or an alkaline earth metal (magnesium, calcium), a silver salt, or a quaternary ammonium salt (tetraethylammonium salt,
Dimethylcetylbenzylammonium salt) and quaternary phosphonium salts. In the formulas (A) and (B), Y ¹ and Y ² represent a —C (＝ O) — group or a —SO ₂ — group.

Next, the preferred range of the compound represented by the formula (A) or (B) will be described. In the formula (A) or the formula (B), Y ¹ and Y ² are preferably -C (=
O)-group. In the formula (A) or the formula (B), X ¹
And X ² are preferably a hydroxy group (or a salt thereof), an alkoxy group, a heterocyclic oxy group, an acylamino group, a mercapto group (or a salt thereof), an alkylthio group,
An arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, a sulfonamide group, or a heterocyclic group, more preferably a hydroxy group (or a salt thereof),
An alkoxy group, a mercapto group (or a salt thereof), an alkylthio group, or a heterocyclic group, particularly preferably a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, or a heterocyclic group, Most preferably, it is a hydroxy group (or a salt thereof) or an alkoxy group. In the formula (A) or the formula (B),
When X ¹ and X ² represent an alkoxy group, the total carbon number is preferably 1 to 18, more preferably 1 to 12, and particularly preferably 1 to 5. In the formula (A) or the formula (B), when X ¹ and X 2 represent a heterocyclic group, the total carbon number is preferably 2 to 20, and more preferably 2 to 16.

In the formula (A), Z ¹ is preferably 5
Group that can form a six- or six-membered cyclic structure,
Specific examples thereof include an atomic group selected from a nitrogen atom, a carbon atom, a sulfur atom and an oxygen atom, for example, -N
-N-, -NC-, -OC-, -CC-, -C =
C-, -S-C-, -C = C-N-, -C = C-O-,
-N-C-N-, -N = C-N-, -C-C-C-,-
C = C—C—, —O—C—O— and the like further have a hydrogen atom or a substituent. Z ¹ is more preferably -NN-, -NC-, -OC-,
-CC-, -C = C-, -S-C-, -N-C-N
-, -C = C-N- or the like further has a hydrogen atom or a substituent, and particularly preferably,
This is a case where an atomic group such as -NN-, -NC-, -C = C- or the like further has a hydrogen atom or a substituent.
Z ¹ itself forms part of an aromatic or non-aromatic carbocycle or an aromatic or non-aromatic heterocycle, and Z ¹ is represented by —Y ¹ —C ((CH—X ¹ ) —C It is also preferable to form a condensed ring structure with a 5- to 7-membered ring structure formed together with (= O)-. Examples of the aromatic or non-aromatic carbon ring or the aromatic or non-aromatic hetero ring in this case include, for example, a benzene ring, a naphthalene ring,
Pyridine ring, cyclohexane ring, piperidine ring, pyrazolidine ring, pyrrolidine ring, 1,2-piperazine ring, 1,
Examples thereof include a 4-piperazine ring, an oxane ring, an oxolan ring, a thiane ring, and a thiolan ring. Among them, a benzene ring, a piperidine ring and a 1,2-piperazine ring are preferred, and a benzene ring is most preferred.

In the formula (B), Z ² is preferably 5
Group that can form a six- or six-membered cyclic structure,
Specific examples thereof include an atomic group selected from a nitrogen atom, a carbon atom, a sulfur atom and an oxygen atom, for example, -N
-, -O-, -S-, -C-, -C = C-, -CC
-, -NC-, -N = C-, -OC-, -S-C-
And the like have a hydrogen atom or a substituent when possible. Z ² itself forms part of an aromatic or non-aromatic carbocyclic ring or an aromatic or non-aromatic heterocyclic ring, and forms —Y ² —C (＝ CH—X
² ) It is also preferable to form a condensed ring structure with a 5- to 7-membered ring structure formed together with —C (Y ³ ) = N—. Examples of the aromatic or non-aromatic carbon ring or the aromatic or non-aromatic hetero ring in this case include, for example, a benzene ring, a naphthalene ring, a pyridine ring, a cyclohexane ring, a piperidine ring, a pyrazolidine ring, and a pyrrolidine ring. ,
Examples thereof include a 1,2-piperazine ring, a 1,4-piperazine ring, an oxane ring, an oxolan ring, a thiane ring, and a thiolan ring. In the formula (B), Z ² is more preferably -N
-, -O-, -S-, -C-, -C = C-, and the like, when possible, further having a hydrogen atom or a substituent, particularly preferably -N-. , —O—, etc., when possible, further have a hydrogen atom or a substituent.

In the formulas (A) and (B), the substituent of Z ¹ or Z ² is preferably an alkyl group, an aryl group, a halogen atom, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, cyano group, hydroxy group, acyloxy group, alkoxy group, amino group, (alkyl,
Aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group,
Imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, nitro group,
Examples include a mercapto group, an (alkyl, aryl, or heterocycle) thio group, an (alkyl or aryl) sulfonyl group, a sulfo group or a salt thereof, and a sulfamoyl group. When Z ¹ and Z ² themselves are part of an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic hetero ring to form a condensed ring structure,
The aromatic or non-aromatic carbon ring or the aromatic or non-aromatic hetero ring may have a substituent, and the substituent is preferably a substituent selected from the same range as described above.

In the formula (B), Y ³ is preferably a hydrogen atom or the following substituent. That is, an alkyl group, an aryl group (particularly, a phenyl group or a naphthyl group), a heterocyclic group,
Cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, (alkyl, aryl or heterocycle)
Amino group, acylamino group, sulfonamide group, ureido group, imide group, alkoxy group, aryloxy group,
(Alkyl, aryl, or heterocycle) thio group. In the formula (B), Y ³ is more preferably a substituent. Specifically, an alkyl group, a phenyl group,
An amino group, anilino group, acylamino group, alkoxy group, aryloxy group, and carbamoyl group are preferred. These substituents may further have a substituent, but preferably have a total carbon number of 1 to 30, more preferably 1 to 21.

The compound represented by the formula (A) preferably has a total carbon number of 6 or more, and the compound represented by the formula (B) preferably has a total carbon number of 12 or more. preferable. Although the upper limit of the total carbon number is not particularly limited, the formula (A)
The compound represented by is preferably 40 or less, more preferably 32 or less. The compound represented by the formula (B) is preferably at most 40, more preferably at most 32. In the formula (A), Z ¹ , including its substituents, preferably has a total carbon number of 2 or more, and more preferably 3 or more. In the formula (B), Z ² , including its substituents, preferably has a sum of the total number of carbon atoms of Y ³ to 8 or more. In the formula (A), Z ¹ includes a substituent thereof,
The total number of carbon atoms is more preferably 3 or more and 40 or less, and particularly preferably 6 or more and 30 or less. Z ² in the formula (B), including the substituent, which the Y ³
Is more preferably 8 or more and 40 or less, particularly preferably 8 or more and 30 or less.

Particularly preferred among the compounds represented by the formula (A)
A new compound is represented by the formula (A) ¹Is a carbonyl group
Represents, Z¹Is -Y¹-C (= CH-X¹) -C (= O)-
An indandione ring, a pyrrolidinedione ring, or a
It is a compound that forms a lazolidinedione ring. Above all
Compounds that form lazolidinedione rings are most preferred.
Particularly preferred compounds among the compounds represented by the formula (B) are
In the formula (B), Y^TwoRepresents a carbonyl group;^TwoIs -Y
^Two-C (= CH-X^Two) -C (Y^Three) = 5-pyrazo with N-
It is a compound that forms a ron ring.

The compounds represented by the formulas (1) to (3), (A) and (B) may have incorporated therein an adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups.
No. 47, JP-A-59-195233 and JP-A-59-200.
No. 231, 59-201045, 59-2010
No. 46, No. 59-201047, No. 59-20104
No. 8, No. 59-201049, JP-A-61-1707.
No. 33, No. 61-270744, No. 62-948,
The groups described in JP-A-63-234244, JP-A-63-234245, and JP-A-63-234246 are exemplified. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

The compounds represented by the formulas (1) to (3), (A) and (B) include a ballast group or a polymer commonly used in immobile photographic additives such as couplers. May be incorporated. 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 inert 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. Examples of the polymer include those described in JP-A-1-100530.

The compounds represented by the formulas (1) to (3), (A) and (B) contain a cationic group (specifically,
A group containing a quaternary ammonium group, or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group,
(Alkyl, aryl, or heterocyclic) thio groups, or a dissociable group (such as a carboxy group, a sulfo group, an acylsulfamoyl group, or a carbamoylsulfamoyl group) that can be dissociated by a base. 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-7-234471, JP-A-5-333466,
JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Patent No. 4,994,365, U.S. Patent No. 4,988,604, JP-A-3-259240,
Compounds described in JP-A-7-5610, JP-A-7-244348, German Patent 4006032, and the like can be mentioned. Next, specific examples of the compounds represented by Formulas (1) to (3), Formula (A), and Formula (B) are shown below. However, the present invention is not limited to the following compounds.

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[0106]

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[0109]

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The compounds represented by the formulas (1) to (3), (A) and (B) may be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol). And ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product 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.

In the formulas (1) to (3), the compounds represented by the formulas (A) and (B) are used on the image recording layer side of the support, that is, the image forming layer or any other layer. May be added to
It is preferably added to the image forming layer or a layer adjacent thereto. The amount of the compound represented by the formulas (1) to (3), (A) and (B) is 1 × 10 ⁻⁶ to 1 mol per 1 mol of silver.
Mol, more preferably from 1 × 10 ^-5 ~5 × 10 ^{-1 mol, 2 × 10 -5 ~2 × 10} -1 mol is most preferred.
The compounds represented by the formulas (1) to (3), (A) and (B) can be easily synthesized by a known method. For example, US Pat. No. 5,545,515, US Pat. Patent 5,6
No. 35,339, U.S. Pat. No. 5,654,130, International Publication WO97 / 34196, or Japanese Patent Application No. 9-309.
No. 813 and Japanese Patent Application No. 9-272002 can be synthesized. The compounds represented by the formulas (1) to (3), (A) and (B) may be used alone or in combination of two or more. In addition to the above, US Pat. No. 5,545,515 and US Pat.
5,339, U.S. Patent 5,654,130, International Publication WO 97/34196, U.S. Patent 5,686,22
No. 8 or Japanese Patent Application No. 9-22888.
No. 1, Japanese Patent Application No. 9-273935, Japanese Patent Application No. 9-3098
No. 13, Japanese Patent Application No. 9-296174, Japanese Patent Application No. 9-282
564, Japanese Patent Application No. 9-272002, Japanese Patent Application No. 9-27
The compounds described in Japanese Patent Application No. 2003 and Japanese Patent Application No. 9-332388 may be used in combination.

In the present invention, the content of formic acid or formate on the side of the photothermographic material having the image forming layer containing the photosensitive silver halide is 5 mmol or less, more preferably 1 mmol, per 1 mol of silver. It is as follows. Further, the concentration of formic acid or formate in the nucleating agent solution or the nucleating agent dispersion is preferably controlled to 10 mol% or less, and most preferably to 2 mol% or less based on the nucleating agent. For this purpose, it is necessary to control the amount of formic acid or formate in the bulk nucleating agent, the dispersing or dissolving conditions (temperature, stirring conditions, etc.) when dispersing the nucleating agent, and the storage conditions of the nucleating agent solution or dispersion. There is.

In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, particularly when a nucleating agent is contained, formic acid or formate is a strong fogging substance. Further, formic acid or formate causes deterioration of dot quality and generation of black spots. Formic acid or formate may be formed by hydrolysis of a compound having the following structure, or may be used as a raw material in synthesizing such a compound and may be mixed into a photosensitive material.

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Particularly, a hydrazine derivative represented by the formula (H), a substituted alkene derivative represented by the formula (1), a substituted isoxazole derivative represented by the formula (2) used as a nucleating agent in the present invention, Among the specific acetal compounds represented by the formula (3) and the cyclic compounds represented by the formulas (A) and (B), there are many compounds having the above structure, and formic acid or formic acid Controlling the amount of salt is important in controlling fogging. In addition, it goes without saying that formic acid or formate may be brought in from any organic compound.

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, the amine compounds described in U.S. Pat.
Acrylonitrile described in 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in 5,558,983, specifically CA-1 to CA-6, JP-A-9-29736
No. 8, onium salts, specifically A-1 to A-4
2, 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 photothermographic material of 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, Examples include sodium hexametaphosphate and ammonium hexametaphosphate. The acid or 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 acid or salt thereof formed by hydration of diphosphorus pentoxide (1m
The per ² coating weight) may be desired amount depending on the performance such as sensitivity and fog, but, 0.1 to 500 mg / m ² Preferably, 0.5 to 100 mg / m ² is more preferable.

The photothermographic material of the present invention preferably 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 used in an amount of 5 to 50 mol based on 1 mol of silver on the surface having the image forming layer.
%, More preferably 10 to 40 mol%. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. 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 utilizing 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-dihydropyridine such as pyridine; bisphenol (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4 2,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2 -Screw
(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 indan-1,3-diones; chromanol, such as tocopherol is there. Particularly preferred reducing agents are bisphenol and chromanol.

When a reducing agent is used in the present invention, it 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. The toning agent may also be advantageous in forming a black silver image. 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, it is contained in an amount of 0.5 to 20% by mole. Further, the toning agent may be a so-called precursor which is derivatized so as to have a function effectively only during development. For photothermographic materials using organic silver salts, a wide range of color
46-6077, 47-10282, 49-5019, 49-5020
Nos. 49-91215, 49-91215, 50-2524, 50-
32927, 50-67132, 50-67641, 50-114217
No. 51-3223, No. 51-27923, No. 52-14788, No. 52-
99813, 53-1020, 53-76020, 54-156524
No. 54-156525, No. 61-183642, JP-A-4-56848
No., JP-B-49-10727, JP-B-54-20333, U.S. Pat.
No. 254, No. 3,446,648, No. 3,782,941, No. 4,123,282
No. 4,510,236, UK Patent 1380795, Belgium 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,
Cyclic imides such as quinazoline and 2,4-thiazolidinedione; naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2 Mercaptans exemplified by 2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximide,
(E.g., (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents ( For example, 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-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone Derivatives or metal salts, or derivatives such as 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalate Combination with acid derivatives such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; phthalazine, phthalazine derivatives
(E.g., 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-iso-butylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, And derivatives such as 2,3-dihydrophthalazine)
Or a metal salt; phthalazine and its derivatives and phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid,
(Nitrophthalic acid and tetrachlorophthalic anhydride, etc.)
Quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes that function not only as color-toning agents but also in-situ as halide ion sources for silver halide formation, such as ammonium hexachlororhodate (III) , Rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III); inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione , 8-Methyl-1,3-benzoxazine-2,4-
Benzoxazine-2,4-diones such as dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric-triazines (eg, 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).

When a toning agent is used in the present invention, it 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 film surface p of the photothermographic material of the present invention before the heat development processing
H is preferably 6.0 or less, and more preferably 5.5 or less. There is no particular lower limit,
It is about 3.

For adjusting the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a nonvolatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is preferable for achieving a low film surface pH since ammonia is easily volatilized and can be removed before the application step and the heat development. When measuring the film surface pH of the photothermographic material of the present invention, the photothermographic material 2.5 cm × 2.5 cm before the photothermographic processing was folded into a boat shape, and 300 μl of distilled water was deposited on the image forming layer side. Dripping water,
After standing for 30 minutes, the dropping solution was added to pH BOY-P2.
(Shindengen Kogyo Co., Ltd., semiconductor type pH meter) 1
It is preferable to measure for minutes.

As the binder, it is preferable to use the polymer latex described below. At least one of the image forming layers containing the photosensitive silver halide of the photothermographic material of the present invention is preferably an image forming layer using the polymer latex described below as 50% by weight or more of the total binder. (Hereinafter, this image forming layer is referred to as "image forming layer in the present invention", and the polymer latex used for the binder is referred to as "polymer latex used in the present invention.") When the photothermographic material of the present invention is used for printing in which dimensional change is a problem, it is preferable to use a polymer latex for the protective layer and the back layer. However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As a dispersion state, a polymer is emulsified in a dispersion medium,
Emulsion polymerization, micellar dispersion, or a polymer having a partially hydrophilic structure in a polymer molecule and molecular chains themselves molecularly dispersed may be used. The polymer latex of the present invention is described in "Synthetic Resin Emulsion (Edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kankokai (197
8))), `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka,
Edited by Souichi Suzuki and Keiji Kasahara, published by The Polymer Publishing Association (199
3)) "and" Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably about 5 to 1000 nm. 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.

The polymer latex used in the present invention may be a so-called core / shell type latex other than the polymer latex having a normal uniform structure. 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 latex preferably used as a binder in the present invention is as follows:
The preferred range differs between the back layer and the image forming layer. In the image forming layer, the temperature is preferably -30 to 40 ° C. in order to promote diffusion of the photographically useful material during thermal development. When used for a protective layer or a back layer, contact with various devices
Glass transition temperatures of ~ 70 ° C are preferred. The minimum film forming temperature (MFT) of the polymer latex used in the present invention is -30 ° C to 90 ° C,
More preferably, about 0 ° C to 70 ° C. A film-forming aid may be added to control the minimum film-forming temperature. An organic compound (usually an organic solvent) that lowers the minimum film forming temperature of a polymer latex, also called a plasticizer
For example, it is described in the above-mentioned "Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Kankokai (1970))".

The polymer species used in the polymer latex used in the present invention include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. and so on. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. Further, 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 preferably from 5000 to 100000, more preferably from about 10,000 to 100,000 in number average molecular weight. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the image forming layer of the photothermographic material of the present invention include the following. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of 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 examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,8
Polyester resins include FINETEX ES650, 611, 675, and 850 (all manufactured by Dainippon Ink and Chemicals), WD-size, WMS (all manufactured by Eastman Chemical) , HYDRAN AP1 as polyurethane resin
0, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
LACSTAR 7310K, 3307B, 4700H, 713 as rubber resin
2C (Dai Nippon Ink Chemical Co., Ltd.), Nipol Lx416, 41
0, 438C, 2507, (Nippon Zeon Co., Ltd.) and other vinyl chloride resins such as G351 and G576 (Nippon Zeon Co., Ltd.)
L502, L513 (manufactured by Asahi Kasei Kogyo Co., Ltd.), Aron D7020, D504, D5071 (manufactured by Mitsui Toatsu Co., Ltd.) Mitsui Petrochemical Co., Ltd.). These polymers may be used alone or as a blend of two or more as necessary.

In the image forming layer of the photothermographic material of the present invention, the polymer latex is preferably used in an amount of 50% by weight or more of the total binder, and more preferably 70% by weight or more. The image forming layer in the photothermographic material of the present invention may contain a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose in the range of 50% by weight or less of the entire binder, if necessary. May be added. The amount of the hydrophilic polymer to be added is preferably 30% by weight or less, more preferably 15% by weight or less of the total binder in the image forming layer.

The image forming layer in the photothermographic material 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. As components other than water of the coating solution, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 9
0/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent% by weight.)

The total amount of the binder in the image forming layer in the photothermographic material of the present invention is 0.2 to 30 g / m ² , more preferably 1 to 15 g.
/ M ² is preferred. A crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added to the image forming layer. As the sensitizing dye used in the present invention, any dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength range 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 holo-holerocyanine 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 Item17643IV-
Item A (December 1978, p.23), Item 1831X (August 1979, p.437)
Or in the literature cited or 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,
Various known dyes, including styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes, can be spectrally sensitized advantageously. 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, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus,
Also includes acidic nuclei such as thiazolinone nuclei, malononitrile nuclei and pyrazolone nuclei. 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.
9, 3,719,495, 3,877,943, UK Patent 1,466,2
No. 01, No. 1,469,117, No. 1,422,057, Tokuhei 3-10391
No. 6-52387, JP-A-5-341432, 6-94781,
The dye may be appropriately selected from known dyes as described in JP-A-6-301141.

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, 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,
U.S. Pat.No. 5,541,054), a dye having a carboxylic acid group (for example, JP-A-3-163440, 6-301141).
No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes
(JP 47-6329, JP 49-105524, JP 51-127719, JP
52-80829, 54-61517, 59-214846, 60-6750
No., 63-159841, JP-A-6-35109, 6-59381,
And the dyes described in JP-A-7-146537, JP-A-7-146537, JP-T-55-50111, British Patent 1,467,638, and US Patent 5,281,515. Further, as a dye forming a J-band, U.S. Pat.No. 5,510,236, the dye described in Example 5 of 3,871,887, JP-A-2-96131, and dyes disclosed in JP-A-59-48753 include These dyes 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 Re.
search Disclosure Volume 176, 17643 (Issued December 1978) p. 23
IV, J, or JP-B-49-25500, JP-B-43-4933, JP-A-59-19032, JP-A-59-192242, and the like.
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-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, dissolved in a solvent alone or a mixture of solvents such as N-dimethylformamide It may be added to the emulsion.

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a luminescent organic solvent, and this solution is dispersed in water or a hydrophilic colloid. Method of adding into the inside, 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 at any stage of the emulsion preparation which has been recognized as being useful.
For example, U.S. Pat.Nos. 2,735,766, 3,628,960, 4,183,
No. 756, 4,225,666, JP-A-58-184142, 60-1967
As disclosed in the specification of No. 49, etc., the stage before silver halide grain formation step and / or before desalting, during the desalting step and / or after desalting and before the start of chemical ripening, As disclosed in the specification of JP-A-58-113920 and the like, at any time during the process immediately before or during chemical ripening, any time after chemical ripening and before coating until the emulsion is coated. May be added. 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 in accordance with the performance such as sensitivity and fog, but is preferably 10 ^-6 to 1 mol, more preferably 10 ^-4 to 1 mol per mol of silver halide in the photosensitive layer. 10 ^-1 mol is more preferred.

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 stock storage. 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.

The antifoggant preferably used in the present invention is an organic halide.
19624, 50-120328, 51-121332, 54-58022
Nos. 56-70543, 56-99335, 59-90842, 61
No. -129642, No. 62-129845, JP-A-6-208191, No. 7-56
No. 21, 7-2781, 8-15809, U.S. Pat.No. 5,340,712
Nos. 5,369,000 and 5,464,737. Further, an organic halide represented by the following formula (P) is preferably used as an antifoggant.

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In the formula (P), Z ₁ and Z ₂ are each independently a halogen atom (fluorine, chlorine, bromine, iodine)
It is most preferred that both Z ₁ and Z ₂ are bromine atoms.

In the formula (P), X is a hydrogen atom or an electron-withdrawing group. The electron-withdrawing group referred to herein is a substituent whose Hammett's substituent constant σ _p can take a positive value. Specifically, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group , A sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a halogen atom, an acyl group, a heterocyclic group and the like. In the formula (P), X is preferably a hydrogen atom or a halogen atom, and most preferably a bromine atom. Y of formula (P) is -CO- or -SO ₂ -, preferably -SO ₂ - is. In equation (P),
Q represents an aryl group or a heterocyclic group.

The aryl group represented by Q in the formula (P) is
It is preferably a monocyclic or condensed aryl group having 6 to 30 carbon atoms, more preferably a monocyclic or condensed aryl group having 6 to 20 carbon atoms, such as phenyl and naphthyl. It is a phenyl group. The aryl 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, A chlorine atom, a bromine atom or an iodine atom), an alkyl group (including an aralkyl group, a cycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group (an N-substituted nitrogen-containing heterocyclic ring) A heterocyclic group containing a quaternized nitrogen atom (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, an imino group substituted with an N atom, a thiocarbonyl group, a carbazoyl group, a cyano group,
A thiocarbamoyl group, 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, (alkoxy or aryloxy), a carbamoyloxy group, a 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 ammonium group, (alkyl or aryl) sulfonyluureide group, nitro group, (alkyl, (Aryl or heterocycle) thio, acylthio, (alkyl or aryl) sulfonyl, (alkyl or aryl)
Examples include a sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, a phosphoryl group, a group having a phosphoric acid amide or a phosphoric ester structure, and a silyl group. These substituents may be further substituted with these substituents.
Particularly preferred as the substituent of the aryl group represented by Q in the formula (P) is an alkyl group, an alkoxy group, an aryloxy group, a halogen, a cyano group, a carboxyl group or a salt thereof, a salt of a sulfo group, a phosphate group. is there.

In the formula (P), the heterocyclic group represented by Q is a 5- to 7-membered saturated or unsaturated heterocyclic ring containing at least one atom of N, O or S. Or a condensed ring with another ring may be formed. Examples of the heterocyclic group represented by Q include a pyridyl group, a pyrazinyl group, a pyrimidyl group, a benzothiazole group, a benzimidazole group, a thiadiazolyl group, a quinolyl group, and an isoquinolyl group. These may have a substituent, and examples thereof include the same groups as the substituents of the aryl group represented by Q. Formula (P)
Q in is preferably an aryl group, particularly preferably a phenyl group.

L in the formula (P) represents a linking group, for example, an alkylene group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 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). , More preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms), and an alkynylene group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms). , Particularly preferably 2 to 10 carbon atoms), heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 1 carbon atoms).
It is 10. ), -O- group, -NR- group, -CO- group,
-COO- group, -OCOO- group, -NRCO- group, -N
RCONR- group, -OCONR- group, -S- group, -SO
Group, a —SO ₂ — group, a —SO ₂ NR— group, a group containing a phosphorus atom, a group formed by combining these, and the like (here, the group represented by R is a hydrogen atom or a substituted An alkyl group which may have a group or an aryl group which may have a substituent).

The linking group represented by L in the formula (P) may have a substituent, and examples thereof include the same substituents as those of the aryl group represented by Q. The linking group represented by L in the formula (P) is preferably an alkylene group, a -O- group, a -N
RCO- group, a group formed by combining -SO ₂ NR- group, and their.

In the formula (P), 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, etc.). , Ammonium salts, 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. Specific examples of the compound represented by the formula (P) are shown below, but the present invention is not limited thereto.

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The compound represented by the formula (P) can be easily synthesized by a usual organic synthesis reaction. A typical synthesis example is shown below.

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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 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,
31 g of intermediate (C) were obtained. White crystals. (2) Synthesis of Exemplified Compound (P-7) A solution of 4.7 g of diethanolamine and 50 ml of methanol was ice-cooled, 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, and methanol was added little by little to precipitate crystals. 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,
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 were dissolved in a small amount of DMAc, and methanol was added until crystals precipitated. As a result of filtering and drying the crystals, 22 g of Exemplified Compound (P-6) was obtained. White crystals. Compounds represented by the formula (P) include water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethylformamide, and dimethyl sulfoxide. ,
It can be used by dissolving it in methylcellosolve or the like.
Further, the compound to which the acidic group is bonded may be neutralized with an equivalent amount of alkali and added as a salt. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product 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 (P) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. It is preferable to add it to the layer to be formed. In the present invention, the compound represented by the formula (Z) is preferably used as an antifoggant. The compound represented by the formula (Z) will be described in detail.

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In the general formula (Z), M is a hydrogen atom or a k-valent cation (eg, a metal ion such as a sodium ion, a potassium ion, a calcium ion, a barium ion, a zinc ion, a tetramethylammonium ion, a tetrabutylammonium ion). Ion, etc.). k is an integer of 1 or more as shown by the exemplified ion, and is usually 1 or 2. Also, M
Is a hydrogen atom, k = 1. In the general formula (Z),
R represents a substituent, for example, a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms)
12, particularly preferably 1 to 8, for example, methyl, ethyl, iso-propyl, t-butyl, n-octyl,
1,1,3,3-tetramethylbutyl, t-amyl, cyclohexyl and the like. ), Alkenyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like), alkynyl Groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 1
2, particularly preferably 2 to 8, for example, propargyl, 3-pentynyl and the like. ), Aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 2 carbon atoms)
0, particularly preferably 7 to 16, for example, benzyl, α-methylbenzyl, α-ethylbenzyl, diphenylmethyl, naphthylmethyl, naphthylphenylmethyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20, and particularly preferably 6 to 12 carbon atoms).
And examples thereof include phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10, more preferably 0 to 6 carbon atoms).
And examples include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably having 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8; examples thereof include methoxy, ethoxy, and butoxy), and an aryloxy group (preferably, carbon Numbers 6 to 20,
More preferably 6 to 16, particularly preferably 6 to 12,
For example, phenyloxy, 2-naphthyloxy and the like can be mentioned. ), An acyl group (preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12 carbon atoms such as acetyl, benzoyl, formyl, pivaloyl, etc.), and an alkoxycarbonyl group (preferably Has 2 to 20, more preferably 2 to 16, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), An aryloxycarbonyl group (preferably 7 to 20 carbon atoms, It is more preferably from 7 to 16, particularly preferably from 7 to 10, for example, phenoxycarbonyl and the like.), An acyloxy group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 2 carbon atoms). 10, for example, acetoxy, benzoyloxy, etc.), an acylamino group (preferably having 1 to 20 carbon atoms, more preferably Ku is 2 to 16, particularly preferably 2 to 10, e.g., acetylamino,
Benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20, more preferably 2 to 16, particularly preferably 2 to 12, for example,
Methoxycarbonylamino and the like. ), An aryloxycarbonylamino group (preferably having 7 to 7 carbon atoms)
20, more preferably 7 to 16, particularly preferably 7 to 12, and examples include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12 carbon atoms)
And examples thereof include methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16,
Particularly preferred is 0 to 12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl,
Phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0
To 16, particularly preferably 0 to 12, and examples include carbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), A ureido group (preferably having 1 carbon atom)
-20, more preferably 1-16, particularly preferably 1-12, for example, ureide, methylureide, phenylurey and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as methylthio and ethylthio, etc.), and an arylthio group (preferably having 6 to carbon atoms). 20, more preferably 6 to 16, particularly preferably 6 to 12
And, for example, phenylthio and the like. ),
A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, mesyl, tosyl, etc.) and a sulfinyl group (preferably having 1 to 20 carbon atoms; More preferably 1 to 16, particularly preferably 1 to 12, for example, methanesulfinyl,
Benzenesulfinyl and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1
6, particularly preferably 1 to 12, for example, diethylphosphoramide, phenylphosphoramide and the like. ),
Hydroxy group, mercapto group, halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxam group, sulfino group, hydrazino group, sulfonylthio group, thiosulfonyl group, heterocyclic group (for example, imidazolyl, Pyridyl, furyl, piperidyl, morpholinyl, etc.), disulfide groups and the like.

These substituents may be further substituted, and if the group is capable of forming a salt, may form a salt. Further, n is an integer of 1 to 4, but when there are two or more substituents, that is, when n ≧ 2, they may be the same or different. n is preferably 1 to 3, and most preferably 2.

These substituents are bonded to each other to form 5
It may form a non-aromatic or aromatic carbon ring (for example, a benzene ring) having 7 to 7 members. Further, this ring may be substituted with another substituent (eg, a halogen atom, a carboxy group). Preferably, the substituent represented by R is an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an amino group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, Sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, alkylthio group, sulfonyl group, hydroxy group,
A mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a nitro group, and a heterocyclic group, and more preferably an alkyl group, an alkenyl group, an aralkyl group, an amino group, an alkoxy group, an alkylthio group, a hydroxy group, and a mercapto group. Group, halogen atom, sulfo group and carboxy group.

Further, in the general formula (Z), it is particularly preferable that the hydroxyl group is substituted with an alkyl group at the ortho position and / or the para position. Further, a bisphenol structure in which the compound of the general formula (Z) is bonded through one carbon is more preferable. Next, specific examples of the antifoggant represented by the formula (Z) are shown, but the present invention is not limited thereto.

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As the antifoggant of the general formula (Z), a commercially available one may be used. For example, the method disclosed in JP-A-2-51838 or the method disclosed in J. Med. Chem., 34, 342 (1991) )) Can be easily synthesized by an acid-catalyzed condensation reaction of salicylic acid and a carbonyl compound. The antifoggant of the general formula (Z) may be water or a suitable organic solvent such as an alcohol.
(Methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide,
It can be used by dissolving it in methylcellosolve or the like.
Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product 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 antifoggant of the general formula (Z) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. Alternatively, it is preferably added to a layer adjacent thereto. The image forming layer is a layer containing a reducible silver salt (organic silver salt), and is preferably a photosensitive layer further containing a photosensitive silver halide. The addition amount of the antifoggant represented by the formula (Z) is a mol amount (mol / mo
lAg), preferably 1 × 10 ^{-5 to} 5 × 10 ^-1 mol
/ MolAg, more preferably 5 × 10 ^-5 to 1 × 10 ^-1 mol
/ MolAg, more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻² mol /
molAg. These may be used alone or in combination of two or more. The antifoggant represented by the formula (Z) is
It 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.

Although not required to practice the present invention,
Mercury (II) salt can be added to the emulsion layer as an antifoggant
It may be advantageous. Preferred mercury (II) salts for this purpose are
Mercury acetate and mercury bromide. Mercury used in the present invention
Is preferably added per mol of the applied silver.
Is 1 × 10^-9Mol ~ 1 x 10^-3Mole, more preferably 1 × 10
^-8Mol ~ 1 x 10^-FourRange of moles. Thermal development feeling of the present invention
Optical materials use benzoic acid for the purpose of increasing sensitivity and preventing fog.
May be contained. What is benzoic acid used in the present invention
Although a benzoic acid derivative may be
U.S. Pat. Nos. 4,784,939 and 4,152,160;
-329,863, 9-329864, 9-28
1637 and the like. benzoic acid
May be added to any part of the photosensitive material.
The layer is preferably added to the layer having the photosensitive layer.
More preferably, it is added to the organic silver salt-containing layer.
No. The timing of addition of benzoic acid
When adding to the organic silver salt-containing layer
Can be used in any process from preparation of organic silver salt to preparation of coating solution.
Although good, it is preferable after the preparation of the organic silver salt and immediately before the coating. Benzo
Powders, solutions, fine particle dispersions, etc.
It may be performed in such a manner. Also, sensitizing dyes, reducing agents,
Even if added as a solution mixed with other additives such as color toning agents
good. Any amount of benzoic acid may be added
But 1 × 10 per mole of silver^-6More than 2 moles and less is preferred
, 1 × 10^-3More preferably, the molar ratio is from 0.5 mol to 0.5 mol.

In the photothermographic material of the present invention, a mercapto compound, a disulfide compound, A thione compound can be contained. When a mercapto compound is used in the present invention, any structure may be used.
-SM and Ar-SS-Ar are preferred. Wherein M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic or fused aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogens (e.g., Br and Cl), hydroxy, amino, carboxy,
Alkyl (eg one or more carbon atoms, preferably 1
Having 4 to 4 carbon atoms), alkoxy (e.g.,
It may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms) and aryl (which may have a substituent). As mercapto-substituted heteroaromatic compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2, 2'-dithiobis- (benzothiazole), 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 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-hydrocyanic-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, sodium 3- (5-mercaptotetrazole) -benzenesulfonate, N-methyl-N '-[3- (5-mercaptotetrazolyl) phenyl] urea, 2-mercapto-4-phenyl Oxazole and the like can be mentioned, but the present invention is not limited to these. The addition amount of these mercapto compounds is preferably in the range of 0.0001 to 1.0 mol per mol of silver in the emulsion layer, more preferably 0.001 to 0.3 mol per mol of silver.

In the photosensitive layer of the photothermographic material of 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. And fatty acids or esters described in US Pat. No. 3,121,060, and silicone resins described in UK Patent No. 955,061 can be used. In the present invention, it is preferable to provide a protective layer on the image formation, as a binder of the protective layer,
As described above, it is preferable to use a polymer latex having a glass transition temperature of 25 ° C. or more and 70 ° C. or less. In this case, it is preferable to use the polymer latex described above in an amount of 50% by weight or more, preferably 70% by weight or more of the total binder of the protective layer. In the present invention, at least such a protective layer is provided.
It is preferable to provide one layer. The binder configuration and coating method of such a protective layer are the same as those of the image forming layer. As the polymer latex for the protective layer, acrylic, styrene, acryl / styrene, vinyl chloride, and vinylidene chloride polymer latexes are preferably used. Specifically, acrylic resin-based VONCORT R337
0, 4280, NipolLx857, methyl acrylate / 2-ethylhexyl (meth) acrylate / hydroxyethyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, Nipol G576 vinyl chloride resin, and Aron D5071 vinylidene chloride resin are preferably used. . The total amount of the binder for the protective layer used in the present invention is 0.2 to 5.0 g /
m ² , more preferably in the range of 0.5 to 4.0 g / m ² .

As the surface protective layer, any anti-adhesion material may be used. Examples of anti-adhesion materials include wax, silica particles, styrene-containing elastomeric block copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and the like. And mixtures. Further, a crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the surface protective layer.

The image forming layer or the protective layer of the image forming layer in the photothermographic material of the present invention may be any of those described in US Pat.
Nos. 921, 2,274,782, 2,527,583 and
It can be used in photographic elements containing light absorbing materials and filter dyes as described in 2,956,879. Further, a dye can be mordant as described in, for example, US Pat. No. 3,282,699. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3, and particularly preferably 0.2 to 1.5.

Various dyes and pigments can be used in the photosensitive layer of the photothermographic material of the present invention from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer may be any, for example, pigments and dyes described in Color Index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, carbocyanine dye , Styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments such as 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, JP-A-5-1651).
No. 47, such as compounds 3-6 to 18 and 3-23 to 38), azomethine dyes (such as compounds 17 to 47 described in JP-A-5-341441),
Indoaniline dyes (e.g., compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441,
5-165147 No. 2-10 to 11) 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 depends on the desired absorption, but generally 1 × 10 ⁻⁶ g per m ²
It is preferable to use it in a range of not less than 1 g and not more than 1 g.

The photothermographic material of the present invention is a so-called single-sided photosensitive material having at least one photosensitive layer containing a silver halide emulsion on one side of a support and a back layer on the other side. Preferably, there is. In the present invention, the back layer preferably has a maximum absorption in a desired range of about 0.3 or more and 2.0 or less. When the desired range is 750 to 1400 nm, the optical density at 750 to 360 nm is 0.005 or more and 0.5
It is preferable that the antihalation layer has an optical density of 0.001 or more and less than 0.3. When the desired range is 750 nm or less, the maximum absorption in the desired range before image formation is 0.3 or more and 2.0 or less, and the optical density of 360 to 750 nm after image formation is
It is preferable that the antihalation layer has a thickness of 0.005 or more and less than 0.3. 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, the dye has a desired absorption in a desired range, has a sufficiently low absorption in the visible region after treatment, and has a desirable absorbance spectrum shape of the back layer. Any compound can be used as long as it is possible. 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, 7-13
No. 295, No. 7-11432, U.S. Pat.
On the ninth line, the same compound as described in JP-A-3-24539, from page 14 lower left column to page 16 lower right column, dyes which can be decolorized by the processing are described in JP-A-52-139136 and JP-A-53-132334. , 56-501480, 5
7-16060, 57-68831, 57-101835, 59-18243
6, JP-A-7-36145, JP-A-7-199409, JP-B-48-33692
No. 50-16648, Japanese Patent Publication No. 2-41734, U.S. Patent 4,088,4
Nos. 97, 4,283,487, 4,548,896, and 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 (vinyl acetal) s (e.g., poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane)
, Phenoxy resin, poly (vinylidene chloride), poly (epoxide) s, poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

When the present invention is a single-sided photosensitive material, it includes:
For improving the transportability, a matting agent may be added to the surface protective layer of the photosensitive emulsion layer and / or the back layer or the surface protective layer of the back layer. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Patent No. 1,939,213,
2,701,245, 2,322,037, 3,262,782, 3,5
Nos. 39,344 and 3,767,448, etc., and organic matting agents described in the respective specifications, such as 1,260,772, 2,192,241, and 3,257,206
No. 3,370,951, 3,523,022, 3,769,020, etc., inorganic matting agents well-known in the art such as the inorganic matting agents described in the respective specifications can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of a water-dispersible vinyl polymer, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer,
Polystyrene, styrene-divinylbenzene copolymer,
Examples of cellulose derivatives, such as polyvinyl acetate, polyethylene carbonate, and polytetrafluoroethylene, such as methyl cellulose, cellulose acetate, and cellulose acetate propionate; examples of starch derivatives such as carboxy starch, carboxynitrophenyl starch, and urea-formaldehyde-starch reactant For example, gelatin hardened with a known hardener and hardened gelatin obtained by coacervate hardening to form hollow microcapsules can be preferably used. As examples of the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth can be preferably used. The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze and surface gloss of the photosensitive material, the particle size, shape, and particle size distribution can be adjusted as needed during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, it is a preferred embodiment to add a matting agent to the backing layer. The matting degree of the backing layer is preferably such that the Bekk smoothness is not more than 1200 seconds and not less than 50 seconds, more preferably not more than 700 seconds and not more than 100 seconds. Seconds or more. In the present invention, the matting agent is preferably contained in the layer functioning as the outermost surface layer or the outermost surface layer of the light-sensitive material, or in a layer close to the outer surface, and is contained in a layer acting as a so-called protective layer. Is preferred. The matte degree of the emulsion surface protective layer may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably 300 seconds or more and 5,000 seconds or less, particularly preferably 500 seconds or more and 2,000 seconds or less.

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 construction is that the first emulsion layer (usually the layer adjacent to the base) contains an organic silver salt and silver halide, and the second layer or both layers do not contain some other components. No. But,
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 photosensitive heat-developable photographic material, each emulsion layer generally uses a functional or non-functional barrier layer between the respective light-sensitive layers, as described in U.S. Patent No. 4,460,681. By doing so, they are kept distinct from each other. U.S. Pat.Nos. 4,460,681 and 4,374,921 as shown in US
heating layer) can also be used in a photosensitive heat-developable photographic image system.

A hardener may be used for each layer such as a photosensitive layer, a protective layer and a back layer in the photothermographic material of the present invention. Examples of hardeners include U.S. Pat. For example, vinyl sulfone compounds described in US Pat. A surfactant may be used in the photothermographic material of the present invention for the purpose of improving coating properties and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically, JP-A-62-170
No. 950, U.S. Pat.
Polysiloxane surfactants described in
Examples include polyalkylene oxides and anionic surfactants described in No. 301140.

The photographic emulsion for thermal development in the present invention can be generally coated on various supports. Typical supports include polyester films, primed polyester films, poly (ethylene terephthalate) films, polyethylene naphthalate films, cellulose nitrate films, cellulose ester films, poly (vinyl acetal) films, polycarbonate films and related or resinous Materials, as well as glass,
Including paper, metal, etc. Flexible substrates, especially coated with partially acetylated or baryta and / or α-olefin polymers, especially polymers of C 2-10 α-olefins such as polyethylene, polypropylene, ethylene-butene copolymers A coated paper support is typically used. The support may be transparent or opaque, but is preferably transparent. Among them, polyethylene terephthalate biaxially stretched to about 75 to 200 μm is particularly preferred. On the other hand, when a plastic film is passed through a heat developing machine at a temperature of 80 ° C. or higher, the dimensions of the film generally expand and contract. When the processed material is used for printing plate making, this expansion and contraction becomes a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having a small dimensional change, which is devised so as to alleviate the internal strain remaining in the film at the time of biaxial stretching and to eliminate the heat shrinkage distortion generated during thermal development. For example, polyethylene terephthalate, which is heat-treated at 100 to 210 ° C. before coating the photographic emulsion for thermal development, is preferably used. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyethersulfone, polyarylate, polycarbonate and the like can be used.

The photothermographic material of the present invention may contain, for example, a soluble salt (eg, chloride, nitrate, etc.) for preventing electrification.
Evaporated metal layers, U.S. Pat.Nos. 2,861,056 and 3,206,3
No. 12 ionic polymer or U.S. Pat.
Insoluble inorganic salts as described in 3,428,451, JP-A-60-25
It may have a layer containing tin oxide fine particles described in JP-A Nos. 2349 and 57-104931. A method for obtaining a color image by using the photothermographic material of the present invention is described in JP-A-7-1329.
No. 5, page 10, left column, line 43 to 11 left column, line 40. In addition, as a stabilizer for color dye images, UK Patent No.
No. 1,326,889, U.S. Pat.Nos. 3,432,300, 3,698,909
No. 3,574,627, No. 3,573,050, No. 3,764,33
No. 7 and No. 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. Additional layers in the photothermographic material of the present invention, for example, a dye-receiving layer for receiving a transfer dye image,
If reflective printing is desired, it can include an opacifying layer, a protective topcoat layer, a primer layer known in the photothermographic art, 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.

In the present invention, the exposure apparatus used for the imagewise exposure may be any apparatus capable of performing an exposure with an exposure time of less than 10 ^-7 seconds.
D), an exposure apparatus using a Light Emitting Diode (LED) 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, for LD,
Dye lasers, gas lasers, solid-state lasers, semiconductor lasers, and the like can be used. The exposure is performed by overlapping the light beams of the light source, and the overlap means that the sub-scanning pitch width is smaller than the beam diameter. For example, the overlap can be quantitatively represented by FWHM / sub-scanning pitch width (overlap coefficient) when the beam diameter is represented by a half width of beam intensity (FWHM). In the present invention, the overlap coefficient is preferably 0.2 or more.

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 this 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 Publication WO95 / 31754 and the like. Methods using a mode laser are known, and it is preferable to use these techniques.

In the heat development step of the image forming method using the photothermographic material of the present invention, any method may be used for development, but usually the imagewise exposed photosensitive material is heated to develop. As a preferred embodiment of the thermal developing machine used, JP-B 5-56499 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,
Patent publication No. 684453, JP-A-9-292695, JP-A-9-2973
No. 85 and the thermal developing machine described in International Publication WO95 / 30934,
Japanese Patent Application Laid-Open No. 7-13294, International Publication W as a non-contact type
There are thermal developing machines described in O97 / 28489, 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. A preferred development temperature is 80 to 250
° C, more preferably 100-140 ° 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 dimensional change during thermal development of the photothermographic material of the present invention, after heating for 5 seconds or more so that an image does not appear at a temperature of 80 ° C or more and less than 115 ° C, 110 ° C or more and 140 ° C or more. A method in which an image is formed by heat development at a temperature of not more than ° C (a so-called multi-stage heating method) is effective.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. The thermal developing machine shown in FIG. 1 is a pair of carry-in rollers 11 (a lower roller is a heat roller) for carrying the thermal development photosensitive material 10 into a heating unit while correcting and preheating the thermal development photosensitive material 10 in a plane, and a photothermographic material after thermal development after thermal development. It has an unloading roller pair 12 that unloads the material 10 from the heating unit while correcting it into a flat 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 transporting means for transporting the photothermographic material 10 during the thermal development, a plurality of rollers 13 are provided on the side in contact with the surface having the image forming layer, and the non-woven fabric (for example, A smooth surface 14 on which polyphenylene sulfite or Teflon) is attached is installed. 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. As the heating means, a heater 15 is provided at an upper portion of the roller 13 and a lower portion of the smooth surface 14 so as to be heated from both sides of the photothermographic material 10. As a heating means in this case, a plate heater or the like can be used. Roller 13 and smooth surface 14
Is different depending on the member having a smooth surface, but is appropriately adjusted so that the photothermographic material 10 can be conveyed. Preferably it is 0 to 1 mm.

The surface material of the roller 13 and the smooth surface 14
May be any material as long as it has high-temperature durability and does not hinder the conveyance of the photothermographic material 10. The material of the roller surface is silicon rubber, and the material of the smooth surface is a nonwoven fabric made of aromatic polyamide or Teflon (PTFE). Is preferred. It is preferable that a plurality of heaters be used as the heating means, and that the heating temperature be set freely. The preliminary heating section upstream of the thermal development processing section is lower than the thermal development temperature (for example, 1
It is desirable to set the temperature and time to be sufficient to evaporate the amount of water in the photothermographic material, which is lower than the glass transition temperature (Tg) of the support of the photothermographic material 10. It is preferable to set at a high temperature so that uneven development is not caused. Further, a guide plate 16 is provided downstream of the thermal development processing section, and a slow cooling section is further provided. The guide plate is preferably made of a material having a low thermal conductivity, and is preferably cooled gradually to prevent deformation of the photothermographic material.

Although the above has been described with reference to the illustrated examples, the invention is not limited to this. For example, the thermal developing machine used in the present invention, such as that described in JP-A-7-13294, may have various structures. 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 in the above-described apparatus, and heating may be performed continuously at different temperatures.

[0198]

The present invention will be described more specifically with reference to the following examples. The materials, amounts, proportions,
Operations and the like can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. 1. Preparation of silver halide emulsion (Emulsion A) Dissolve 11 g of alkali-treated gelatin (2700 ppm or less as calcium content), 30 mg of potassium bromide, and 10 mg of sodium benzenethiosulfonate in 700 ml of water and adjust the pH to 5.0 at a temperature of 40 ° C. After combining, 159m of aqueous solution containing 18.6g of silver nitrate
l and potassium bromide at 1 mol / l (NH ₄ ) ₂ RhCl ₅
(H ₂ O) at 5 × 10 ⁻⁶ mol / L and K ₃ IrCl ₆
An aqueous solution containing 2 × 10 ⁻⁵ mol / l was added over 6 minutes and 30 seconds by the control double jet method while maintaining the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / l of potassium bromide and 2 × 10 ₃ of K ₃ IrCl ₆ were added.
^An aqueous solution of a halogen salt containing ^-5 mol / l was added over 28 minutes and 30 seconds by a control double jet method while maintaining the pAg at 7.7. Thereafter, the pH was lowered to cause coagulation and sedimentation, followed by desalting treatment. 0.17 g of compound A, low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) 51.
The solution was adjusted to pH 5.9 and pAg 8.0 by adding 1 g. The obtained particles were cubic particles having an average particle size of 0.08 μm, a projected area variation coefficient of 9%, and a (100) plane ratio of 90%. The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and 3 minutes later, 71 μmol of triethylthiourea was added, followed by aging for 100 minutes.
After adding 5 × 10 ⁻⁴ mol of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, the temperature was lowered to 40 ° C.
Thereafter, the temperature was maintained at 40 ° C., and 12.8 × 10 ⁻⁴ mol of the following sensitizing dye A and 6.4 × 10 ⁻³ mol of compound B were added to 1 mol of silver halide with stirring. The mixture was rapidly cooled to ° C. to complete the preparation of silver halide emulsion A.

[0199]

Embedded image

[0200] 2. Preparation of Organic Acid Silver Dispersion (Organic Acid A)
A mixture of 7.6 g, 423 ml of distilled water, 49.2 ml of 5N-NaOH aqueous solution and 120 ml of tert-butyl alcohol was stirred and reacted at 75 ° C. for 1 hour to obtain a sodium behenate solution. Separately, silver nitrate
206.2 ml of a 40.4 g aqueous solution was prepared and kept at 10 ° C. 63
A reaction vessel containing 5 ml of distilled water and 30 ml of tert-butyl alcohol was kept at 30 ° C., and while stirring, the entire amount of the sodium behenate solution and the entire amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes, 10 seconds and 60 minutes, respectively. Added over minutes. At this time, only the aqueous solution of silver nitrate was added for 7 minutes and 20 seconds after the start of the aqueous solution of silver nitrate, and then the addition of the sodium behenate solution was started. It was made to be added. At this time, the temperature in the reaction vessel was set at 30 ° C., and the liquid temperature was controlled so as not to rise. In addition, the piping of the addition system of the sodium behenate solution is kept warm by steam tracing,
The amount of steam was controlled so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution.

After the addition of the sodium behenate solution was completed, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° 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 thus obtained was stored as a wet cake without drying. The morphology of the obtained silver behenate particles was evaluated by electron microscopic photographing. As a result, it was found to be flaky crystals having an average projected area diameter of 0.52 μm, an average particle thickness of 0.14 μm, and a variation coefficient of the average equivalent spherical diameter of 15%. Next, a dispersion of silver behenate was prepared by the following method. For a wet cake equivalent to 100 g of dry solids, polyvinyl alcohol (trade name: PVA-217,
(Average degree of polymerization: about 1700)
After 385 g, it was predispersed with a homomixer. Next, the pre-dispersed undiluted solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, G10Z).
Pressure of 1750 kg /
Adjusted to cm ² and processed three times to obtain a silver behenate dispersion. 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. The silver behenate particles contained in the silver behenate dispersion thus obtained have a volume-weighted average diameter of 0.
The particles had a particle diameter of 52 μm and a variation coefficient of 15%. The particle size was measured by using MasterSizerX manufactured by Malvern Instruments Ltd. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.5, the grain thickness was 0.14 μm, and the average aspect ratio (the ratio of the projected area of the grain to the circle equivalent diameter and the grain thickness) was 5.1.

3. 1,1-bis (2-hydroxy-3,5-dimethyl
Phenyl) -3,5,5-trimethylhexane: Reducing agent solid fine particles
Preparation of child dispersion 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-
To 25 g of trimethylhexane, 25 g of a 20 wt% aqueous solution of MP-203 of Kuraray Co., Ltd., 0.1 g of Safinol 104E manufactured by Nissin Chemical Co., Ltd., 2 g of methanol and 48 ml of water were added, and the mixture was stirred well. The slurry was left for 3 hours. Thereafter, 360 g of 1 mm zirconia beads were prepared, put into a vessel together with the slurry, and dispersed for 3 hours with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) to prepare a dispersion of solid fine particles of a reducing agent. . Particle size is 80wt of particle
% Was 0.3 μm or more and 1.0 μm or less.

[0203] 4. Solid fine particle dispersion of polyhalogen compound
Preparation of product To 30 g of the polyhalogen compound-A, add 4 g of MP-203 of MP polymer manufactured by Kuraray Co., Ltd., 0.25 g of compound C, and 66 g of water, stir well, and then add 0.5 mm zirconia silicate beads. 200 g of the slurry was put into a vessel together with the slurry, and dispersed in a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) for 5 hours to prepare a solid fine particle dispersion. Particle size, 80% by weight of particles is 0.3μm or more and 1.0μm
It was below. Regarding polyhalogen compound-B, a solid fine particle dispersion was prepared in the same manner as polyhalogen compound-A, and had the same particle diameter.

[0204] 5. Preparation of solid fine particle dispersion of nucleating agent The raw powder of the nucleating agent was prepared after recrystallization purification and not. Next, the nucleating agents (compounds) shown in Table 5
No. 39, 43, 46, 50, 59, 62, 63, 67, 69) To 10 g, add 2.5 g of polyvinyl alcohol (Kuraray PVA-217) and 87.5 g of water, and mix well to obtain a slurry. Left for hours. Thereafter, 240 g of 0.5 mm zirconia beads were prepared, put into a vessel together with the slurry, and dispersed for 10 hours with a dispersing machine (1 / 16G sand grinder mill: manufactured by IMEX Co., Ltd.) to prepare a solid fine particle dispersion. . Particle size is 80
wt% was 0.1 μm or more and 1.0 μm or less, and the average particle size was 0.5 μm. After preparing a part of the dispersion, the dispersion was aged at 50 ° C. for 30 days. Table 5 shows the formic acid concentration in the dispersion measured using H ¹ -NMR.

[0205] 6. Preparation of methanol solution of nucleating agent The raw powder of the nucleating agent was prepared after recrystallization purification and not. Next, the nucleating agents (compounds) shown in Table 5
No. 1a, 2) 2 g of methanol was dissolved in 100 ml. After preparing a part of the solution, the solution was aged at 50 ° C. for 30 days. H ¹ -NM
Table 5 shows the formic acid concentration in the solution measured using R.

[0206] 7. Solid fine particles of antifoggant of formula (Z)
Against 30g antifoggants Preparation formula of the dispersion (Z), Kuraray Co.
3 g of MP-203 made of MP polymer and 87 ml of water were added, and the mixture was stirred well and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the antifoggant of formula (Z) was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

[0207] 8. 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. Liquid.

NaI Amount shown in Table 5 Binder; Luckstar 3307B 397 g as solids (manufactured by Dainippon Ink and Chemicals, Incorporated; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3 , 5-Dimethylphenyl) -3,5,5-trimethylhexane 100 g as solid content Polyhalogen compound-A 0.06 mol as solid content Nucleating agent Kind and amount shown in Table 5 Organic halogen compound P- of formula (P) 61 0.03 mol as a solid content Polyhalogen compound-B 0.06 mol as a solid content Sodium ethylthiosulfonate 0.30 g Benzotriazole 1.04 g Polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 10.8 g 6-iso-propylphthalazine 15.0 g Sodium dihydrogen orthophosphate dihydrate 0.37 g Antifoggant A-26 of the formula (Z) 0.02 mol as solids Compound W 5.0 g as solids Dye A 0.06 mol of 0.37 g) silver halide emulsion A Ag amount as safe

[0209]

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[0210]

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[0211] 9. Preparation of Coating Solution for Lower Protective Layer on Emulsion Surface Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) particle size 120
956 g of a polymer latex solution having a glass transition temperature of 57 ° C., a solid content of 21.5 wt% as a copolymer, and 15 wt% of a compound D as a film-forming aid based on the solid content of the latex.
Of H ₂ O was added to the compound E1.62G, matting agent (polystyrene particles, average particle size 7 [mu] m) 1.98 g of polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) and 23.6g was added further H ₂ O
Was added to prepare a coating solution.

[0212] 10. Preparation of Coating Solution for Upper Protective Layer on Emulsion Surface Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) particle size 70n
630 g of a polymer latex solution having a glass transition temperature of 54 ° C., a solid content of 21.5 wt% as a copolymer, and a compound D as a film-forming aid containing 15 wt% based on the solid content of the latex.
Of H ₂ O was added to the carnauba wax (Chukyo Yushi Co.,
Cellosol 524) 30 wt% solution 6.30 g, compound E 0.72 g,
7.95 g of compound F, 1.18 g of matting agent (polystyrene particles, average particle size 7 μm) and polyvinyl alcohol (Kuraray
8.30 g of PVA-235 (manufactured by Co., Ltd.) was added, and 10 mmol of compound S and further H ₂ O were added to 1 mol of silver in the emulsion layer to prepare a coating solution.

[0213]

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[0214]

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[0215] 11. PET support with back / undercoat layer
Preparation of body (1) Support Using a terephthalic acid and ethylene glycol, a PET having an IV (intrinsic viscosity) of 0.66 (measured at 25 ° C. in phenol / tetrachloroethane = 6/4 (weight ratio)) was obtained according to a conventional method. Obtained. After pelletizing this, it was dried at 130 ° C for 4 hours, melted at 300 ° C, extruded from a T-die, and quenched,
An unstretched film having a thickness of 120 μm after heat setting was produced. Using rolls with different peripheral speeds,
The film was stretched longitudinally by a factor of 3.3 and then stretched laterally by a factor of 4.5 with 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 lateral direction at the same temperature. Then, after slitting the chuck part of the tenter, knurling is performed on both ends, and 4.8 kg / cm ²
Rolled up. In this way, width 2.4m, length 3500m,
A roll having a thickness of 120 μm was obtained.

(2) Undercoat layer (a) Polymer latex- (1) (a core-shell type latex having a core portion of 90 wt% and a shell portion of 10 wt%, core portion: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic) Acid = 93/3/3 / 0.9 / 0.1 (wt%), shell: weight consisting of vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (wt%) Polymer latex having an average molecular weight of 38000) As 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

(3) Undercoat layer (b) Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) 50 mg / m ² (4) Conductive layer Julimer 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, manufactured by Sumitomo Chemical Co., Ltd.) 18 mg / m ² Dye A Coating amount to give an optical density of 783 nm of 1.2 SnO ₂ / Sb (9/1 weight ratio, needle shape Fine particles, major axis / minor axis = 20-30, manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² matting agent (polymethyl methacrylate, average particle diameter 5 μm) 7 mg / m ²

(5) Protective Layer Polymer Latex- (2) (Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer) )) 1000mg / m ² polystyrenesulfonate solid basis (molecular weight 1000~5000) 2.6mg / m ² Cellosol 524 (Chukyo Yushi (Co.)) 25mg / m ² Sumitex resin M-3 (water-soluble melamine compound, Sumitomo chemical Co., Ltd.) 218 mg / m ² (6) both sides undercoat layer prepared support of the back / subbing layers marked with PET support (base) (a) and undercoat layer (b) applied sequentially to the Each was dried at 180 ° C. for 4 minutes. Then, the undercoat layer (a) and the undercoat layer (b) were applied, and a conductive layer and a protective layer were sequentially applied to one surface on one side.
After drying for minutes, a PET support with a back / subbing layer was prepared. The dry thickness of the undercoat layer (a) was 2.0 μm.

(7) Heat treatment for transport (7-1) Heat treatment PET with back / undercoat layer produced in this way
Place the support in a heat treatment zone with a total length of 200 m set at 160 ° C,
It was 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 carried out by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time is 10
kg / cm ² .

[0220]

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[0221] 12. Preparation of photothermographic material The above-mentioned undercoat layer (a) and the undercoat layer on the side of the PET support coated with the undercoat layer (b) were coated with the emulsion layer coating solution described above in an amount of 1.6 g of silver.
/ m ² . Further, the emulsion layer lower layer protective layer coating solution was coated simultaneously with the emulsion coating solution so that the solid content of the polymer latex was 1.31 g / m ² . 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 side of the obtained photothermographic material was 5.1,
The Beck smoothness is 660 seconds, the pH of the opposite film surface is 5.9,
Beck smoothness was 560.

13. Evaluation of photographic performance (exposure processing) The obtained photothermographic material was subjected to a beam diameter (FWHM of 1/2 of beam intensity) of 12.56 μm and a laser output of 50 m.
W, using a single-channel cylindrical inner surface type laser exposure device equipped with a semiconductor laser with an output wavelength of 783 nm, adjust the exposure time by changing the number of rotations of the mirror, adjust the exposure amount by changing the output value, 2 Exposure was performed in × 10 ⁻⁸ seconds. The overlap coefficient at this time was set to 0.449. (Heat development processing) The exposed photothermographic material was heated using the thermal developing machine shown in FIG.
Preliminary heating unit 90 to 110 ° C for 15 seconds at a linear velocity of 20mm / sec %), Heat development processing unit 12
A heat development process was performed at 0 ° C. for 22 seconds and a slow cooling section for 15 seconds. In addition,
Temperature accuracy in the width direction was ± 1 ° C.

(Evaluation of Photographic Performance) The obtained images were evaluated using a Macbeth TD904 densitometer (visible density). The measurement results were evaluated in terms of Dmax, Dmin (fog), and γ (contrast). γ is represented by the slope of a straight line connecting the points of density 0.3 and 3.0 excluding the Dmin part, with the logarithm of the exposure amount as the horizontal axis.
Dmax is practically required to be 3.5 or more, preferably 4.0 or more, and γ is practically required to be 10 or more, and preferably 15 or more. In addition, exposure and development were carried out in the same manner as described above except that the temperature of the heat development processing section was set to 123 ° C., and the generated black pot was visually evaluated. “5” represents the best quality and “1” represents the worst quality. "3" is the practical limit. Further, a flat screen sample having a blackening area of 50% was prepared by the above-mentioned exposure method, subjected to a heat development treatment under the above standard conditions, and visually evaluated for dot quality. “5” represents the best quality and “1” represents the worst quality.
"3" is the practical limit. Table 5 shows the results of the above evaluations performed on each photothermographic material.

[0224]

[Table 5]

From the above results, it can be seen that the photothermographic material of the present invention has a very high contrast, a high Dmax, is hardly fogged, hardly generates black spots, and has excellent halftone dot quality. Further, in the photosensitive material containing a nucleating agent, it is found that iodide has an adverse effect on black spots and fog. The present invention has clarified the effect of formic acid on a super-high contrast photosensitive material containing a nucleating agent. In this embodiment, an example in which formic acid caused by a nucleating agent is particularly problematic was shown.However, formic acid mixed from other materials is naturally set to have a formic acid content within the range specified in the present specification. It needs to be controlled.

[0226]

According to the present invention, especially for photoengraving, especially for scanners and imagesetters, it is super-hard, hard to fog, does not generate black spots, and has good Dmax (maximum density) and halftone dot quality. It has become possible to provide a photothermographic material capable of obtaining an optimum image for photolithography.

[Brief description of the drawings]

FIG. 1 is a side view illustrating a configuration example of a heat developing machine.

[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

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroyuki Suzuki 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo F-term in Ashigara Research Laboratory, Film Co., Ltd. 2H123 AB00 AB03 AB23 AB25 BB00 BB03 BB31 BB33 CB00 CB03 DA06 EA07

Claims (6)

[Claims] 1. A photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, wherein a nucleating agent is contained on the side of the support having the photosensitive silver halide, and A photothermographic material characterized in that the content of formic acid or formate is not more than 5 mmol per mol of silver. 2. The nucleating agent contains at least one compound selected from the group consisting of a compound represented by the following formula (1), (2) or (3) and a hydrazine derivative. Item 6. The photothermographic material according to item 1. Embedded image [In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹¹ and Z, R ¹² and R ¹³ ,
R ¹¹ and R ¹² , and R ¹³ and Z may combine with each other to form a cyclic structure. In the formula (2), R ¹⁴ represents a substituent. In the formula (3), X and Y each independently represent a hydrogen atom or a substituent, and 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 thio group or a heterocyclic amino group. In the formula (3), X and Y, and A and B may be bonded to each other to form a cyclic structure. ] 3. The photothermographic material according to claim 2, wherein the nucleating agent contains at least one compound selected from the compounds represented by the following formulas (A) and (B). Embedded image [In the formula (A) or the formula (B), Z ¹ and Z ² each represent a nonmetallic atomic group that can form a 5- to 7-membered ring structure, and Y ¹ and Y ² each represent- X represents a C (＝ O) — group or —SO ₂ — group, and X ¹ and X ² are each a hydroxy group or a salt thereof, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a mercapto group or a salt thereof,
Represents an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an acylamino group, a sulfonamide group, or a heterocyclic group. Y ³ represents a hydrogen atom or a substituent. ] 4. The method according to claim 1, wherein the content of formic acid or formate on the support having the photosensitive silver halide is not more than 1 mmol per mol of silver.
4. The photothermographic material according to any one of items 1 to 3, 5. The photothermographic material according to claim 1, which does not contain iodide. 6. The method according to claim 1, further comprising adding a nucleating agent using a nucleating agent solution or a nucleating agent dispersion having a formic acid or formate concentration of 10 mol% or less based on the nucleating agent.
A method for producing the photothermographic material according to any one of the above.