JP2000284402A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure ultrahigh contrast, to prevent the occurrence of black spots and unevenness in processing and to obtain an image having high Dmax (maximum density) and optimum for use in a photomechanical process by incorporating at least two specified compounds on the side with an image forming layer containing photosensitive silver halide. SOLUTION: The heat developable photosensitive material has a nonphotosensitive silver salt, photosensitive silver halide and a binder on the substrate and contains at least one compound of formula I, II or the like and at least one compound of formula III on the side with an image forming layer containing the photosensitive silver halide. In the formulae I and II, R1-R3 are each H or a substituent, Z is an electron withdrawing group or silyl and R4 is a substituent. In the formula III, Z1 and Z2 are each halogen, X1 is H or an electron withdrawing group, Y1 is -CO- or -SO2-, Q is allylene or a divalent heterocyclic group, L is a combining group, W is carboxyl, its slat, sulfo, its salt or the like and (n) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a scanner suitable for photolithography.
More specifically, the photothermographic material for an image setter has a super-high contrast, does not generate black spots and uneven processing, and has a high Dmax (maximum density). The present invention relates to a photothermographic material for plate making.

[0002]

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

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

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

Accordingly, a photosensitive layer (hereinafter also referred to as "aqueous photosensitive layer") is prepared by using a coating solution of a water solvent which does not have such a concern.
A method of forming the slab has been considered. For example, JP-A-49-526
No. 26, JP-A-53-116144, etc., 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, when such a binder is used, the photosensitive layer can be formed using a coating solution of an aqueous solvent, and the advantages in terms of environment and cost are great.

However, when a polymer such as gelatin, polyvinyl alcohol, or water-soluble polyacetal is used as a binder, the compatibility with the organic silver salt is poor, and not only a coated material which can be practically used due to the coated surface quality cannot be obtained, but also
The silver tone of the developed part becomes brown or yellow, which is far from the black which is originally preferred, and the blackened density of the exposed part is low and the density of the unexposed part is high. Was.

In European Patent 762,196, JP-A-9-90550, etc., a photosensitive silver halide grain used in a photothermographic material is added to a metal ion or a metal of Group VII or VIII (Group 7 to 10) of the periodic table. It is disclosed that a complex ion is contained and that a hydrazine derivative is contained in a light-sensitive material to obtain high-contrast photographic characteristics.
However, when a nucleating agent such as a hydrazine derivative is used in combination with the binder used in the above-described aqueous solvent coating solution, a high-contrast image can be obtained. Frequent fog was a problem. Further, density unevenness called processing unevenness, which is caused by minute variations in the developing temperature of the same plane which cannot be avoided due to the structure of the heat developing machine, has been a serious problem.

Therefore, a photothermographic material which is super-hard and free of black spots and processing unevenness, and which is advantageous in terms of environment and cost, and which has a high Dmax (maximum density), is most suitable for photolithography. Techniques for providing materials have been desired.

[0012]

Accordingly, an object of the present invention is to provide a super-high contrast, especially for photolithography, especially for scanners and imagesetters, without causing black spots and processing unevenness. Dmax (highest concentration)
The object of the present invention is to provide a photothermographic material capable of obtaining an optimum image for photolithography applications having high image quality.

[0013]

This object has been achieved by the following means. That is, the present invention is as follows. (1) In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, the following formula (1) is provided on the side having the image forming layer containing the photosensitive silver halide. A photothermographic material comprising at least one compound selected from the compounds represented by the formulas (2) and (3) and at least one compound represented by the following formula (P).

[0014]

Embedded image

[In the formula (1), R ¹ , R ² and R
³ independently represent a hydrogen atom or a substituent;
Represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z are
They may combine with each other to form a ring structure. Equation (2)
In the formula, R ⁴ represents a substituent. In the formula (3), X and Y each independently represent a hydrogen atom or a substituent,
A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group. In equation (3), X
And Y, and A and B may be bonded to each other to form a cyclic structure. In the formula (P), Z ¹ and Z ² each represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, and Y ¹ represents a —CO— group or —SO ₂ —.
Represents a group, Q represents an arylene group or a divalent heterocyclic group, L represents a linking group, W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphate group, a hydroxyl group,
Represents a quaternary ammonium group or a polyethyleneoxy group. n represents 0 or 1. (2) In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, the following formula (A) is provided on the side having the image forming layer containing the photosensitive silver halide. And at least one compound selected from compounds represented by the formula (B), and the following formula (P)
A photothermographic material comprising at least one compound represented by the formula:

[0016]

Embedded image

[In the formula (A) or (B), Z ¹¹ and Z ¹² each represent a non-metallic atomic group capable of forming a 5- to 7-membered ring structure, including Y ¹¹ and Y ¹² Is-
A C ((O) — group or a —SO ₂ — group, and X ¹¹ and X
¹² is 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, and an aryl group, respectively. Amino group, heterocyclic amino group, acylamino group,
Represents a sulfonamide group or a heterocyclic group. Y ¹³ represents a hydrogen atom or a substituent. In the formula (P), Z ¹ and Z ² represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, Y ¹ represents a —CO— group or a —SO ₂ — group, and Q represents an arylene group. Or L represents a divalent heterocyclic group, L represents a linking group, W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphate group, a hydroxyl group,
Represents a quaternary ammonium group or a polyethyleneoxy group. n represents 0 or 1. (3) The photothermographic material according to the above (1) or (2), further comprising at least one compound represented by the following formula (Z).

[0018]

Embedded image

[In the formula (Z), M represents a hydrogen atom or a k-valent cation, and R represents a substituent. m is 1 to 4
When n ≧ 2, a plurality of Rs may be the same or different. k is an integer of 1 or more, and when M is a hydrogen atom, k = 1. (4) The photothermographic material according to any one of the above (1) to (3), wherein the film pH is 6.0 or less.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below 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 photothermographic method containing a nucleating agent represented by Formula (1), Formula (2) or Formula (3) and an organic halogen compound represented by Formula (P) in the layer on the image forming layer side. Material. By containing these compounds, a photothermographic material can be obtained which has a high contrast and hardly causes black spots and processing unevenness. On the other hand, when only the conventional hydrazine derivative is used as a nucleating agent or the compound of the formula (P) is not used, black spots and processing unevenness occur.
When only an organic halogen compound having no water-soluble group other than the formula (P) is used in place of the compound of the formula (P), nucleating agents that are not practical in terms of processing unevenness include black pots, In order to suppress the occurrence of processing unevenness, it is preferable to use the compound represented by the formula (A) or (B).

When the compound represented by the formula (Z) is used as an antifoggant, the occurrence of black spots and processing unevenness can be further suppressed.

In order to obtain an image having a higher contrast and a higher Dmax, it is preferable to adjust the film pH to 6.0 or less.

The organic silver salt that can be used in the present invention includes:
Relatively stable to light, but forms a silver image when heated to 80 ° C or higher in the presence of an exposed photocatalyst (such as a photosensitive silver halide image) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, in particular silver salts of long-chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor is preferably present in about 5-70 of the imaging layer.
% By weight. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate,
Silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, it is preferable to use silver organic acid having a silver behenate content of 75 mol% or more, and more preferably 85 mol% or more, of the above-mentioned organic acid silver or a mixture of the organic acid silver. . . Here, the content of silver behenate indicates the molar fraction of silver behenate with respect to the organic acid silver used. As the organic acid silver other than silver behenate contained in the organic acid silver used in the present invention, those mentioned above can be preferably used.

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

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

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

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

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

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but needle crystals having a short axis and a long axis are preferred. In the present invention, the minor axis is 0.01 μm or more and 0.2 μm or more.
0 μm or less, major axis of 0.10 μm or more and 5.0 μm or less, minor axis of 0.01 μm or more and 0.15 μm or less, and major axis of 0.10 μm or more and 4.0 μm or less are more preferred. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by the minor axis and major axis, respectively, is preferably 80% or less, more preferably 50% or less, and still more preferably 30% or less. is there. 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 which can be used in the present invention is
Preferably, desalting can be performed. The method for desalting is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, and floc-forming water washing by a coagulation method can be preferably used.

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

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

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

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

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

As a dispersion apparatus suitable for the present invention, a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation is used.
(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, an aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and fed into a pipe, and then passed through a narrow slit provided in the pipe to obtain a desired pressure. Is applied, and thereafter, the pressure in the pipe is rapidly returned to the atmospheric pressure, or the like, and a sudden pressure drop is caused in the dispersion to obtain an organic silver salt dispersion optimal for the present invention. .

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

In the organic silver salt dispersion of the present invention, the flow rate,
It is possible to disperse to the desired particle size by adjusting the pressure difference during pressure drop and the number of treatments.However, from the viewpoint of photographic characteristics and particle size, the flow rate is 200 m / sec to 600 m / sec, is preferably in the range pressure is 900~3000kg / cm ^2, flow rate 300
m / sec ～600M / sec, the pressure difference at the pressure drop 1500~3000kg / cm ²
More preferably, it is within the range. The number of times of the dispersion processing can be selected as needed, and usually 1 to 10 times is selected, but from the viewpoint of productivity, about 1 to 3 times is selected. It is not preferable to raise the temperature of such an aqueous dispersion under high pressure from the viewpoint of dispersibility and photographic characteristics.At a temperature higher than 90 ° C., the particle size tends to increase, and the fog tends to increase. is there. Therefore, in the present invention, the high pressure, the step before converting to a high flow rate, or
The step after the pressure is reduced, or both of these steps include a cooling step, and the temperature of such aqueous dispersion is preferably kept in the range of 5 to 90 ° C. by the cooling step, and more preferably 5 to 90 ° C. It is preferred that the temperature be kept in the range of 80 ° C, particularly 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 is 20 ° C
Well water, cold water of 5 to 10 ° C treated by a refrigerator, or a refrigerant such as ethylene glycol / water at -30 ° C can be used if necessary.

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

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

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

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

The 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 15% by weight is preferred.

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

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

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

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

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

The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. . The distribution of the halogen composition in the grains may be uniform, the halogen composition may 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.

Methods for forming photosensitive silver halide are well known in the art, for example, Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458.
Can be used.Specifically, a photosensitive silver halide is prepared by adding a silver-supplying compound and a halogen-supplying compound to a gelatin or other polymer solution, and then the organic silver halide is added. A method of mixing with a silver salt is used. The grain size of the photosensitive silver halide is
For the purpose of suppressing white turbidity after image formation, it is preferably small, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.02 μm or more and 0.1 μm or more.
It is preferably 12 μm or less. The grain size as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

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

The photosensitive silver halide grains of the present invention contain a metal or metal complex of Group VII or VIII (Groups 7 to 10) of the periodic table. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One of these metal complexes may be used,
Two or more complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per mol of silver, more preferably in the range of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (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 to stabilize a solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) etc),
Alternatively, an alkali halide (eg, KCl, NaCl, KBr,
NaBr) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

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

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

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

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

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

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

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

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

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

For 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. 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 a method of adding an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain doped with iridium in advance during the preparation of silver halide.

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

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

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

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

The amount of the gold sensitizer to be added varies depending on various conditions. As a guide, the amount is from 10 ^-7 mol to 10 ^-3 mol, preferably from 10 ^-6 mol to 5 mol, per mol of silver halide.
× 10 ^-4 mol or less.

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

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, 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 and 4-324855 can be used. In particular, the general formula (VIII) in JP-A-4-324855
It is preferable to use the compound represented by (IX).

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 a silver halide emulsion is described in JP-A-5-3132.
It can be tested by the method described in No. 84. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals,
Tellurosulfonates, compounds having a P-Te bond, containing T
e Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, UK Patent 235,211 and 1,121,496,
No. 1,295,462, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-204640, JP-A-3-53693, JP-A-3-31598, JP-A-4
-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Che)
m.Commun.) 635 (1980), ibid 1102 (1979), ibid 645 (197
9), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Tran)
s.) 1,2191 (1980), edited by S. Patai, The Chemistry of Organic S, edited by The Chemistry of Organic Selenium and Tellurium
erenium and Tellunium Compounds), Vol. 1 (1986), V
ol. 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 varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

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

In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also, when the pH of the emulsion is 7 or more or p
Reduction sensitization can be achieved by aging while keeping Ag at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

The silver halide emulsion of the present invention may be added with a thiosulfonic acid compound by the method described in European Patent Publication 293,917.

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

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, and more preferably 0.03 to 0.3 mol per 1 mol of the organic silver salt. It is particularly preferably at least 0.25 mol and not more than 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, and a homogenizer. Etc., or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, or the like.
There is no particular limitation as long as the effects of the present invention are sufficiently exhibited.

The compound of the formula (P) used in the present invention will be described in detail. Formula (P) is shown below.

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

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

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

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

In the formula (P), Q is preferably an arylene group, particularly preferably a phenylene group.

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

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

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

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

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

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The compound of the present invention can be easily synthesized by a usual organic synthesis reaction. A typical synthesis example is shown below.

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

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

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

(2) Synthesis of Exemplified Compound (P-7) A solution of 4.7 g of diethanolamine and 50 ml of methanol was cooled on ice, and 4.1 g of the intermediate (C) was added. After stirring for 5 minutes, 50 ml of water was added, and white crystals precipitated. This was filtered, dissolved in a small amount of DMAc (dimethylacetamide), and 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 (tetrahydrofuran), and the mixture was stirred at room temperature for 5 minutes. After diluting hydrochloric acid to neutralize the reaction solution, 200 ml of water was added and the precipitated crystals were filtered. The obtained crude crystals are treated with a small amount of DMAc
And methanol was added until crystals precipitated.
The crystals were filtered and dried, and as a result, Exemplified Compound (P-6) was 2
2 g were obtained. White crystals.

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

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

The compound represented by the formula (P) of the present invention is
It may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side, but is preferably added to the image forming layer or a layer adjacent thereto. These may be used alone or in combination of two or more, and the amount used may be a desired amount according to the performance such as sensitivity and fog. It is preferably 10 ^-4 to 1 mol per mol, and 10 ^{-3 to} 5 × 10 ^-1.
Mole is more preferred.

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

The substituted alkene derivative represented by the formula (1), the substituted isoxazole derivative represented by the formula (2), and the specific acetal compound represented by the formula (3) used in the present invention will be described.

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In the formula (1), R¹, R^Two, R^ThreeEach
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing property.
Represents a group or a silyl group. In the formula (1), R¹And Z, R^Two
And R ^Three, R¹And R^TwoOr R^ThreeAnd Z are joined together
An annular structure may be formed. In the formula (2), R
^FourRepresents a substituent. In the formula (3), X and Y are each
A and B each independently represent a hydrogen atom or a substituent.
Independently, an alkoxy group, an alkylthio group, an alkylamido
Group, aryloxy group, arylthio group, anilino
Group, heterocyclic oxy group, heterocyclic thio group, or hetero
Represents a ring amino group. In equation (3), X and Y or A
And B may combine with each other to form a cyclic structure
No.

The compound represented by the formula (1) will be described in detail.
I will tell. In the formula (1), R¹, R^Two, R^ThreeIs German
Represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group.
Or a silyl group. In the formula (1), R¹And Z, R^TwoAnd R
^Three, R¹And R^TwoOr R^ThreeAnd Z are linked together to form a ring
A structure may be formed.

When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group and a cycloalkyl group). An alkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including an N-substituted nitrogen-containing heterocyclic group), and a heterocyclic group containing a quaternized nitrogen atom ( For example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfonylcarbamoyl group, an acylcarbamoyl group, Famoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, A droxy group or a salt thereof, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, and a carbamoyloxy group , Sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle)
Thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoryl group, phosphorus Examples thereof include a group having an acid amide or phosphate structure, a silyl group and a stannyl group. These substituents may be further substituted with these substituents.

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

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

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

Next, preferred ranges 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.

In the formula (1), the electron-withdrawing group represented by Z is preferably a group having a total number of carbon atoms of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carbonyl group,
Imino group, imino group substituted with N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acyloxy group, acylthio group, or any electron withdrawing And a phenyl group substituted with a functional group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group,
An alkylsulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group, and particularly preferably a cyano group, a formyl group, an acyl group. , An alkoxycarbonyl group, an imino group or a carbamoyl group. The group represented by Z in the formula (1) is more preferably an electron-withdrawing group.

In the formula (1), the substituent represented by R ¹ , R ² and R ³ 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 ¹ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom, or a silyl group.

When R ¹ represents an electron-withdrawing group, it is preferably a group having the following total number of carbon atoms, 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 ¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 6 to 30 carbon atoms. Examples of the substituent include any substituent.
Among them, an electron-withdrawing substituent is preferable.

In the formula (1), R ¹ is more preferably
It is time to represent an electron withdrawing group or an aryl group.

In the formula (1), the substituents represented by R ² and R ³ are preferably, specifically, groups having the same meaning as the electron-withdrawing group represented by Z in the above-mentioned formula (1), and alkyl groups. , A hydroxy group (or a salt thereof), a mercapto group (or a salt thereof),
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
Examples include an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group.

In formula (1), R ² and R ³ are more preferably when one of them is a hydrogen atom and the other is a substituent. The substituent is preferably an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group. Group, alkylamino group, anilino group,
Heterocyclic amino group, acylamino group (particularly perfluoroalkaneamide group), sulfonamide group, substituted or unsubstituted phenyl group, or a heterocyclic group, more preferably a hydroxy group (or a salt thereof), a mercapto group ( Or a salt thereof), an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
A heterocyclic thio group or a heterocyclic group, particularly preferably a hydroxy group (or a salt thereof), an alkoxy group, or a heterocyclic group.

In the formula (1), it is also preferred that Z and R ¹ , or R ² and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number including a substituent of 1 to 7. 40,
Further, 3 to 30 is preferable.

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

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

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

When R ⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and the substituent is represented by R ¹ , R ² , R ³ of the formula (1). When represents a substituent, the same as those described as the substituent can be mentioned.

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

Next, the compound represented by the formula (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 R ^{1 to} R ^{3 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 group, arylsulfonyl group, sulfamoyl group, phosphoryl group, carboxy Group (or its salt), sulfo group (or its salt), hydroxy group (or its salt), mercapto group (or its salt), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero group Ring thio group, amino group, alkylami Group, anilino group, heterocyclic amino group, a silyl group, and the like.

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

In the formula (3), the substituents represented by X and Y are preferably groups having 1 to 40 carbon atoms in total, more preferably 1 to 30 carbon atoms in total, 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, nitro, alkoxycarbonyl, carbamoyl, acyl, formyl, acylthio, acylamino, thiocarbonyl, sulfamoyl, alkylsulfonyl. Group, an arylsulfonyl group, an imino group, an imino group substituted with an N atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group Group, alkylsulfonyl group,
An arylsulfonyl group, an acyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, or a phenyl group substituted with any electron-withdrawing group; is there.

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

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

In the formula (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.

[0161]

Embedded image

In the formula (A), Z ¹¹ is -Y ¹¹ -C (=
^{CH-X 11) -C (=} O) - represents a nonmetallic atomic group capable to form a 5-membered to 7-membered ring structure with. Z ¹¹ 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. ^{Te, -Y 11 -C (= CH-} X 11) -C (= O) - form a 5- to 7-membered ring structure with. Z ¹¹ may have a substituent, and Z ¹¹ itself may be a part of an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic hetero ring. , Z ¹¹ are -Y ¹¹ -C (=
The 5- to 7-membered ring structure formed together with CH—X ¹¹ ) —C (＝ O) — forms a fused ring structure.

In the formula (B), Z ¹² is -Y ¹² -C (=
Represents a ^{CH-X 12) -C (Y} 13) = non-metallic atomic group capable to form a 5-membered to 7-membered ring structure with N-. Z ¹² 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. ^{Te, -Y 12 -C (= CH-} X 12) -C (Y 13) =
Together with N-, a 5- to 7-membered ring structure is formed. Z ¹² may have a substituent, and Z ¹² itself may be a part of an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic hetero ring. , Z ¹² is -Y
Ring structures ^{12 -C (= CH-X 12} ) -C (Y 13) = 5 -membered to 7-membered formed together with N- will form a condensed ring structure.

When Z ¹¹ and Z ¹² have a substituent, examples of the substituent are selected from the following.

That is, typical substituents include, for example, a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (including an aralkyl group, a cycloalkyl group, an active methine group, etc.), an alkenyl group Group, alkynyl group, aryl group, heterocyclic group, quaternized heterocyclic group containing a nitrogen atom (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof , A sulfonylcarbamoyl group, an acylcarbamoyl group, a sulfamoylcarbamoyl group, a carbazoyl group, an oxalyl group, an oxamoyl group, a cyano group, a thiocarbamoyl group, a hydroxy group, an alkoxy group (a group having a repeating ethyleneoxy or propyleneoxy group unit. Including aryloxy groups Heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, 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, 4
Grade ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle)
A thio group, an (alkyl or aryl) sulfonyl group,
(Alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, group containing a phosphoric acid amide or phosphate ester structure, silyl group, stannyl group, etc. Is mentioned. These substituents may be further substituted with these substituents.

Next, Y ^{13 in the} formula (B) will be described. In the formula (B), Y ¹³ represents a hydrogen atom or a substituent,
When Y ¹³ represents a substituent, examples of the substituent include the following groups. That is, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an amino group, an (alkyl, aryl, or heterocyclic) amino group, an acylamino group, and a 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 ¹¹ or Z ¹² may have.

In the formula (A) or (B), X ¹¹ and X ¹² 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 group) 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.

The salt herein means a salt, a silver salt, a zinc salt or a quaternary ammonium salt (tetraethylammonium salt, dimethylcetylbenzyl) of an alkali metal (sodium, potassium, lithium) or an alkaline earth metal (magnesium, calcium). Ammonium salt), 4
Represents a phosphonium salt or the like.

In the formulas (A) and (B), Y ¹¹ and Y ¹² represent a —C (＝ O) — group or a —SO ₂ — group.
Next, a preferred range of the compound represented by the formula (A) or (B) will be described. In the formula (A) or the formula (B), Y ¹¹ and Y ¹² are preferably a —C (＝ O) — group.

In the formula (A) or (B), X ¹¹ and X ¹² 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), 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 (B), when X ¹¹ and X ¹² represent an alkoxy group, the total number of carbon atoms is 1 to
18 is preferable, 1 to 12 is more preferable, and 1 to 5 is particularly preferable. In formula (A) or (B), when X ¹¹ and X ¹² represent a heterocyclic group, the total carbon number is preferably 2 to 20, and more preferably 2 to 16.

In the formula (A), Z ¹¹ 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 ¹¹ is more preferably -NN-, -N
-C-, -OC-, -CC-, -C = C-, -S-
An atomic group such as C-, -NCN-, -C = CN-,
Further, it is a case having a hydrogen atom or a substituent, particularly preferably -NN-, -NC-, -C =
This is the case where the atomic group such as C- further has a hydrogen atom or a substituent.

Z ¹¹ itself forms part of an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic hetero ring, and Z ¹¹ is represented by —Y ¹¹ —C (＝ CH—X ¹¹ ) -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,
Examples include a naphthalene ring, a pyridine ring, a cyclohexane ring, a piperidine ring, a pyrazolidine ring, a pyrrolidine ring, a 1,2-piperazine ring, a 1,4-piperazine ring, an oxane ring, an oxolane ring, a thiane ring, and a thiolane 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 ¹² 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 ¹² itself forms part of an aromatic or non-aromatic carbocyclic ring or an aromatic or non-aromatic heterocyclic ring, and forms —Y ¹² —C (＝ CH—X ¹² ) —C (Y ¹³ ) =
It is also preferable to form a condensed ring structure with a 5- to 7-membered ring structure formed together with 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. , 1,2-piperazine ring, 1,4-piperazine ring, oxane ring, oxolane ring, thiane ring, thiolane ring and the like.

In the formula (B), Z ¹² is more preferably an atomic group such as —N—, —O—, —S—, —C—, —C ＝ C—, and if possible, further a hydrogen atom or It is a case where a substituent is present, and particularly preferably a case where an atomic group such as -N- or -O- further has a hydrogen atom or a substituent when possible.

In the formulas (A) and (B), the substituent of Z ¹¹ or Z ¹² 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 ¹¹ and Z ¹² 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 ¹³ 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 ¹³ is more preferably a substituent. Specifically, an alkyl group, a phenyl group, an amino group, an anilino group, an acylamino group, an alkoxy group, an aryloxy group, a carbamoyl group Is 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 ¹¹ preferably has 2 or more carbon atoms, including its substituent, and more preferably 3
More preferably, it is the above. In the formula (B), Z ¹²
It is preferable that the sum of the total number of carbon atoms of this and Y ¹³ including its substituents is 8 or more. In the formula (A), Z
¹¹ has a total carbon number of 3 or more and 40 or less including its substituents, and particularly preferably 6 or more and 30 or less. In the formula (B), Z ¹² , including its substituents, preferably has a sum of the total number of carbon atoms of Y ¹³ with Y ¹³ of from 8 to 40, and more preferably from 8 to 30. Is particularly preferred.

Among the compounds represented by the formula (A) of the present invention, a particularly preferred compound is that, in the formula (A), Y ¹¹ represents a carbonyl group, and Z ¹¹ represents —Y ¹¹ —C (＝ CH—X ¹¹ ) -C
(= O)-is a compound that forms an indandione ring, a pyrrolidinedione ring, or a pyrazolidinedione ring. Among them, compounds that form a pyrazolidinedione ring are most preferred. Particularly preferred compounds among the compounds represented by the formula (B) of the present invention are those wherein, in the formula (B), Y ¹² represents a carbonyl group, and Z ¹² represents -Y ¹² -C (= CH-X ¹² ) -C
(Y ¹³⁾ = a compound that forms a 5-pyrazolone ring with N-.

The compounds represented by the formulas (1) to (3), (A) and (B) of the present invention have a structure in which an adsorptive group that adsorbs to silver halide is incorporated. Good. Examples of such adsorptive groups include U.S. Pat. Nos. 4,385,108 and 4,485, such as alkylthio, arylthio, thiourea, thioamide, mercaptoheterocyclic, and triazole groups.
459,347, JP-A-59-195233, 5
Nos. 9-200231, 59-201045, 59
No.-201046, No.59-201047, No.59-
No. 201048, No. 59-201049, JP-A-61-61
-170733, 61-270744, 62-
No. 948, No. 63-234244, No. 63-2342
45 and 63-234246. 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) of the present invention may be used in ballasts commonly used in immobile photographic additives such as couplers. It may have incorporated groups or polymers. Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. As a polymer,
For example, those described in JP-A-1-100530 can be mentioned.

The compounds represented by the formulas (1) to (3), (A) and (B) of the present invention contain a cationic group (specifically, a quaternary ammonium group). A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocyclic) thio group, or a base. It may contain a dissociable dissociable group (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.). 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 and JP-A-5-33346.
6, JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat. No. 4,994,365.
No. 4,988,604, JP-A-3-25924.
No. 0, JP-A-7-5610, JP-A-7-244348
And the compounds described in German Patent No. 4006032.

Next, the formulas (1) to (3) of the present invention, the formula (A),
Specific examples of the compound represented by the formula (B) are shown below. However, the present invention is not limited to the following compounds.

[0190]

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[0191]

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[0192]

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[0193]

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The compounds represented by the formulas (1) to (3), (A) and (B) of the present invention can be prepared by using water or a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used.

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

The compounds represented by the formulas (A) and (B) in the formulas (1) to (3) of the present invention may be used as a layer on the image recording layer side with respect to the support, that is, the image forming layer or other layers. May be added to any of the layers, but is preferably added to the image forming layer or a layer adjacent thereto.

The amounts of the compounds represented by the formulas (1) to (3), (A) and (B) of the present invention are 1 to 1 mol of silver.
× 10 ^-6 to 1 mol is preferable, and 1 × 10 ^{-5 to} 5 × 10 ^-1.
Mole is more preferable, and 2 × 10 ⁻⁵ to 2 × 10 ⁻¹ mole is most preferable.

The compounds represented by the formulas (1) to (3), (A) and (B) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515 and US Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, International Patent WO-97 / 34196, or Japanese Patent Application No. 9-30.
No. 9813 and Japanese Patent Application No. 9-272002 can be synthesized.

The compounds represented by the formulas (1) to (3), (A) and (B) of the present invention may be used alone or in combination of two or more. In addition to the above, U.S. Pat. No. 5,545,515, U.S. Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, International Patent WO-97 / 34196.
Or the compounds described in U.S. Pat. No. 5,686,228, or Japanese Patent Application Nos. 8-279962 and 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, a hydrazine derivative can be used in combination as a nucleating agent. Preferably, a hydrazine derivative represented by the following formula (H) is used.

[0201]

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Where R²⁰Is an aliphatic group, an aromatic group, or
R represents a heterocyclic group;^TenRepresents a hydrogen atom or a blocking group
Represents, G¹Is -CO-, -COCO-, -C (= S)-,
-SO_Two-, -SO-, -PO (R³⁰) -Group (R³⁰Is R^Ten
Selected from the same range as the group defined in^TenDifferent from
May be. ) Or iminomethylene group.
A ¹, A^TwoAre both hydrogen atoms, or one is a hydrogen atom
The other is a substituted or unsubstituted alkylsulfonyl group,
Represents an arylsulfonyl group or an acyl group. m ¹Is
0 or 1, and m¹Is 0, R^TenIs an aliphatic group,
Represents an aromatic group or a heterocyclic group.

The hydrazine derivative represented by the formula (H) will be described in detail. The aliphatic group represented by R ²⁰ in the formula (H) 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 ²⁰ is a monocyclic or condensed-ring aryl group, such as a phenyl group or a naphthyl group derived from a benzene ring or a naphthalene ring. The heterocyclic group represented by R ²⁰ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group. Examples of the heterocyclic ring in these groups include a pyridine ring , Pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, thiophene ring, triazine ring, morpholine ring, piperidine ring,
Examples include a piperazine ring and a benzo [1,3] dioxole ring. R ²⁰ may be substituted with any substituent.

Preferred as R ²⁰ are an aryl group, an alkyl group and an aromatic heterocyclic group, more preferably a substituted or unsubstituted phenyl group and a C 1 -C 1 group.
3 substituted alkyl groups or aromatic heterocyclic groups.

R²⁰Represents a substituted alkyl group having 1 to 3 carbon atoms.
Then R²⁰Is more preferably a substituted methyl group,
Is preferably a disubstituted or trisubstituted methyl group
No. R ²⁰Is a preferred specific example when represents a substituted methyl group.
T-butyl, dicyanomethyl, dicyanophen
Nilmethyl group, triphenylmethyl group (trityl group),
Phenylmethyl group, methoxycarbonyldiphenylmethyl
Group, cyanodiphenylmethyl group, methylthiodiphenyl
Methyl group, cyclopropyldiphenylmethyl group, etc.
Among them, a trityl group is most preferable.

When R ²⁰ 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 ²⁰ is most preferably a substituted or unsubstituted phenyl group.

In the formula (H), R ¹⁰ represents a hydrogen atom or a block group, and the block 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 ¹⁰ is preferably an alkyl group (a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a trifluoromethyl group, a difluoromethyl group and a 2-carboxytetrafluoroethyl group). , Pyridiniomethyl, difluoromethoxymethyl, difluoro (methylthio) methyl, difluorocarboxymethyl, hydroxymethyl, methanesulfonamidomethyl, benzenesulfonamidomethyl, trifluoroacetylmethyl, dimethylaminomethyl, phenylsulfonyl Methyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxymethyl group, 4-
Ethylphenoxymethyl group, phenylthiomethyl group, t
-Butyl group, dicyanomethyl group, diphenylmethyl group,
A triphenylmethyl group, a methoxycarbonyldiphenylmethyl group, a cyanodiphenylmethyl group, a methylthiodiphenylmethyl group, etc., an alkenyl group (an alkenyl group having 1 to 10 carbon atoms, for example, a vinyl group, a 2-ethoxycarbonylvinyl group, Fluoro-2-methoxycarbonylvinyl group, 2,2-dicyanovinyl group, 2-cyano-2-methoxycarbonylvinyl group, 2-cyano-2-
An ethoxycarbonylvinyl group, a 2-acetyl-2-ethoxycarbonylvinyl group or the like), an aryl group (monocyclic or condensed-ring aryl group containing a benzene ring, and particularly preferably a phenyl group, a 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, an ethoxy group,
Hydroxyethoxy group, benzyloxy group, t-butoxy group, etc.), amino group (unsubstituted amino group,
Preferred are an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group (including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom) of, for example, 2, 2, 6, 6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, 3-hydroxypropylamino group,
Anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.). The group represented by R ¹⁰ may be substituted with any substituent.

Among the groups represented by R ¹⁰ , preferred are a hydrogen atom, an alkyl group and an alkenyl group when R ²⁰ represents a phenyl group or an aromatic heterocyclic group and G ¹ is a —CO— 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 ¹⁰ 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. .

R²⁰Represents a substituted methyl group, and G¹But-
In the case of a CO- group, R^TenIs preferably a hydrogen atom,
Kill group, aryl group, heterocyclic group, alkoxy group,
Group (unsubstituted amino group, alkylamino group, aryl group
Amino group, heterocyclic amino group), more preferably
Hydrogen atom, alkyl group, aryl group, heterocyclic group, al
Coxy group, alkylamino group, arylamino group, hete
It is a ro-ring amino group. G ¹Is a -COCO- group
Is R²⁰Regardless of R^TenIs an alkoxy group, arylo
Xyl groups and amino groups are preferred, particularly substituted amino groups.
Or alkylamino, arylamino, or saturated
Alternatively, an unsaturated heterocyclic amino group is preferable.

When G ¹ is a —SO ₂ — group, R ²⁰
Regardless, R ¹⁰ is preferably an alkyl group, an aryl group or a substituted amino group.

In the formula (H), G ¹ is preferably -CO
Or a -COCO- group, particularly preferably -C
O- group.

In the formula (H), A ¹ and A ² represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a sum of substituent constants of Hammett is -0.5 or more) Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more, or a linear group. , A branched or cyclic, substituted or unsubstituted aliphatic acyl group, and A ¹ and A ² are most preferably hydrogen atoms.

In the formula (H), m ¹ represents 1 or 0. When m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group or a heterocyclic group. When m ¹ is 0, R ¹⁰ is particularly preferably a phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an alkenyl group. Of these, for the phenyl group and the substituted alkyl group having 1 to 3 carbon atoms, its preferred range is the same as the preferable ranges of R ²⁰ as described above.
When R ¹⁰ is an alkenyl group, preferably R ¹⁰ is a vinyl group, and is a substituent selected from the following substituents: a cyano group, an acyl group, an alkoxycarbonyl group, a nitro group, a trifluoromethyl group, a carbamoyl group and the like. Vinyl groups having one or two groups are particularly preferred. In particular,
Examples thereof include a 2,2-dicyanovinyl group, a 2-cyano-2-methoxycarbonylvinyl group, a 2-cyano-2-ethoxycarbonylvinyl group, and a 2-acetyl-2-ethoxycarbonylvinyl group. m ¹ is preferably 1.

In the formula (H), R^TenIs G¹-R^TenPart of
From the residual molecule, and -G¹-R ^TenIncluding partial atoms
That cause a cyclization reaction that produces a cyclic structure
And a hydrazine derivative represented by the formula (H).
The conductor has an adsorptive group that adsorbs to silver halide.
It may be incorporated. R of formula (H)^TenOr R²⁰To
Is used in immobile photographic additives such as couplers.
Incorporates commonly used ballast groups or polymers
And R in formula (H)^TenOr R
²⁰May have a plurality of hydrazino groups as substituents.
Often, the compound represented by the formula (H) is hydrazino
Represents a multimer for the group. Further, R of the formula (H)^TenAlso
Is R²⁰Has a cationic group (specifically, a quaternary
A group containing an ammonium group or a quaternized nitrogen atom
Including nitrogen-containing heterocyclic group), ethyleneoxy group or
Groups containing repeating units of a propyleneoxy group, (alkyl
, Aryl, or heterocycle) thio group or base
Dissociable groups (carboxy group, sulfo group,
Acylsulfamoyl group, carbamoylsulfamoyl
And the like) may be contained. These examples include
For example, JP-A-63-29751, U.S. Pat.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948 and 63-234244
No. 63-234245, No. 63-234246
JP-A-2-285344, JP-A-1-005305
No. 0, JP-A-64-86134, JP-A-4-16938, JP-A-5
-199701, WO95-32452, WO95-32
No. 453, JP-A-9-235264, JP-A-9-235265, JP
Hei 9-235266, JP Hei 9-235267, JP Hei 9-179229,
JP-A-7-234471, JP-A-5-333466
JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat. No. 4,994,365.
No. 4,988,604, JP-A-73-2592.
No. 40, JP-A-7-5610, JP-A-7-24434
No. 8, German Patent 4006032 and the like.
I can do it.

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.

[0218]

[Table 1]

[0219]

[Table 2]

[0220]

[Table 3]

[0221]

[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 also 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-9-304870, JP-A-9-304872,
JP-A-9-304871, JP-A-10-31282
No. 5,496,695, European Patent 714320
All the hydrazine derivatives described in A.

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.

Further, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and co-solvents such as ethyl acetate and cyclohexanone are prepared by the well-known emulsification dispersion method. And then mechanically produce and use an emulsified dispersion. 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 layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side, but may be added to the image forming layer or a layer adjacent thereto. I prefer to.

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 × 1.
0 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is most preferred.

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

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

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

The acid or 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 from the viewpoint that the desired effect is exhibited in a small amount. .

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

The photothermographic material of the present invention 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 preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The 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 using organic silver salts, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
47-33621, 49-46427, 49-115540, 50-14
No. 334, No. 50-36110, No. 50-147711, No. 51-32632,
No. 51-1023721, No. 51-32324, No. 51-51933, No. 52-8
4727, 55-108654, 56-146133, 57-82828
No. 57-82829, JP-A-6-3793, U.S. Pat.
No. 6, 3,751,252, 3,751,255, 3,761,270,
3,782,949, 3,839,048, 3,928,686, 5,4
64,738, German Patent 2321328, European Patent 692732 and the like. For example, phenylamide oxime,
Amidoximes such as 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2′-bis (hydroxymethyl) propionyl-β-
A combination of an aliphatic carboxylic acid aryl hydrazide such as a combination of phenylhydrazine and ascorbic acid with ascorbic acid; a combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis (ethoxyethyl) hydroxyl Amines, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; azine and sulfonamide phenol (E.g., phenothiazine and 2,6-dichloro-4-
Benzenesulfonamidophenol); ethyl-α-
Α-cyanophenylacetic acid derivatives such as cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′- Dihydroxy-1,1'-binaphthyl and bis (2
Bis-β-naphthol as exemplified by -hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxy Acetophenone); 5-pyrazolone, such as 3-methyl-1-phenyl-5-pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone. Reductones as exemplified; sulfonamide phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2- Chromanes such as dimethyl-7-t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydrogen 1,4-dihydropyridines such as lopyridine; bisphenols (eg, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4 , 4-Ethylidene-bis (2-t-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2 -Bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and Certain indane-1,3-diones; chromanol (such as tocopherol).
Particularly preferred reducing agents are bisphenol and chromanol.

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

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

In a photothermographic material utilizing an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077 and JP-A-47-10282.
Nos. 49-5019, 49-5020, 49-91215, 49-9
No. 1215, No. 50-2524, No. 50-32927, No. 50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-279
No. 23, No. 52-14788, No. 52-99813, No. 53-1020, No. 5
3-76020, 54-156524, 54-156525, 61-1836
No. 42, JP-A-4-56848, JP-B-49-10727, 54-2033
No. 3, U.S. Pat.Nos. 3,080,254, 3,446,648, 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent 138079
No. 5, Belgian Patent No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimides (eg, N
-Hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-
Mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole N- (aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide ); And blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N'-hexamethylenebis (1-
Carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl- 5 [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4
-Oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione A combination of phthalazinone and a phthalic acid derivative (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); phthalazine,
Phthalazine derivatives (e.g., 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine,
6-iso-propylphthalazine, 6-iso-butylphthalazine,
6-tert-butylphthalazine, 5,7-dimethylphthalazine,
And metal salts; and phthalazine and its derivatives with phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride). Combinations; quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes, such as hexachlororhodium, which function not only as color-toning agents but also in-situ as sources of halide ions for silver halide formation
(III) ammonium, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine- 2,4-
Benzoxazine-2,4-diones such as dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric -Triazines (e.g., 2,4-dihydroxypyrimidine,
2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (e.g., 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6
-Dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).

The color tone agent of the present invention may be added by any method such as a solution, a powder, and a solid fine particle dispersion. 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 surface pH of the photothermographic material of the present invention before the heat development processing is preferably 6.0 or less, more preferably 5.5 or less. The lower limit is not particularly limited, but 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.

The film surface pH of the photothermographic material of the present invention
When measuring the photothermographic material 2.5 mm × 2.5 cm before the heat development processing, the film was folded into a boat shape, 300 μl of distilled water was dropped on the image forming layer side, and the solution was allowed to stand for 30 minutes. It is preferable to measure the dropped solution for 1 minute with a pH BOY-P2 (a semiconductor type pH meter manufactured by Shindengen Kogyo Co., Ltd.).

As the binder of the present invention, the following polymer latex is preferably used.

In the photothermographic material of the present invention, at least one of the image forming layers containing the photosensitive silver halide contains the polymer latex described below at 50% by weight of the total binder.
The image forming layer used as described above is preferable.
(Hereinafter, this image forming layer is referred to as "the image forming layer of the present invention", and the polymer latex used for the binder is referred to as "the polymer latex of the present invention.") The polymer latex is not limited to the image forming layer, but may be a protective layer or a back layer. In particular, when the photothermographic material of the 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. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. Regarding the polymer latex of the present invention, `` Synthetic resin emulsion (Hei Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (1978)) '', `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, edited by Keiji Kasahara, Published by Kobunshi Kankokai (1993)), `` Chemistry of Synthetic Latex (Souichi Muroi,
Published by Kobunshi Kankokai (1970)). The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably 5 to 100.
A range of about 0 nm is preferable. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

As the polymer latex of the present invention, other than the polymer latex having a normal uniform structure, a so-called core / polymer latex may be used.
Shell type latex may be used. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

The glass transition temperature (Tg) of the polymer latex preferably used for the binder of the present invention differs between the protective layer, 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 as a protective layer or back layer, 25 to 25
A glass transition temperature of 70 ° C. is preferred.

The minimum film forming temperature (MFT) of the polymer latex of the present invention is preferably from -30 ° C to 90 ° C, more preferably from about 0 ° C to 70 ° C. A film-forming aid may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex, also called a plasticizer. )"It is described in.

Examples of the polymer used in the polymer latex of the present invention include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. There is. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. 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 for 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 Lx811,814,821,820,857
(Nippon Zeon Co., Ltd.) and other polyester resins, such as FINETEX ES650, 611, 675, 850 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical Co., Ltd.), etc. HYDRAN AP10 as polyurethane resin,
LACSTAR 7310K, 3307B, 4700H, 7132C as rubber resins such as 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
(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 present invention, the above-mentioned polymer latex is preferably used as 50% by weight or more of the total binder, and more preferably 70% by weight or more of the above-mentioned polymer latex.

In the image forming layer of the present invention, if necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose or the like is added in an amount of 50% by weight or less of the whole binder. May be. 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 of the present invention is preferably prepared by applying an aqueous coating solution and then drying it. 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 in addition to water. Water / methanol = 90
/ 10, water / methanol = 70/30, water / ethanol = 90/1
0, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide
= 80/15/5, water / methanol / dimethylformamide = 9
0/5/5. (However, the numbers represent% by weight.)

The total amount of the binder in the image forming layer of the present invention is 0.1.
The range is preferably ^{2 to} 30 g / m ² , more preferably 1 to 15 g / m ² . A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer of the invention.

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

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

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
No. 72661, No. 6-222491, No. 2-230506, No. 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-30114
No. 1, U.S. Pat.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.

As the dyes forming the J-band, the dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131 and JP-A-59-48753 are disclosed. There are dyes, and 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
It may be added to the emulsion by dissolving it in a solvent such as 1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, alone or in a mixed solvent.

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

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

The amount of the sensitizing dye used in the present invention may be a desired amount in accordance with the performance such as sensitivity and fog.
The amount is preferably from 10 ^-6 to 1 mol, more preferably from 10 ^-4 to 10 ^-1 mol, per mol of silver halide in the photosensitive layer.

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

The antifoggant preferably used in the present invention is an organic halide other than formula (P). For example, JP-A Nos. 50-119624, 50-120328, and 51-121332.
Nos. 54-58022, 56-70543, 56-99335, 59
-90842, 61-129642, 62-129845, JP-A-6-20
Nos. 8,191, 7-5621, 7-2781, 8-15809, and US Pat. Nos. 5,340,712, 5,369,000 and 5,464,737.

In the present invention, the compound represented by the formula (Z) is preferably used as an antifoggant. Formula (Z)
The compound represented by is described in detail.

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In the formula (Z), M is a hydrogen atom or k
It represents a valent cation (eg, a metal ion such as a sodium ion, a potassium ion, a calcium ion, a barium ion, and a zinc ion, and an ammonium ion such as a tetramethylammonium ion and a tetrabutylammonium ion). k is an integer of 1 or more as shown by the exemplified ion, and is usually 1 or 2. When M is a hydrogen atom, k = 1.

In the formula (Z), R represents a substituent,
For example, a linear, branched or cyclic alkyl group (preferably having 1 to 20, more preferably 1 to 12, particularly preferably 1 to 8, for example, methyl, ethyl, iso-propyl, t-butyl, n -Octyl, 1,1,3,3-tetramethylbutyl, t-amyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 12, particularly preferably 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 12 carbon atoms)
To 8, for example, propargyl, 3-pentynyl and the like. ), An aralkyl group (preferably having 7 carbon atoms)
~ 30, more preferably 7 ~ 20, particularly preferably 7 ~
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 carbon atoms)
~ 20, particularly preferably 6 ~ 12, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20, more preferably 0 to 10, and still more preferably 0 to 6, for example,
Amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like can be mentioned. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms)
2, particularly preferably 1 to 8, for example, methoxy,
Ethoxy, butoxy and the like can be mentioned. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 20 carbon atoms)
16, particularly preferably 6 to 12, for example, phenyloxy, 2-naphthyloxy and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16,
Particularly preferred is 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ),
An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably carbon The number is 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10, and examples thereof include phenoxycarbonyl and the like, and an acyloxy group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms). Particularly preferably, 2 to 10
And examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 1 carbon atom)
-20, more preferably 2-16, particularly preferably 2-10, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), and an aryloxycarbonylamino group (preferably Has 7 to 20 carbon atoms, more preferably 7 carbon atoms
To 16, particularly preferably 7 to 12, and examples include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably Has 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms.
And include, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 0 to 20, more preferably 0 to 16, particularly preferably 0 to 16 carbon atoms)
To 12, for example, carbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), A ureido group (preferably having 1 to 20 carbon atoms, more preferably 1
To 16, particularly preferably 1 to 12, and examples thereof include ureido, methylureide, and phenylureide. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include methylthio and ethylthio).
An arylthio group (preferably having 6 to 20, more preferably 6 to 16, particularly preferably 6 to 12, and examples thereof include phenylthio, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably Is 1 to 16, particularly preferably 1 to 12, and examples thereof include mesyl and tosyl.) And a sulfinyl group (preferably having 1 to 1 carbon atoms)
20, more preferably 1 to 16, particularly preferably 1 to 12, for example, methanesulfinyl, benzenesulfinyl and the like. ), A phosphoramide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 16 carbon atoms).
To 12, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxy, nitro, hydroxam, sulfino, sulfino, hydrazino, sulfonylthio Thiosulfonyl group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholinyl, etc.),
And a disulfide group.

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

In addition, 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).

The substituent represented by R is preferably
Alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, amino group, alkoxy group, acyl group,
Alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, alkylthio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxy Group, a nitro group, a heterocyclic group, more preferably an alkyl group, an alkenyl group, an aralkyl group, an amino group, an alkoxy group, an alkylthio group, a hydroxy group,
A mercapto group, a halogen atom, a sulfo group, and a carboxy group.

Further, in the formula (Z), it is particularly preferred that the hydroxyl group is substituted with an alkyl group (including an aralkyl group) at the ortho position and / or the para position.

Further, a bisphenol structure in which the compound of the formula (Z) is bonded through one carbon is more preferable.

Next, specific examples of the antifoggant represented by the formula (Z) will be shown, but the present invention is not limited thereto.

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As the antifoggant of the formula (Z) of the present invention, a commercially available one may be used.
And the acid-catalyzed condensation reaction of salicylic acid with a carbonyl compound described in J. Med. Chem., 34, 342 (1991).

The antifoggant of the formula (Z) according to the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl It can be used by dissolving it in sulfoxide, methylcellosolve and the like.

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

The antifoggant of the formula (Z) of the present invention 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 this layer side. It is preferably added to the forming layer or a layer adjacent thereto.
The image forming layer is a layer containing a reducible silver salt (organic silver salt), and as described above, is a photosensitive layer further containing a photosensitive silver halide.

The amount of the antifoggant represented by the formula (Z) is represented by a mol amount per mol of Ag (mol / mol Ag).
Preferably ^{1 × 10 -5 ~5 × 10 -1} mol / molAg, more ^{preferably, 5 × 10 -5 ~1 × 10} -1 mol / molAg, more ^{preferably, 1 × 10 -4 ~5 × 10} - ² mol / molAg. These may be used alone or in combination of two or more.

The antifoggant represented by the formula (Z) 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.

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

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

When a mercapto compound is used in the present invention, it may have any structure, but may be any of Ar-SM ⁰ , Ar-SSA
Those represented by r are preferred. In the formula, M ⁰ is a hydrogen atom or an alkali metal atom, and Ar is an aromatic or fused aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic rings in these groups are benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, carbazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, Tetrazole, triazine, pyrimidine,
Pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is, for example,
Halogen (e.g., Br and Cl), hydroxy, amino,
Carboxy, alkyl (e.g., having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy
(E.g., those having one or more carbon atoms, preferably those having 1 to 4 carbon atoms) and aryl (which may have a substituent) selected from the group consisting of substituents Is also good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
Mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5
-Diphenyl-2-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-hydrochiroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methyl Pyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole,
1-phenyl-5-mercaptotetrazole, 3- (5-mercaptotetrazole) -sodium benzenesulfonate, N-
Methyl-N '-[3- (5-mercaptotetrazolyl) phenyl] urea, 2-mercapto-4-phenyloxazole, N- [3-
(Mercaptoacetylamino) propyl] carbazole and the like, but the present invention is not limited thereto.

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, and more preferably 0.001 to 0.1 mol per mol of silver.
3 moles.

In the image forming layer (photosensitive layer) 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 British Patent No. 955,061.

In the present invention, it is preferable to provide a protective layer on the image forming layer. As a binder for the protective layer, as described above, a polymer latex having a glass transition temperature of 25 ° C. or more and 70 ° C. or less is used. Is preferred. In this case, at least 50% by weight of the total binder of the protective layer, preferably
It is preferable to use the above-mentioned polymer latex at 70% by weight or more. In the present invention, it is preferable to provide at least one such protective 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, Nipol Lx857, methyl (meth) acrylate /
2-ethylhexyl (meth) acrylate / hydroxyethyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, Nipol G576 vinyl chloride resin, and Alon 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 0.5 to 4.0 g / m ^2.
Range.

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

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

In the photosensitive layer of the present invention, various dyes and pigments can be used from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer of the present invention may be any, for example, pigments and dyes described in the color index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye,
Oxonol dyes, carbocyanine dyes, 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, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), azomethine Dyes (e.g., compounds 17 to 47 described in JP-A-5-341441) and indoaniline dyes (e.g., compound 11 described in JP-A-5-289227).
To 19, compound 47 described in JP-A-5-341441, JP-A-5-1651
No. 47, compounds 2-10 to 11) and azo dyes (JP
Compounds 10 to 16) described in 5-341441 are exemplified. As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds used is determined depending on the desired absorption amount, but it is generally preferable to use them in a range of 1 × 10 ⁻⁶ g to 1 g per 1 m ^{2 of the} photographic material.

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

When antihalation dyes are used in the present invention, such dyes have the desired absorption in the desired range,
Any compound may be used as long as it has a sufficiently low absorption in the visible region after the treatment and a desirable absorbance spectrum shape of the back layer is obtained. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458, JP-A-2-216140,
No. 7-13295, No. 7-11432, U.S. Pat.No.5,380,635, JP-A-2-688539, page 13, lower left column, line 1 to line 14,
The lower left column of the page, line 9, from the lower left column of page 14 of JP-A-3-24539
There are compounds described in the lower right column of page 16, and as dyes which can be decolorized by treatment, JP-A Nos. 52-139136, 53-132334, 56-50148.
No. 0, No. 57-16060, No. 57-68831, No. 57-101835, No.
59-182436, JP-A-7-36145, JP-A-7-199409, Tokubo Akira
Nos. 48-33692, 50-16648, Tokuhei Hei 2-41734, U.S. Pat.Nos. 4,088,497, 4,283,487, 4,548,896, 5,1
There is 87,049.

In the present invention, suitable binders for the backing layer are transparent or translucent, generally colorless, and include natural polymers, synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly ( (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (e.g., poly (vinyl formal) and poly (vinyl formal)
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the single-sided light-sensitive material of the present invention, 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 for improving transportability. 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 Nos. 1,939,213 and 2,70
1,245, 2,322,037, 3,262,782, 3,539,344
No. 3,767,448 No., organic matting agents described in each specification such as No. 1,260,772, No. 2,192,241, No. 3,257,206,
Inorganic matting agents well-known in the art, such as inorganic matting agents described in the specifications of JP-A Nos. 3,370,951, 3,523,022, and 3,769,020 can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of water-dispersible vinyl polymers, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, etc., and starch derivatives such as carboxy starch, carboxynitrophenyl Gelatin hardened with a known hardener such as starch, urea-formaldehyde-starch reactant, and hardened gelatin formed into microcapsule hollow granules by coacervate hardening are preferably used. Can be. 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 carrying out 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 light-sensitive material, the particle size, shape, and particle size distribution can be changed as necessary 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 a Beck smoothness of 1200 seconds or less and 50 seconds or more, more preferably 700 seconds or less and 100 seconds or more. It is.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferable to be contained. Also, the matte degree of the emulsion surface protective layer may be any value as long as stardust failure does not occur, but the Bekk smoothness is 300 seconds or more.
It is preferably 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 is composed of organic silver salt, silver halide, developer and binder,
As well as optional additional materials such as toning agents, coating aids and other auxiliaries. The two-layer configuration is that the first emulsion layer (usually the layer adjacent to the support) contains an organic silver salt and silver halide, and the second layer or both layers do not contain some other components. No. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, or may include all components in a single layer as described in U.S. Pat.No.4,708,928. Is also good. In the case of a multi-dye, multi-color photosensitive heat-developable photographic material, each emulsion layer is generally functionalized or non-functional between the emulsion layers (photosensitive layers) as described in U.S. Pat.No. 4,460,681. Are kept distinct from each other by using the barrier layer.

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

The image forming layer (photosensitive layer) of the present invention, a protective layer,
A hardener may be used for each layer such as the back layer. Examples of hardeners include polyisocyanates described in U.S. Pat.No. 4,281,060, JP-A-6-208193, and U.S. Pat.
Epoxy compounds described in 4,791,042 and the like,
Vinyl sulfone compounds described in JP-A-62-89048 and the like are used.

In the present invention, a surfactant may be used 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,
No. 62-170950, Fluoropolymer surfactants described in U.S. Pat.No. 5,380,644, JP-A-60-244945, JP-A-63-18
8135 No. fluorinated surfactants described in U.S. Pat.
Examples thereof include polysiloxane surfactants described in JP-A-5,965 and the like, polyalkylene oxides and anionic surfactants described in JP-A-6-301140 and the like.

The heat-developable photographic emulsion of 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, particularly coated with baryta and / or partially acetylated α-olefin polymers, especially polymers of C 2-10 α-olefins such as polyethylene, polypropylene, ethylene-butene copolymers A paper support is typically used. Such a support may be transparent or opaque, but is preferably transparent. Among them, biaxially stretched polyethylene terephthalate (PET) of 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 more, the dimensions of the film generally expand and contract. If the processed material is used for printing plate making,
This expansion and contraction is 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 temperature 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 be, for example, a soluble salt (for example, chloride or nitrate), a vapor-deposited metal layer, US Pat. No. 2,861,056 and US Pat.
206, 312 or an insoluble inorganic salt as described in U.S. Pat.No. 3,428,451, JP-A-60-252349, a layer containing tin oxide fine particles and the like described in JP 57-104931 May be provided.

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

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

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

In the present invention, the exposure apparatus used for imagewise exposure may be any apparatus capable of performing 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 of the present invention is performed by overlapping the light beams of the light source with each other. The term “overlap” means that the sub-scanning pitch is smaller than the beam diameter. The overlap means, for example, that the beam diameter is equal to the full width at half maximum of the beam intensity (FWHM).
Can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient). In the present invention, 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 upon exposure and tends to cause interference fringes. Examples of the interference fringe prevention technology include a technology disclosed in Japanese Patent Application Laid-Open No. HEI 5-113548 and the like, in which a laser beam is obliquely incident on a photosensitive material, and a technology disclosed in International Patent WO95 / 31754 and the like. Methods using a mode laser are known, and it is preferable to use these techniques.

The heating and developing step of the image forming method of the present invention may be any method, but usually, the photosensitive material exposed imagewise is heated and developed. As a preferred embodiment of the heat developing machine used, as a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum, Japanese Patent Publication No. Hei 5-56499, Japanese Patent Publication No.
-292695, JP-A-9-297385 and International Patent WO95 / 30
As the non-contact type heat developing machine described in JP-A-934, there is a heat developing machine described in JP-A-7-13294, International Patents WO97 / 28489, 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C., more preferably 1 to 250 ° C.
00-140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

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

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

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

The heating section is composed of a preheating section A having a carry-in roller pair 11 and a heat treatment section B having a heater 15. The preheating section A upstream of the heat development processing section B is , Lower than the heat development temperature (for example, 10 to 30 ° C.)
It is desirable to set the temperature and time to be sufficient to evaporate the amount of water in the photothermographic material, and at a temperature higher than the glass transition temperature (Tg) of the support of the photothermographic material 10, It is preferable to set so as not to cause development unevenness.

A guide plate 16 is provided downstream of the heat development processing section B, and a slow cooling section having the carry-out roller pair 12 and the guide plate 16 is provided. The guide plate 16 is preferably made of a material having a low thermal conductivity, and is preferably cooled gradually to prevent the photothermographic material 10 from being deformed.

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.

[0326]

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

Example 1 << Preparation of Silver Halide Emulsion >> (Emulsion A) 11 g of alkali-treated gelatin (2700 ppm or less in terms of calcium content) and potassium bromide 30 in 700 ml of water
and 10 mg of sodium benzenethiosulfonate were dissolved and the pH was adjusted to 5.0 at a temperature of 40 ° C., and 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 mol / l of potassium bromide, (N
An aqueous solution containing 5 × 10 ⁻⁶ mol / L of H ₄ ) ₂ RhCl ₅ (H ₂ O) and 2 × 10 ⁻⁵ mol / L of K ₃ IrCl ₆ was maintained at a pAg of 7.7 by a control double jet method. Minutes over 30 seconds. Then, while maintaining 476 ml of an aqueous solution containing 55.5 g of silver nitrate and an aqueous solution of a halogen salt containing 1 mol / l of potassium bromide and 2 × 10 ^-5 mol / l of K ₃ IrCl ₆ at a pAg of 7.7, a control double jet method was used. Minutes over 30 seconds. Thereafter, the pH was lowered to cause coagulation sedimentation and desalting treatment, and 0.17 g of compound A and 51.1 g of low molecular weight gelatin (average molecular weight: 15,000, low molecular weight gelatin: 20 ppm or less) were added, pH 5.9, pAg 8.0 Was adjusted. 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 after 3 minutes, 71 μm of triethylthiourea was added.
Mol, and the mixture was aged for 100 minutes.
Methyl-1,3,3a, 7-tetrazaindene is 5 × 10
After adding ^-4 mol, the temperature was lowered to 40 ° C.

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

[0330]

Embedded image

<Preparation of Organic Acid Silver Dispersion><Organic Acid Silver A> Behenic acid manufactured by Henkel (product name Eden)
or C22-85R) 87.6 g, distilled water 423 ml, 5N-NaOH aqueous solution 49.
2 ml, tert-butyl alcohol 120 ml mixed, at 75 ℃
The mixture was stirred and reacted for 1 hour to obtain a sodium behenate solution. Separately, prepare 206.2 ml of an aqueous solution of 40.4 g of silver nitrate,
Was kept warm. The reaction vessel containing 635 ml of deionized water and 30 ml of tert-butyl alcohol was kept at 30 ° C., and the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were stirred at a constant flow rate of 62 minutes and 10 seconds, respectively, while stirring. Added over 60 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.
For 9 minutes and 30 seconds, only the sodium behenate solution was added. At this time, the temperature in the reaction vessel was 30 ° C,
The liquid temperature was controlled so as not to rise. In addition, the piping of the addition system for the sodium behenate solution was kept warm by steam tracing, and the liquid temperature at the outlet of the addition nozzle tip was 75%.
The steam amount was controlled so as to reach ℃. Also,
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.

When the morphology of the obtained silver behenate grains was evaluated by electron microscopic photographing, the average projected area diameter was 0.52 μm.
m, average particle thickness 0.14μm, variation coefficient of average sphere equivalent diameter 15
% Scaly crystals.

Next, a dispersion of silver behenate was prepared by the following method. To a wet cake having a dry solid content of 100 g, 7.4 g of polyvinyl alcohol (trade name: PVA-217, average degree of polymerization: about 1700) and water are added, and the total amount is 385 g.
And then predispersed with a homomixer. Next, the pressure of the predispersed undiluted solution was adjusted to 1750 kg / cm ² with a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber), and This was repeated 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 were particles having a volume-weighted average diameter of 0.52 μm and a coefficient of variation of 15%. Particle size measurements are made using the Malvern I
Performed with MasterSizerX manufactured by nstruments Ltd. When evaluated by electron microscopy, the ratio of long side to short side was 1.5,
The grain thickness was 0.14 μm, and the average aspect ratio (ratio of the circle equivalent diameter of the projected area of the grain to the grain thickness) was 5.1.

<< Preparation of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane: Reducing Agent Solid Fine Particle Dispersion >> 1,1-bis (2-hydroxy- 3,5-dimethylphenyl) -3,5,5-trimethylhexane
25 g of a 20 wt% aqueous solution of MP-203 (manufactured by MP Polymer 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, stirred well, and left as a slurry 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. . As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

<< Preparation of solid fine particle dispersion of polyhalogen compound >> For 30 g of polyhalogen compound-A, 4 g of MP-203, an MP polymer manufactured by Kuraray Co., Ltd., and 0.25 g of compound C
Then, 66 g of water was added and stirred well, and then 200 g of 0.5 mm zirconia silicate beads were prepared and put into a vessel together with the slurry, and then dispersed in a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.). The mixture was dispersed for a time to prepare a solid fine particle dispersion. Particle size is 80μ% of particles 0.3μ
m or more and 1.0 μm or less. 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.

<< Preparation of Solid Fine Particle Dispersion of Nucleating Agent >> Table 5
2.5 g of polyvinyl alcohol (PVA-217 manufactured by Kuraray) and 87.5 g of water were added to 10 g of the nucleating agent described in 1 above, and the mixture was stirred well and allowed to stand as a slurry for 3 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, 80 wt% of the particles is 0.1 μm or more 1.
It was 0 μm or less and the average particle size was 0.5 μm.

<< Preparation of Solid Fine Particle Dispersion of Formula (Z) Antifoggant >> With respect to 30 g of the formula (Z) antifoggant,
3 g of MP-203 (manufactured by Kuraray Co., Ltd.) 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 the 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.

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

Binder; Luckstar 3307B 397 g as solid content (manufactured by Dainippon Ink and Chemicals, Inc .; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl)- 3,5,5-trimethylhexane 100 g as solid content Polyhalogen compound-A 0.06 mol as solid content Nucleating agent Type and amount shown in Table 5 Organic halogen compound of formula (P) Type and amount shown in Table 5 Poly Halogen compound-B Amount shown in Table 5 as solid content Sodium ethylthiosulfonate 0.30 g Benzotriazole 1.04 g Polyvinyl alcohol (Kuraray PVA-235) 10.8 g 6-iso-propylphthalazine 15.0 g Orthophosphoric acid Sodium dihydrogen dihydrate 0.37 g Antifoggant of formula (Z) Amount shown in Table 5 as solid content Compound W (methanol solution) 5.0 g Dye A Coating amount at which optical density of 783 nm becomes 0.3 (as a guide) 0.37 g) Silver halide emulsion A 0.06 mol as Ag content Film pH adjuster (sulfuric acid or NaOH) Add as appropriate to achieve the film pH shown in Table 5.

[0342]

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<< Preparation of Emulsion Surface Lower Layer Protective Layer Coating Solution >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) particle size 120 nm Polymer latex solution (copolymer with glass transition temperature 57
° C, solids concentration 21.5wt%, compound D as film-forming aid containing 15wt% based on solids of latex) 956g of H ₂ O
Was added, 1.62 g of compound E, 1.98 g of a matting agent (polystyrene particles, average particle size of 7 μm) and 23.6 g of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.) were added, and H ₂ O was further added. Was prepared.

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

[0345]

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<< Preparation of PET Support with Back / Undercoat Layer >> (1) Support Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6 / 4 (measured at 25 ° C. in weight ratio). After pelletizing this, it was dried at 130 ° C for 4 hours,
After being melted at 00 ° C., the film was extruded from a T-die and rapidly cooled to prepare an unstretched film having a thickness of 120 μm after heat setting.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the 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 (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 with 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 diameter 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 Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 42 mg / m ² deionized gelatin (Ca ^{2 +} content 0.6 ppm) 8 mg / m ² compound A 0.2 mg / m ² polyoxyethylene phenyl ether 10 mg / m ² Sumitex resin M-3 (water-soluble melamine compound, Sumitomo chemical Co., Ltd.) 18 mg / m ² dye A Amount of coating at which the optical density of 783 nm becomes 1.2 SnO ₂ / Sb (9/1 weight ratio, acicular fine particles, major axis / minor axis = 20 to 30, manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² matting agent ( Polymethyl methacrylate, average particle size 5μm) 7mg / m ²

(5) Protective layer Polymer latex-(methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer)) solid 1000 mg / m ² polystyrenesulfonate as quantity (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 ( 218mg / m ²

(6) Preparation of PET support with back / undercoat layer Undercoat layer (a) and undercoat layer (b) were sequentially applied on both sides of the support (base), and dried at 180 ° C. for 4 minutes each. . 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 .

[0354]

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<< Preparation of Photothermographic Material >> Undercoat Layer
The emulsion layer coating solution described above was applied onto the undercoat layer of the PET support on the side coated with (a) and the undercoat layer (b) so that the coating amount of silver was 1.6 g / m ² . Furthermore, the coating liquid for the solid content of the polymer latex was 1.31 g / m ^2.
At the same time as the emulsion coating solution. Thereafter, the coating solution for the upper protective layer on the emulsion surface was applied thereon so that the coating amount of the solid content of the polymer latex was 3.02 g / m ² , to produce a photothermographic material. As shown in Table 5, the film surface pH on the image forming layer side of the obtained photothermographic material was Beck smoothness of 660 seconds, the film surface pH on the opposite side was 5.9, and the Beck smoothness was 560 seconds.

<< 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.

(Thermal Development Process) The exposed photothermographic material was heated using a thermal developing machine shown in FIG. 1 and the roller surface material of the thermal development processing section was made of silicon rubber and the smooth surface was made of Teflon (registered trademark) nonwoven fabric. Preheating section 90 to 110 at a linear speed of 20 mm / sec
15 seconds at ℃ (the drive system of the pre-heating unit and the heat development unit are independent, and the speed difference with the heat development unit is set to -0.5% to -1%), 20 seconds at 121 ° C. The heat development was performed in the slow cooling section for 15 seconds. The 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 and γ (contrast). γ is the density of 0.3 minus the Dmin part, with the logarithm of the exposure amount as the horizontal axis
It was expressed by the slope of a straight line connecting the points 3.0 and 3.0. 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.

The 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 spots were visually evaluated. “5” represents the best quality and “1” represents the worst quality. "3" is the practical limit.

Further, a flat screen sample (A2 size) having a blackening area of 95% was prepared by the above-mentioned exposure method, subjected to a heat development process under the above-mentioned standard conditions, and visually evaluated for processing unevenness. "5"
Is the best 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.

[0361]

[Table 5]

It can be seen that the photothermographic material of the present invention provides high contrast, black spots, and performance in which processing unevenness is less likely to occur. Also, it can be seen that a lower film pH is more advantageous in terms of contrast and Dmax. Moreover, when using the cyclic compound represented by the formula (A) or (B) as a nucleating agent,
It can be seen that black spots and processing unevenness are advantageous. Also,
It can be seen that the use of the antifoggant of the formula (Z) is more advantageous in terms of black spots and processing unevenness. From the above, the effect of the present invention is clear.

[0363]

According to the present invention, high Dmax and high contrast are obtained, and no black spots and no processing unevenness occur.

[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

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H123 AB00 AB03 AB23 AB25 AB28 AB29 BA00 BA01 BB00 BB02 BB03 BB09 BB27 BB31 BB33 BB34 CA00 CA05 CB00 CB03 EA07

Claims (4)

[Claims] In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, the following formula (1) is provided on the side having the image forming layer containing the photosensitive silver halide. ), At least one compound selected from the compounds represented by the formulas (2) and (3), and at least one compound represented by the following formula (P). material. Embedded image [In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be bonded to each other to form a cyclic structure. In the formula (2), R ⁴ 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 group. Represents an 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. In the formula (P), Z ¹ and Z ² each represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, Y ¹ represents a —CO— group or a —SO ₂ — group, and Q represents an arylene. L represents a linking group; W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphate group, a hydroxyl group, a quaternary ammonium group or a polyethyleneoxy group. n is 0 or 1
Represents ] 2. In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder on a support, the following formula (A) is provided on the side having the image forming layer containing the photosensitive silver halide. ) And a compound represented by the formula (B), and a photothermographic material comprising at least one compound represented by the following formula (P). Embedded image [In the formula (A) or the formula (B), Z ¹¹ and Z ¹² each represent a nonmetallic atomic group capable of forming a 5- to 7-membered ring structure, and Y ¹¹ and Y ¹² each represent- X represents a C (＝ O) — group or —SO ₂ — group, and X ¹¹ and X ¹² each represent 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, a heterocyclic amino group, an acylamino group, a sulfonamide group or a heterocyclic group. Y ¹³ represents a hydrogen atom or a substituent. In the formula (P), Z ¹ and Z ² represent a halogen atom, X ¹ represents a hydrogen atom or an electron-withdrawing group, Y ¹ represents a —CO— group or a —SO ₂ — group, and Q represents an arylene group. Alternatively, L represents a divalent heterocyclic group, L represents a linking group, and W represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphoric acid group, a hydroxyl group, a quaternary ammonium group or a polyethyleneoxy group. n represents 0 or 1. ] 3. The photothermographic material according to claim 1, further comprising at least one compound represented by the following formula (Z). Embedded image [In the formula (Z), M represents a hydrogen atom or a k-valent cation, and R represents a substituent. m is an integer of 1 to 4;
When ≧ 2, a plurality of Rs may be the same or different. k is an integer of 1 or more, and when M is a hydrogen atom, k = 1
It is. ] 4. The photothermographic material according to claim 1, wherein the film pH is 6.0 or less.