JP2005301148A - Heat developable photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material (especially, a heat developable photosensitive material) in which dye stability at the time of raw stock preservation is improved. <P>SOLUTION: In a silver halide photographic sensitive material having an image forming layer including a photosensitive silver halide on a supporting body, on at least one surface of the supporting body, it contains a compound of formula (1): DM. In the formula (1), D expresses a cation part of a formula (A). Designated at M is an anion part of the formula (A). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photothermographic material.

  In recent years, in the medical field, reduction of waste processing liquid has been strongly desired from the viewpoint of environmental protection and space saving. Therefore, the photosensitive heat for medical diagnosis and photographic technology that can be efficiently exposed by a laser image setter or a laser imager and can form a clear black image having high resolution and sharpness. There is a need for techniques relating to developed photographic materials. These photosensitive photothermographic materials can eliminate the use of solution processing chemicals and supply customers with a simpler heat development processing system that does not damage the environment.

Although there is a similar request in the field of general image forming materials, medical images are required to have high image quality with excellent sharpness and graininess because fine depiction is required. It is usual to add a dye to the photographic light-sensitive material for the purpose of filtering, preventing halation and preventing irradiation.
These dyes usually function during image exposure and are completely removed during development processing so that the image is not colored by absorption of the visible region of the dye after image formation.

In the conventional wet development processing, it is relatively easy to elute and remove the dye from the photosensitive material in the processing solution. However, it is difficult for a dry development process such as heat development. Therefore, a method for decolorizing the dye by the heat of heat development has already been proposed. For example, there is a technique for controlling the melting point of a base precursor and decolorizing a dye with a base generated during thermal development (see, for example, Patent Document 1).
However, these technologies have insufficient dye decolorization in response to the user's request to heat-process the photosensitive material more quickly, resulting in residual dye in the photothermographic material after processing. Had the disadvantage of
On the other hand, a method in which a non-photosensitive layer of a photothermographic material contains a cyanine dye or a salt thereof and a base precursor which are stable at room temperature is disclosed (for example, see Patent Document 2).
JP-A-11-352626 Japanese Patent Laid-Open No. 11-231457

Patent Documents 1 and 2 disclose that a cyanine dye is emulsified or solid-dispersed, but the dye concentration is low and the coating amount fluctuates during storage until use after preparation of the dispersion. There was a problem. Also, since a large amount (several times) of the polymer dispersant is used for the dye during dispersion, the coating film becomes cloudy, making it difficult to observe the image after heat development, or used during dispersion. There was a problem that the anionic dispersant excessively discolored the cyanine dye in the film during storage of the coating light-sensitive material, and the antihalation effect was reduced.
Accordingly, an object of the present invention is to solve the conventional problems and achieve the following objects. That is, the object of the present invention is to prevent the fluctuation of the coating amount due to the sedimentation of the dye during storage of the dye dispersion and to enable stable production, and the stability of the dye during raw storage is improved and always stable and excellent. Another object of the present invention is to provide a silver halide photographic light-sensitive material (especially a heat-developable light-sensitive material) that can achieve high photographic performance.

The object of the present invention has been achieved by the following photothermographic materials.
<1> A silver halide light-sensitive material having an image forming layer containing a photosensitive silver halide on a support, containing a compound represented by the following general formula (1) on at least one surface of the support And a silver halide photographic light-sensitive material.

General formula (1) DM
[Wherein D represents a cation moiety of the following general formula (A). M represents an anion moiety of the following general formula (A). ]

[In General Formula (A), R ¹ is a hydrogen atom, an aliphatic group, an aromatic group, —NR ²¹ R ²⁴ , —OR ²¹ or —SR ²¹ , and R ²¹ and R ²⁴ are each independently hydrogen. It is an atom, an aliphatic group or an aromatic group, or R ²¹ and R ²⁴ are combined to form a nitrogen-containing heterocycle. R ² is a hydrogen atom, an aliphatic group or an aromatic group. Z ¹ is an atomic group forming a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring, and the nitrogen-containing heterocycle and its condensed ring May have a substituent. Q ₁ represents a group necessary for forming a cyanine dye, a styryl dye, a hemicyanine dye, a rhodacyanine dye, a complex cyanine dye, an allopolar dye, a squalium dye, a croconium dye, or an azamethine dye. M represents a charge balance counter anion having 8 or more carbon atoms. However, M has 3 or less sulfonic acid groups. ]

<2> An image forming layer wherein the silver halide photographic light-sensitive material according to the above <1> further contains a non-photosensitive organic silver salt, a reducing agent and a binder on the surface of the support having the photosensitive silver halide. A photothermographic material having a non-photosensitive layer on at least one surface of the support, wherein the non-photosensitive layer contains a compound represented by the general formula (1) A photothermographic material.

<3> The photothermographic material according to <2>, wherein the non-photosensitive layer is formed using the compound represented by the general formula (1) as a solid dispersion.

<4> The compound represented by the general formula (1) in the solid dispersion according to the above <3> is formed by mixing and dispersing the following general formula (2) and the following general formula (3). A heat-developable photosensitive material.
General formula (2) DA
General formula (3) BM

[In General Formula (2), D represents the cation part of the said General formula (1), and A represents the anion part which does not contain M of General formula (1). In the general formula (3), B represents a cation moiety not containing D in the general formula (1), and M represents an anion moiety in the general formula (1). ]

<5> The thermal development according to <4>, wherein the production rate of the general formula (1) in the solid dispersion is 60 mol% or more based on the total molar amount of the general formula (2). Photosensitive material.

<6> The heat according to any one of <3> to <5>, wherein the concentration of the compound represented by the general formula (1) in the solid dispersion is 10% by mass or more. Development photosensitive material.

<7> The photothermographic material according to any one of <3> to <6>, wherein the solid dispersion contains a water-soluble polymer dispersant.

<8> The photothermographic material according to <7>, wherein the solid dispersion contains a water-soluble polymer dispersant in an amount of 10 to 40% by weight based on the compound represented by the general formula (1). material.

<9> The water-soluble polymer dispersant is at least one member selected from the group consisting of polyvinyl alcohols, modified polyvinyl alcohols, hydroxyalkyl celluloses, carboxymethyl celluloses, polyacrylamides, and polyvinyl pyrrolidones. The photothermographic material according to <7> or <8>, wherein the photothermographic material is characterized.

  According to the present invention, the coating amount variation due to the precipitation of the dye during storage of the cyanine dye dispersion can be prevented to enable stable production, the dye stability during raw storage has been improved, and the photographic performance has always been excellent and stable. Can be provided.

The present invention is described in detail below.
The silver halide photographic light-sensitive material of the present invention contains a photosensitive silver halide and contains a compound represented by the following general formula (1) on at least one surface of a support.
By using a solid dispersion of the compound of the general formula (1), it is possible to stably produce the silver halide photographic light-sensitive material which can be stably produced with small fluctuations in the coating amount of the dye and excellent in storage stability of the coated photosensitive material. Can do.

Furthermore, the silver halide photographic light-sensitive material of the present invention further has an image forming layer containing a non-photosensitive organic silver salt, a reducing agent and a binder on the surface of the support having the photosensitive silver halide, A photothermographic material having a non-photosensitive layer on at least one surface of the support is preferred.
On the image forming surface side, the non-photosensitive layer is an undercoat layer, a protective layer or a plurality of image forming layers provided between the image forming layer and the support, or between the image forming layer and the protective layer. And an antihalation layer provided on the side farther from the light source than the image forming layer.
Further, the non-photosensitive layer is provided on the back surface side as an undercoat layer provided as a layer closest to the support on the back surface side, an antihalation layer on the back surface side, and on the back surface side on the side farthest from the support. It can provide as a back surface protective layer etc. which are provided.

The general formula (1) may be added to at least one of the image forming layer surface side and the back surface side on the support. Among these, the non-photosensitive layer on the back surface side is preferable, and the back surface is particularly preferable. It is preferably contained in the antihalation layer on the side (hereinafter also referred to as “halation prevention layer”).
Hereinafter, the present invention will be described by taking a photothermographic material as an example.

  Examples of the method for incorporating the compound represented by the general formula (1) in the present invention into the non-photosensitive layer of the photothermographic material include various methods such as a solution, an emulsion, a polymer impregnation, and a solid dispersion. The non-photosensitive layer is preferably formed using a solid dispersion obtained by dispersing the compound represented by the general formula (1) in a dispersion medium.

(Solid dispersion)
As a method for preparing a solid dispersion containing a compound represented by the general formula (1) in the present invention, (a) a method of directly dispersing a compound represented by the general formula (1) with a dispersant, B) A method of preparing a compound represented by the general formula (1) by mixing the compound represented by the following general formula (2) and the following general formula (3) in advance and dispersing the compound in the dispersion. The solid dispersion can be prepared by, for example, but is not limited thereto.

  The solid dispersion in the present invention is prepared by pre-mixing the powder of the compound of the present invention together with a dispersant and water, and then dispersing by ball mill, colloid mill, vibrating ball mill, sand mill, jet mill, roller mill or ultrasonic. can do.

Specifically, for example, in (A), a water-soluble polymer dispersant as a dispersant is added to the powder of the compound of the general formula (1) in an amount of 10 to 40% by weight (preferably 12%). To 35 wt%, more preferably 15 to 30 wt%), and if necessary, an anionic surfactant is used in combination, and water is further added to add the general formula (1) in the solid dispersion. The compound can be prepared by dispersing with a sand grinder mill or the like so that the concentration of the compound becomes 10% by weight or more.
In (b), the compound of the general formula (2) and the compound of the general formula (3) (general formula (3) with respect to general formula (2) in a molar ratio of 0.8 to 1.5, preferably Is 0.9 to 1.4, more preferably 1.0 to 1.2), and the water-soluble polymer dispersant is 10 to 40% by weight (preferably with respect to the general formula (2)). 12 to 35% by weight, more preferably 15 to 30% by weight), and water is further added so that the concentration of the compound of the general formula (2) in the solid dispersion becomes 10% by weight or more. It can be prepared by dispersing with a sand grinder mill or the like.
In the dispersion of (b), a water-soluble salt is produced according to the amount of the general formula (1), but it is the dispersion stability and coating film that is removed by ultrafiltration after the dispersion treatment. Is preferable in terms of storage stability.

The yield of the general formula (1) in (b) in the solid dispersion is determined by subjecting the obtained solid dispersion to ultracentrifugation and analyzing the anion species contained in the supernatant by ion chromatography. The ratio of the analytical amount to the amount can be determined as the dye production rate (also referred to as “salt exchange rate”) of the general formula (1).
The production rate of the general formula (1) is preferably 60 mol% or more, because the unreacted general formula (3) affects the storage stability of the dye in the coating film, and is preferably 75 mol% or more. More preferably, it is more preferably 90 mol% or more.

The dispersibility of the solid dispersion can be measured and evaluated by measuring the spectral absorption by diluting the dispersion with water and taking the ratio of absorbance at a specific wavelength. The dye dispersion of the present invention can be used as an index of dispersibility by looking at the ratio between the wavelength near the absorption peak of the dye itself and the absorbance at a specific wavelength of about 100 nm long from the peak.
Further, the dispersion can be evaluated by comparing the presence or absence of aggregates and the degree of generation by observing the dispersion state with an optical microscope after diluting the dispersion with water.

  The sedimentation property of the solid dispersion can be evaluated by comparing the content of the dispersion near the liquid surface, the content near the bottom, the presence or absence of the sediment, and the hardness after natural storage. Since it takes time to evaluate in natural standing, it can be evaluated by measuring with LUMIFUGE (manufactured by LUM, Germany) which can observe the change in dye concentration in the dispersion while simply centrifuging. it can.

  As the concentration of the compound represented by the general formula (1) in the solid dispersion, the dispersion cost per unit bulk powder can be kept low by shortening the time required for dispersion and the viscosity of the dispersion. From the viewpoint of suppression of sedimentation with time due to the rise, it is preferably 10% by mass or more, more preferably 12% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the concentration is not particularly limited, but is usually 40% by mass in view of dispersibility and handling properties (dispersion viscosity, etc.)

The compound represented by the general formula (1) contained in the solid dispersion may be used alone or in combination.
Furthermore, known dyes can be added within a range that does not impair the effects of the present invention. It is preferable that the addition amount of a well-known dye becomes the said range for the total amount with the amount of the compound represented by General formula (1).

The dispersion medium used for the preparation of the solid dispersion is not particularly limited, and examples thereof include water-miscible alcohols such as water and methanol.
Among these, water is preferable because the solid dispersed dye is present in the dispersion without dissolving it.

  In the present invention, the solid dispersion preferably contains a water-soluble polymer dispersant in order to suppress aggregation of the dye fine particles in the solid dispersion and suppress sedimentation during storage.

Any of the water-soluble polymer dispersants can be used as long as the effects of the present invention are not impaired. Examples thereof include polyvinyl alcohols, modified polyvinyl alcohols, hydroxyalkyl celluloses, and carboxymethyl celluloses.
For example, in the case of polyvinyl alcohol, Kuraray Co., Ltd. Kuraray Poval PVA105, PVA-205, PVA-235, PVA-405, etc. In the modified polyvinyl alcohol system, Kuraray Poval MP-202, MP-203, etc., hydroxyalkyl cellulose In systems, Daicel Chemical Industries, Ltd. HEC Daicel SP-200, SP-400, SP-500, etc., Shin-Etsu Chemical Co., Ltd. Metroose 60SH-03, 60SH-15, 65SH-50, 90SH-50 For example, HPC-L and HPC-5L manufactured by Nippon Soda Co., Ltd., CMC Daicel <3403> manufactured by Daicel Chemical Industries, Ltd., etc. for carboxymethyl cellulose, polyacrylamide, polyvinylpyrrolidone, etc. should be used. Is preferred.
Among these, from the viewpoint of aggregation of particles in the solid dispersion and stability of the dispersion over time, polyvinyl alcohol and modified polyvinyl alcohol are preferable, and modified polyvinyl alcohol is more preferable. Specifically, in the modified polyvinyl alcohol system, Kuraray Poval MP-203 (manufactured by Kuraray Co., Ltd.) is most preferable. These water-soluble polymer dispersants may be used alone or in combination.

  The amount of the water-soluble polymer dispersant used in the dye solid dispersion of the present invention is preferably based on the compound represented by the general formula (1), although it depends on the type of the water-soluble polymer dispersant. It is 10-40 mass%, More preferably, it is 12-35 mass%, More preferably, it is 15-30 mass%. By setting the content of the water-soluble polymer dispersant in the dye solid dispersion to 10 to 40% by mass, the dispersion stability over time can be improved, the dispersion is less likely to agglomerate, and the viscosity increases during dispersion. Furthermore, there is little tendency to cause haze in the coating film.

The solid dispersion in the present invention can contain a dispersant (surfactant) in order to suppress aggregation of disperse dye particles in the solid dispersion and suppress sedimentation during storage.
Examples of the dispersant (surfactant) include anionic surfactants having 8 or more carbon atoms. When there are a plurality of polyvalent anions or monovalent anions, the number of carbon atoms per charged monovalent is 8 or more. It is preferable that Examples of the anionic species of the dispersant include sulfonic acid, carboxylic acid, phosphoric acid, boric acid, sulfuric acid and the like. The dispersant preferably has 1 to 2 anionic species per molecule, more preferably 1 or 2 anionic species, and particularly preferably one anionic species. A polymer type having these anionic species as a repeating unit tends to be difficult to obtain sufficient dispersibility and storage sedimentation stability, and is not preferable for dispersion of the cyanine dye according to the present invention.

  As the addition amount of the dispersant used for the preparation of the solid dispersion, when only the dispersant is used as a dispersant, 1 to 100% by mass with respect to the compound represented by the general formula (1) is used. Preferably, 2-50 mass% is more preferable, and 5-25 mass% is especially preferable.

  The solid dispersion in the present invention may contain an antifoaming agent (Surfinol 104E (Nisshin Chemical Co., Ltd.), preservative (benzisothiazolinone sodium salt), etc., as other additives, if necessary. it can.

(Description of compounds (A) and (1) to (3) in the present invention)
The compound in the present invention is a compound represented by the following general formula (1).
General formula (1) DM

  In general formula (1), D represents the cation part of the following general formula (A), and M represents the anion part of the following general formula (A).

In General Formula (A), R ¹ is a hydrogen atom, an aliphatic group, an aromatic group, —NR ²¹ R ²⁴ , —OR ^21, or —SR ²¹ , and R ²¹ and R ²⁴ are each independently a hydrogen atom. , An aliphatic group or an aromatic group, or R ²¹ and R ²⁴ combine to form a nitrogen-containing heterocycle. R ² is a hydrogen atom, an aliphatic group or an aromatic group. Z ¹ is an atomic group that independently forms a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring. The ring may have a substituent. Q ₁ represents a group necessary for forming a cyanine dye, a styryl dye, a hemicyanine dye, a rhodacyanine dye, a complex cyanine dye, an allopolar dye, a squalium dye, a croconium dye, or an azamethine dye. M represents a charge balanced counter anion having 8 or more carbon atoms, provided that M is 3 or less sulfonic acid groups.
In the general formula (Aa), M represents a charge balanced counter anion having 8 or more carbon atoms, and has 1 to 3 charges necessary to neutralize the charge of the molecule. The number of carbons in M is preferably 8 or more per charge.
General formula (Aa) is a tautomer and an equivalent compound of the compound represented by general formula (A). In the present invention, the description of the general formula (A) includes the description of the general formula (Aa) unless otherwise specified.

Hereinafter, the general formula (A) will be described in detail.
The compound represented by the general formula (A) can be used as a photographic dye or dye, and particularly preferably used as a decoloring dye.
The M is not particularly limited as long as it is a charge balanced counter anion having 8 or more carbon atoms, and the upper limit of the carbon number is not particularly limited, but is preferably 45 or less. More preferably, it is C9-C35, More preferably, it is C10-25, Most preferably, it is C12-20. The number of charges that can be taken to neutralize the charge of the molecule is 1 to 3.

  As specific examples of M, counter anions represented by the following (a) to (g) can be preferably used.

In the formulas (a) to (g), Y ¹ represents an aliphatic group having 8 or more carbon atoms or an aromatic group.
Y ² represents an aliphatic group or an aromatic group. Y ³ represents an aliphatic group, an aromatic group, a hydrogen atom, or an anion. However, the total number of carbon atoms of Y ² and Y ³ is 8 or more.
Y ⁴ and Y ⁵ each independently represents an aliphatic group, an aromatic group, a hydrogen atom, or an anion. However, the total number of carbon atoms of Y ⁴ and Y ⁵ is 8 or more.
Y ⁶ represents an aliphatic group or an aromatic group.
Y ⁷ and Y ⁸ each independently represents an aliphatic group, an aromatic group, a hydrogen atom, or an anion. However, the total number of carbon atoms of Y ⁶ , Y ⁷ and Y ⁸ is 8 or more.
Y ⁹ , Y ¹⁰ , and Y ¹¹ each independently represents an aliphatic group, an aromatic group, a hydrogen atom, or an anion. However, the total number of carbon atoms of Y ⁹ , Y ¹⁰ , and Y ¹¹ is 8 or more.
The preferable range of the carbon number of 8 or more described here is as described above.

Next, Y ^{1 to} Y ¹¹ will be described in detail.
In the present specification, the “aliphatic group” means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group or a substituted aralkyl group. An alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group is preferred, and an alkyl group, a substituted alkyl group, an aralkyl group or a substituted aralkyl group is more preferred. A chain aliphatic group is preferred to a cyclic aliphatic group. The chain aliphatic group may have a branch.

The alkyl group preferably has 1 to 45 carbon atoms, more preferably 1 to 35, still more preferably 1 to 25, and most preferably 1 to 20. The alkyl part of the substituted alkyl group is the same as the alkyl group.
The number of carbon atoms in the alkenyl group and alkynyl group is preferably 2 to 45, more preferably 2 to 35, still more preferably 2 to 25, and most preferably 2 to 20.
The alkenyl part of the substituted alkenyl group and the alkynyl part of the substituted alkynyl group are the same as the alkenyl group and alkynyl group, respectively.
The number of carbon atoms in the aralkyl group is preferably 7 to 45, more preferably 7 to 35, still more preferably 7 to 25, and most preferably 7 to 20. The aralkyl part of the substituted aralkyl group is the same as the aralkyl group.

  Any substituent of the aliphatic group may be used. For example, a halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl group, nitro group, carboxyl group, sulfo group, acyl group, alkoxy group, alkoxycarbonyl group, Examples thereof include an alkylthio group, an alkylthiocarbonyl group, an aryloxy group, an aryloxycarbonyl group, and a carbamoyl group. The carboxyl group and the sulfo group may be in a salt state. As a cation forming a salt with a carboxyl group and a sulfo group, alkali metal ions (eg, sodium ions and potassium ions) are preferable.

In the present specification, the “aromatic group” means an aryl group, a substituted aryl group, an aromatic heterocyclic group, or a substituted aromatic heterocyclic group.
The aryl group preferably has 6 to 45 carbon atoms, more preferably 6 to 35 carbon atoms, still more preferably 6 to 25 carbon atoms, and most preferably 6 to 20 carbon atoms. The aryl part of the substituted aryl group is the same as the aryl group.
The aromatic heterocyclic group preferably has 2 to 45 carbon atoms, more preferably 3 to 35, still more preferably 3 to 25, and most preferably 3 to 20. The aromatic heterocyclic group part of the substituted aromatic heterocyclic group is the same as the aromatic heterocyclic group.
Any aromatic substituent may be used, for example, halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl, nitro, carboxyl, sulfo, alkyl group, acyl group, alkoxy group, alkoxycarbonyl group, alkylthio group. Group, alkylthiocarbonyl group, aryloxy group, aryloxycarbonyl group and carbamoyl group. Carboxyl and sulfo may be in a salt state. The cation that forms a salt with carboxyl and sulfo is preferably an alkali metal ion (eg, sodium ion, potassium ion).

Specific examples of the aliphatic group include octyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl, 4-dodecylcyclohexyl, chlorododecyl, cyanododecyl, octadecenyl, hexadecynyl, 4-octadecylcyclohexenyl, 6-phenylhexyl, 3 -(1-Naphtyl) butyl, 1-dodecyl-4-piperidinyl.
Specific examples of the aromatic group include p-dodecylphenyl (LAB type, BAB type, preferably LAB type), p-hexadecylphenyl, p-octadecylphenyl, o, p-di (t-butyl) phenyl. O-hexadecanoylaminophenyl, 4- (t-butyl) -1-naphthyl, 4- (t-butyl) -2-quinolyl.

Y ¹ , Y ² , Y ⁴ , Y ⁶ and Y ⁹ are preferably an alkyl group, a substituted alkyl group and a substituted aryl group, more preferably an alkyl group and an alkyl-substituted aryl group, and still more preferably an alkyl-substituted group. An aryl group, particularly preferably an alkyl-substituted aryl group. Specifically, what was shown as said aliphatic group or aromatic group is mentioned.
Y ³ , Y ⁵ , Y ⁷ , Y ⁸ , Y ¹⁰ , and Y ¹¹ are preferably a hydrogen atom or an anion.

  Among the (a) to (g), preferably (a) to (e), more preferably (a) to (c), and particularly preferably (a).

  The number of charges of M represents an integer of 1 to 3 required for neutralizing the charge of the molecule, preferably an integer of 1 or 2, and more preferably 1.

  Although the preferable specific example of M is shown below, this invention is not limited to these.

In the present invention, the general formula (A) is preferably a case where Q ₁ is a group necessary for forming a cyanine dye and / or a styryl dye, and more preferably a cyanine dye is used.
The styryl dye is preferably a dye represented by the general formula (1) described in JP-A No. 2002-169248 having a counter ion, and Q ₁ of the general formula (A) in the present invention is represented by the following formula: This is the case.

L ¹ and L ^{2 in the} above formula are each independently substituted or unsubstituted methine, and the substituents of methine may be bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring.
R ³ represents an aliphatic group, an aromatic group, or a heterocyclic group. The definitions of aliphatic and aromatic are as described above. R ³ is preferably an aliphatic group, an aromatic group, or a heterocyclic group. More preferably, an unsubstituted aliphatic group (for example, methyl, ethyl, butyl), a substituted aliphatic group (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 2-carboxyethyl), unsubstituted An aromatic group (for example, phenyl, naphthyl), an unsubstituted heterocyclic group (for example, 2-pyridyl, 2-thiazolyl), and a substituted or unsubstituted aliphatic group is particularly preferable. V ¹ represents a monovalent substituent and may be any monovalent substituent, and examples thereof include the substituent represented by R ¹ in the general formula (A) of the present invention. Preferred is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and more preferred is an unsubstituted alkyl group. n is 1. m is an integer from 0 to 4.
Specifically, in the specific example of the general formula (1) described in the patent publication, a dye having M in the general formula (A) as a counter ion can be preferably used.

  The cyanine dye particularly preferably used in the present invention is preferably a cyanine dye represented by the following formula (I).

In the formula (I), R ¹ is a hydrogen atom, an aliphatic group, an aromatic group, —NR ²¹ R ²⁴ , —OR ²¹ or —SR ²¹ . R ²¹ and R ²⁴ are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²⁴ are combined to form a nitrogen-containing heterocycle. The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle may have a hetero atom other than nitrogen (eg, oxygen atom, sulfur atom). R ²¹ is preferably an aliphatic group or an aromatic group, and more preferably an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group.
R ²⁴ is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an alkyl group, or a substituted alkyl group.

In the present specification, the “aliphatic group” means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group or a substituted aralkyl group.
An alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group or a substituted aralkyl group is preferred, and an alkyl group, a substituted alkyl group, an aralkyl group or a substituted aralkyl group is more preferred. A chain aliphatic group is preferred to a cyclic aliphatic group. The chain aliphatic group may have a branch.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, and most preferably 1 to 12 carbon atoms. The alkyl part of the substituted alkyl group is the same as the alkyl group.
The alkenyl group and alkynyl group preferably have 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms, and most preferably 2 to 12 carbon atoms.
The alkenyl part of the substituted alkenyl group and the alkynyl part of the substituted alkynyl group are the same as the alkenyl group and alkynyl group, respectively.
The number of carbon atoms in the aralkyl group is preferably 7 to 35, more preferably 7 to 25, still more preferably 7 to 20, and most preferably 7 to 15. The aralkyl part of the substituted aralkyl group is the same as the aralkyl group.
Any substituent of the aliphatic group may be used, but preferably a halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl, nitro, carboxyl, sulfo, acyl group, alkoxy group, alkoxycarbonyl group, alkylthio group, Examples thereof include an alkylthiocarbonyl group, an aryloxy group, an aryloxycarbonyl group, and a carbamoyl group. Carboxyl and sulfo may be in a salt state. The cation that forms a salt with carboxyl and sulfo is preferably an alkali metal ion (eg, sodium ion, potassium ion).

In the formula (I), L ¹ is a methine chain composed of an odd number of methines. The number of methines in the methine chain is preferably 3, 5, 7 or 9, more preferably 3, 5 or 7, still more preferably 5 or 7, most preferably 5. preferable.
Methine may have a substituent. Examples of the substituent for methine include a halogen atom, an aliphatic group, an aromatic group, —NR ⁵ R ⁶ , —OR ⁵ and —SR ⁵ . R ⁵ and R ⁶ are each independently a hydrogen atom, an aliphatic group, or an aromatic group. The definition of the aliphatic group and the aromatic group is the same as the definition of R ¹ .
A methine substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. An unsaturated aliphatic ring is preferred to an unsaturated heterocyclic ring. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cycloheptene ring or a cyclohexene ring. It is particularly preferred that the methine chain is unsubstituted or a methine substituent is bonded to form a cycloheptene ring or a cyclohexene ring.

In the formula (I), Z ¹ and Z ² are each an atomic group that independently forms a 5-membered or 6-membered nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrroline ring, an imidazole ring and a pyridine ring. A 5-membered ring is preferred over a 6-membered ring. The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring or naphthalene ring). The nitrogen-containing heterocycle and its condensed ring may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl, nitro, carboxyl, sulfo, and an alkyl group. Carboxyl and sulfo may be in a salt state. The cation that forms a salt with carboxyl and sulfo is preferably an alkali metal ion (eg, sodium ion, potassium ion).

  The cyanine dye represented by the formula (I) is used after forming a salt with an anion. M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

  In the formula (I), a more preferred cyanine dye is represented by the following formula (Ia).

In the formula (Ia), R ¹¹ is a hydrogen atom, an aliphatic group, an aromatic group, —NR ³¹ R ³⁴ , —OR ³¹ or —SR ³¹ . R ³¹ and R ³⁴ are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ³¹ and R ³⁴ combine to form a nitrogen-containing heterocycle.
R ³¹ is preferably an aliphatic group or an aromatic group, and more preferably an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group. R ³⁴ is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an alkyl group, or a substituted alkyl group.
In the formula (Ia), R ¹² is a hydrogen atom, an aliphatic group or an aromatic group. R ¹² is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, Most preferably.

In the formula (Ia), R ¹³ is an aliphatic group. R ¹³ is preferably a substituted alkyl group. From the viewpoint of easy synthesis, R ¹³ is particularly preferably a substituted alkyl group having the same definition as —CHR ¹² — and —CO—R ¹¹ .

In the formula (Ia), L ¹¹ is a methine chain composed of an odd number of methines. The number of methines in the methine chain is preferably 3, 5, 7 or 9, more preferably 3, 5 or 7, still more preferably 5 or 7, most preferably 5. preferable. Methine may have a substituent. Examples of the substituent of methine include a halogen atom, an aliphatic group, an aromatic group, —NR ¹⁵ R ¹⁶ , —OR ¹⁵ and —SR ¹⁵ . R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic group or an aromatic group. The definition of the aliphatic group and the aromatic group is as described above. A methine substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. An unsaturated aliphatic ring is preferred to an unsaturated heterocyclic ring. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cycloheptene ring or a cyclohexene ring. It is particularly preferred that the methine chain is unsubstituted or a methine substituent is bonded to form a cycloheptene ring or a cyclohexene ring.

In formula (Ia), Y ¹¹ and Y ¹² are each independently —CR ¹⁴ R ¹⁵ —, —NR ¹⁴ —, —O—, —S— or —Se—.
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an aliphatic group, or R ¹⁴ and R ¹⁵ are bonded to form an aliphatic ring. The aliphatic group is particularly preferably an alkyl group or a substituted alkyl group. The aliphatic ring is preferably a saturated aliphatic ring, more preferably a 5-membered ring (cyclopentane ring), a 6-membered ring (cyclohexane ring), or a 7-membered ring (cycloheptane ring), and a cyclohexane ring. Most preferred.

In the formula (Ia), the benzene rings Z ¹¹ and Z ¹² may be condensed with other benzene rings. The benzene rings Z ¹¹ and Z ¹² and their condensed rings may have a substituent. Examples of the substituent include a halogen atom, hydroxyl, nitro, carboxyl, sulfo and alkyl groups. Carboxyl and sulfo may be in a salt state. The cation forming a salt with carboxyl and sulfo is preferably an alkali metal ion.

The cyanine dye represented by the formula (Ia) is used after forming a salt with an anion.
M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

  In formula (Ia), a particularly preferred cyanine dye is represented by the following formula (Ib).

In the formula (Ib), two R ^{41 s} are the same group and are a hydrogen atom, an aliphatic group, an aromatic group, —NR ⁵¹ R ⁵² , —OR ⁵¹ or —SR ⁵¹ , and R ⁴¹ is — It is preferably NR ⁵¹ R ⁵² , —OR ⁵¹ or —S ⁵¹ .
R ⁵¹ and R ⁵² are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ⁵¹ and R ⁵² are combined to form a nitrogen-containing heterocycle.
R ⁵¹ is preferably an aliphatic group or an aromatic group, and more preferably an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group. R ⁵² is preferably a hydrogen atom or an aliphatic group, and more preferably a hydrogen atom, an alkyl group, or a substituted alkyl group.
The nitrogen-containing heterocyclic ring formed by combining R ⁵¹ and R ⁵² is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle may have a hetero atom other than nitrogen (eg, oxygen atom, sulfur atom).
The cyanine dye represented by the formula (Ib) is used after forming a salt with an anion.
M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

In the present invention, R ¹ in the formula (I) is preferably —NR ²¹ R ²⁴ , —OR ²¹ or —SR ²¹ .
When R ¹ in formula (I) is a hydrogen atom, an aliphatic group or an aromatic group, the decoloring reaction due to the action of the base under heating conditions proceeds rapidly, but the cyanine dye is somewhat unstable. However, there is a problem that the decoloring reaction proceeds slightly during storage of the dye.
When R ¹ in formula (I) is —R ²¹ R ²⁴ , —OR ²⁴ or —SR ²⁴ , the stability of the cyanine dye is improved. Such a cyanine dye is represented by the following formula (II).

In the formula (II), X ²¹ is —NR ²⁴ —, —O— or —S—.
R ²¹ and R ²⁴ are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ²¹ and R ²⁴ are combined to form a nitrogen-containing heterocycle. The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocyclic ring may have a hetero atom other than nitrogen (eg, oxygen atom, sulfur atom). R ²¹ and R ²⁴ have the same definition as in formula (I), and the preferred range is also the same.

In the formula (II), R ²² is a hydrogen atom, an aliphatic group or an aromatic group.
R ²² is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, Most preferably.

In the formula (II), R ²³ is an aliphatic group. R ²³ is preferably a substituted alkyl group. From the viewpoint of easy synthesis, R ²³ is particularly preferably a substituted alkyl group having the same definition as —CHR ²² and —CO—X ²¹ —R ²¹ .

In the formula (II), L ²¹ is a methine chain composed of an odd number of methines. The number of methines in the methine chain is preferably 3, 5, 7 or 9, more preferably 3, 5 or 7, still more preferably 5 or 7, most preferably 5. preferable. Methine may have a substituent. Examples of the substituent of methine include a halogen atom, an aliphatic group, an aromatic group, —NR ²⁵ R ²⁶ , —OR ²⁵ and —SR ²⁵ .
R ²⁵ and R ²⁶ are each independently a hydrogen atom, an aliphatic group or an aromatic group. The definition of the aliphatic group and the aromatic group is as described above.
A methine substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. An unsaturated aliphatic ring is preferred to an unsaturated heterocyclic ring. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cycloheptene ring or a cyclohexene ring.
It is particularly preferred that the methine chain is unsubstituted or a methine substituent is bonded to form a cycloheptene ring or a cyclohexene ring.

In the formula (II), Z ²¹ and Z ²² each independently represent an atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle include an oxazole ring, a thiazole ring, a selenazole ring, a pyrroline ring, an imidazole ring and a pyridine ring. A 5-membered ring is preferred over a 6-membered ring. An aromatic ring may be condensed with the nitrogen-containing heterocycle. The nitrogen-containing heterocycle and its condensed ring may have a substituent. Examples of the substituent include a halogen atom, hydroxyl, nitro, carboxyl, sulfo and alkyl groups. Carboxyl and sulfo may be in a salt state. The cation forming a salt with carboxyl and sulfo is preferably an alkali metal ion.
The cyanine dye represented by the formula (II) is used after forming a salt with an anion.
M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

R ¹¹ in the formula (Ia) is preferably —NR ³¹ R ³⁴ , —OR ³¹ or —SR ³¹ . Such a cyanine dye is represented by the following formula (IIa).

In the formula (IIa), X ³¹ is —NR ³⁴ —, —O— or —S—. R ³¹ and R ³⁴ are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ³¹ and R ³⁴ combine to form a nitrogen-containing heterocycle.
R ³¹ is preferably an aliphatic group or an aromatic group, and more preferably an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group.
R ³⁴ is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an alkyl group, or a substituted alkyl group.
The nitrogen-containing heterocyclic ring formed by combining R ³¹ and R ³⁴ is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle may have a heteroatom other than nitrogen.

In the formula (IIa), R ³² is a hydrogen atom, an aliphatic group or an aromatic group. R ³² is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, Most preferably.

In the formula (IIa), R ³³ is an aliphatic group. R ³³ is preferably a substituted alkyl group. From the viewpoint of easy synthesis, R ³³ is particularly preferably a substituted alkyl group having the same definition as —CHR ³² —CO—X ³¹ —R ³¹ .

In the formula (IIa), L ³¹ is a methine chain composed of an odd number of methines. The number of methines in the methine chain is preferably 3, 5, 7 or 9, more preferably 3, 5 or 7, still more preferably 5 or 7, most preferably 5. preferable. Methine may have a substituent. Examples of the substituent of methine include a halogen atom, an aliphatic group, an aromatic group, —NR ³⁵ R ³⁶ , —OR ³⁵ and —SR ³⁵ . R ³⁵ and R ³⁶ are each independently a hydrogen atom, an aliphatic group or an aromatic group. The definition of the aliphatic group and the aromatic group is as described above.
A methine substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. An unsaturated aliphatic ring is preferred to an unsaturated heterocyclic ring. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cycloheptene ring or a cyclohexene ring. It is particularly preferred that the methine chain is unsubstituted or a methine substituent is bonded to form a cycloheptene ring or a cyclohexene ring.

In formula (IIa), Y ³¹ and Y ³² are each independently —CR ³⁷ R ³⁸ —, —NR ³⁷ —, —O—, —S— or —Se—. R ³⁷ and R ³⁸ are each independently a hydrogen atom or an aliphatic group, or R ³⁷ and R ³⁸ combine to form a nitrogen-containing heterocycle. The aliphatic group is particularly preferably an alkyl group or a substituted alkyl group.

In the formula (IIa), the benzene rings Z ³¹ and Z ³² may be condensed with other benzene rings. The benzene rings Z ³¹ and Z ³² and their condensed rings may have a substituent. Examples of the substituent include a halogen atom, hydroxyl, nitro, carboxyl, sulfo and alkyl groups. Carboxyl and sulfo may be in a salt state. The cation forming a salt with carboxyl and sulfo is preferably an alkali metal ion.
The cyanine dye represented by the formula (IIa) is used after forming a salt with an anion. M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

In the present invention, R ⁴¹ in the above-described formula (Ib) is preferably —NR ⁵¹ R ⁵² , —OR ⁵² or —SR ⁵¹ . Such a cyanine dye is represented by the following formula (IIb).

In the formula (IIb), X ⁵¹ is —NR ⁵² —, —O— or —S—. R ⁵¹ and R ⁵² are each independently a hydrogen atom, an aliphatic group or an aromatic group, or R ⁵¹ and R ⁵² are combined to form a nitrogen-containing heterocycle.
R ⁵¹ is preferably an aliphatic group or an aromatic group, and more preferably an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group.
R ⁵² is preferably a hydrogen atom or an aliphatic group, and more preferably a hydrogen atom, an alkyl group, or a substituted alkyl group.
The nitrogen-containing heterocyclic ring formed by combining R ⁵¹ and R ⁵² is preferably a 5-membered ring or a 6-membered ring.
The nitrogen-containing heterocycle may have a heteroatom other than nitrogen.
The cyanine dye represented by the formula (IIb) is used after forming a salt with an anion. M is synonymous with what is represented by the above-mentioned general formula (A), and the same thing is preferable.

Specific examples of the cyanine dye represented by the formula (Ib) are shown below.
In the following specific examples, only the anion M and R ^{41 of the} formula (Ib) are shown. The counter anion is represented by the symbol shown in the preferred specific example of M.

  Hereinafter, the synthesis of the compound of the cyanine dye represented by the formula (Ib) will be described in detail, but the invention is not limited thereto.

(Synthesis of exemplary compounds)
-Synthesis Example of Exemplified Compound 33-
Example compound 33 of JP-A-11-231457 33 g
Sodium dodecylbenzenesulfonate 35.5 g
200 g ethyl acetate
100 g of water

After mixing at the above weight ratio, the mixture was kept at 55 ° C. and stirred for 1 hour 30 minutes. Thereafter, the mixture was cooled with stirring and kept at 10 ° C. to 15 ° C. for crystal precipitation. Suction filtered and the crystals washed with 1 kg water. The obtained crystals were taken out in a petri dish and dried at 60 ° C. The weight of the crystals after drying was 116.3 g (yield 93 mass% vs. theoretical yield).
As a result of analyzing the obtained crystal by ¹ H-NMR, the ratio of the cation structure portion to the anion structure portion was 1: 1.

-Synthesis Example of Exemplified Compound 43-
In the synthesis of Exemplified Compound 33, Exemplified Compound 33 of JP-A-11-231457 was changed to Exemplified Compound 43 in equimolar amount, and sodium dodecylbenzenesulfonate was changed to equimolar M-3 sodium salt of the anion exemplified in the present application. The compound was synthesized in the same manner as in the synthesis of Exemplified Compound 33 except that.
As a result of ¹ H-NMR analysis of the obtained crystal, the ratio of the cation to the anion structure portion was 1: 0.98.

Furthermore, the compound represented by the general formula (1) in the present invention is formed using the following general formula (2) and the following general formula (3).
General formula (2) DA
General formula (3) BM
In general formula (2), D represents the cation part of the said general formula (1), and A represents the anion part which does not contain M of general formula (1). In the general formula (3), B represents a cation moiety not containing D in the general formula (1), and M represents an anion moiety in the general formula (1).
The anion represented by A is not particularly limited as long as it is an anion other than M, but is preferably monovalent or divalent, and more preferably monovalent. Examples of anions include halogen ions (Cl, Br, I), p-toluene sulfonate ions, ethyl sulfate ions, 1,5-disulfonaphthalene dianions, PF ₆ , BF ₄ , and ClO ₄ .
The cation represented by B is not particularly limited as long as it is a cation other than D, but is preferably monovalent. Examples of the cation include alkali metal ions (Li, Na, K), ammonium ions, tetramethylammonium ions, tetraethylammonium ions, and the like.

(Description of organic silver salt)
1) Composition The organic silver salt that can be used in the present invention is relatively stable to light, but is heated to 80 ° C. or higher in the presence of exposed photosensitive silver halide and a reducing agent. In this case, the silver salt functions as a silver ion supplier to form a silver image. The organic silver salt may be any organic substance that can supply silver ions that can be reduced by a reducing agent. As for such non-photosensitive organic silver salt, paragraph numbers 0048 to 0049 of JP-A-10-62899, page 18 line 24 to page 19 line 37 of European Patent Publication No. 0803764A1, European Patent Publication. No. 0968212A1, JP-A-11-349591, JP-A-2000-7683, JP-A-2000-72711, and the like. Silver salts of organic acids, particularly silver salts of long-chain aliphatic carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Preferable examples of the fatty acid silver salt include silver lignocerate, silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver erucate and the like. Including a mixture of In the present invention, among these fatty acid silvers, the silver behenate content is preferably 50 mol% to 100 mol%, more preferably 85 mol% to 100 mol%, still more preferably 95 mol% to 100 mol%. The following fatty acid silver is preferably used. Furthermore, it is preferable to use fatty acid silver having a silver erucate content of 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0.1 mol% or less.

  Moreover, it is preferable that silver stearate content rate is 1 mol% or less. By making the stearic acid content 1 mol% or less, a silver salt of an organic acid having a low Dmin, high sensitivity and excellent image storage stability can be obtained. As said stearic acid content rate, 0.5 mol% or less is preferable and it is especially preferable not to contain substantially.

  Furthermore, when silver arachidate is included as the silver salt of the organic acid, the silver arachidate content is 6 mol% or less to obtain a low Dmin and an organic acid silver salt excellent in image storability. It is preferable at a point and it is still more preferable that it is 3 mol% or less.

2) Shape The shape of the organic silver salt that can be used in the present invention is not particularly limited, and may be any of a needle shape, a rod shape, a flat plate shape, and a flake shape.
In the present invention, scaly organic silver salts are preferred. In addition, short needle-like, rectangular parallelepiped, cubic or potato-like amorphous particles having a major axis / uniaxial length ratio of less than 5 are also preferably used. These organic silver particles have a feature that there is less fog at the time of thermal development than long needle-like particles having a ratio of the major axis to the uniaxial length of 5 or more. In particular, particles having a major axis / uniaxial ratio of 3 or less are preferable because the mechanical stability of the coating film is improved. In the present specification, the scaly organic silver salt is defined as follows. The organic acid silver salt was observed with an electron microscope, the shape of the organic acid silver salt particle was approximated to a rectangular parallelepiped, and the sides of the rectangular parallelepiped were designated as a, b, and c from the shortest side (c was the same as b). Then, the shorter numerical values a and b are calculated, and x is obtained as follows.
x = b / a

  In this way, x is obtained for about 200 particles, and when the average value x (average) is obtained, particles satisfying the relationship of x (average) ≧ 1.5 are defined as flakes. Preferably, 30 ≧ x (average) ≧ 1.5, more preferably 15 ≧ x (average) ≧ 1.5. Incidentally, the needle shape is 1 ≦ x (average) <1.5.

  In the flake shaped particle, a can be regarded as a thickness of a tabular particle having a main plane with b and c as sides. The average of a is preferably 0.01 μm or more and 0.3 μm or less, and more preferably 0.1 μm or more and 0.23 μm or less. The average c / b is preferably 1 or more and 9 or less, more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less, and most preferably 1 or more and 3 or less.

By setting the equivalent sphere diameter to 0.05 μm or more and 1 μm or less, aggregation is hardly caused in the photosensitive material, and image storability is improved. The sphere equivalent diameter is preferably 0.1 μm or more and 1 μm or less. In the present invention, the method for measuring the equivalent sphere diameter is obtained by directly photographing a sample using an electron microscope and then image-processing the negative.
In the flake shaped particles, the spherical equivalent diameter / a of the particles is defined as the aspect ratio. The aspect ratio of the flake shaped particles is preferably 1.1 or more and 30 or less, more preferably 1.1 or more and 15 or less, from the viewpoint of preventing aggregation in the photosensitive material and improving the image storage stability. .

  The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is preferably 100% or less, more preferably 80% or less, and even more preferably 50% of the value obtained by dividing the standard deviation of the lengths of the short and long axes by the short and long axes. It is as follows. The method for measuring the shape of the organic silver salt can be determined from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring monodispersity, there is a method for obtaining the standard deviation of the volume weighted average diameter of the organic silver salt, and the percentage (variation coefficient) of the value divided by the volume weighted average diameter is preferably 100% or less, more Preferably it is 80% or less, More preferably, it is 50% or less. As a measuring method, for example, it is obtained from the particle size (volume weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with laser light and obtaining an autocorrelation function with respect to the temporal change of the fluctuation of the scattered light. Can do.

3) Preparation Known methods and the like can be applied to the production and dispersion method of organic acid silver used in the present invention. For example, the above-mentioned JP-A-10-62899, European Patent Publication No. 0803763A1, European Patent Publication No. 0968212A1, JP-A-11-349591, JP-A-2000-7683, JP-A-2000-72711, JP-A-2001-163889, 2001-163890, 2001-163825, 2001-33907, 2001-188313, 2001-83651, 2002-6442, 2002-49117, 2002-31870, 2002-107868 You can refer to the issue.

  In addition, when the photosensitive silver salt is allowed to coexist at the time of dispersion of the organic silver salt, the fog is increased and the sensitivity is remarkably reduced. Therefore, it is more preferable that the photosensitive silver salt is not substantially contained at the time of dispersion. In the present invention, the amount of the photosensitive silver salt in the aqueous dispersion to be dispersed is preferably 1 mol% or less, more preferably 0.1 mol% or less with respect to 1 mol of the organic acid silver salt in the liquid. Further, it is more preferable that no positive photosensitive silver salt is added.

  In the present invention, it is possible to produce a photosensitive material by mixing an organic silver salt aqueous dispersion and a photosensitive silver salt aqueous dispersion, but the mixing ratio of the organic silver salt and the photosensitive silver salt can be selected according to the purpose, The ratio of the photosensitive silver salt to the organic silver salt is preferably in the range of 1 mol% to 30 mol%, more preferably 2 mol% to 20 mol%, particularly preferably 3 mol% to 15 mol%. Mixing two or more organic silver salt water dispersions and two or more photosensitive silver salt water dispersions when mixing is a method preferably used for adjusting photographic properties.

4) Addition amount Although the organic silver salt in the present invention can be used in a desired amount, the total amount of coated silver including silver halide is preferably 0.1 g / m ² or more and 5.0 g / m ² or less, more preferably. It is 0.3 g / m ² or more and 3.0 g / m ² or less, more preferably 0.5 g / m ² or more and 2.0 g / m ² or less. In particular, in order to improve image storability, the total coated silver amount is preferably 1.8 g / m ² or less, more preferably 1.6 g / m ² or less. If the preferred reducing agent in the present invention is used, a sufficient image density can be obtained even with such a low silver amount.

(Description of reducing agent)
The photothermographic material of the present invention contains a heat developer that is a reducing agent for the organic silver salt.
The reducing agent may be any substance (preferably an organic substance) that reduces silver ions to metallic silver. Examples of such reducing agents are described in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 0803764A1, page 7, line 34 to page 18, line 12.
In the present invention, the reducing agent is preferably a so-called hindered phenol-based reducing agent or bisphenol-based reducing agent having a substituent at the ortho position of the phenolic hydroxyl group, and more preferably a compound represented by the following general formula (R).
General formula (R)

(In the general formula (R), R ¹¹ and R ¹¹ ′ each independently represents an alkyl group having 1 to 20 carbon atoms. R ¹² and R ¹² ′ can each independently be substituted with a hydrogen atom or a benzene ring. represents a substituent .L is, -S- group or a -CHR ¹³ - .X ¹ and X ¹ .R ¹³ represents a group represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms' each independently represent a hydrogen atom Or represents a substitutable group on the benzene ring.)

The general formula (R) will be described in detail.
In the following, when referred to as an alkyl group, a cycloalkyl group is also included in this unless otherwise specified.
1) R ¹¹ and R ¹¹ '
R ¹¹ and R ¹¹ ′ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The substituent of the alkyl group is not particularly limited, but preferably an aryl group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamido group, a sulfonyl group, a phosphoryl group, Examples thereof include an acyl group, a carbamoyl group, an ester group, a ureido group, a urethane group, and a halogen atom.

2) R ¹² and R ¹² ', X ¹ and X ¹ '
R ¹² and R ¹² ′ each independently represent a hydrogen atom or a substituent capable of substituting for a benzene ring, and X ¹ and X ¹ ′ each independently represent a hydrogen atom or a group capable of substituting for a benzene ring. Preferred examples of each group that can be substituted on the benzene ring include an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acylamino group.

3) L
L represents an —S— group or a —CHR ¹³ — group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may have a substituent. Specific examples of the unsubstituted alkyl group for R ¹³ are methyl group, ethyl group, propyl group, butyl group, heptyl group, undecyl group, isopropyl group, 1-ethylpentyl group, 2,4,4-trimethylpentyl group, cyclohexyl group. Group, 2,4-dimethyl-3-cyclohexenyl group, 2,4-dimethyl-3-cyclohexenyl group and the like. Examples of the substituent of the alkyl group are the same as the substituent of R ¹¹ , and are a halogen atom, alkoxy group, alkylthio group, aryloxy group, arylthio group, acylamino group, sulfonamido group, sulfonyl group, phosphoryl group, oxycarbonyl group, Examples thereof include a carbamoyl group and a sulfamoyl group.

4) Preferred substituents R ¹¹ and R ¹¹ ′ are preferably primary, secondary or tertiary alkyl groups having 1 to 15 carbon atoms, specifically methyl, isopropyl, t-butyl, t -Amyl group, t-octyl group, cyclohexyl group, cyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclopropyl group and the like can be mentioned. R ¹¹ and R ¹¹ ′ are more preferably an alkyl group having 1 to 4 carbon atoms, and among them, a methyl group, a t-butyl group, a t-amyl group, and a 1-methylcyclohexyl group are more preferable, and a methyl group and a t-butyl group are preferable. Groups are most preferred.

R ¹² and R ¹² ′ are preferably an alkyl group having 1 to 20 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a t-butyl group, a t-amyl group, and a cyclohexyl group. Group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group, methoxyethyl group and the like. More preferred are methyl group, ethyl group, propyl group, isopropyl group and t-butyl group, and particularly preferred are methyl group and ethyl group.
X ¹ and X ¹ ′ are preferably a hydrogen atom, a halogen atom, or an alkyl group, and more preferably a hydrogen atom.

L is preferably a —CHR ¹³ — group.
R ¹³ is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. As the alkyl group, a cyclic alkyl group is also preferably used in addition to a chain alkyl group. Moreover, what has a C = C bond in these alkyl groups can also be used preferably. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, 2,4,4-trimethylpentyl group, cyclohexyl group, 2,4-dimethyl-3-cyclohexenyl group, 3,5-dimethyl-3- A cyclohexenyl group and the like are preferable. R ¹³ is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a 2,4-dimethyl-3-cyclohexenyl group.

When R ¹¹ and R ¹¹ ′ are tertiary alkyl groups and R ¹² and R ¹² ′ are methyl groups, R ¹³ is a primary or secondary alkyl group having 1 to 8 carbon atoms (methyl group, ethyl group, propyl group). Group, isopropyl group, 2,4-dimethyl-3-cyclohexenyl group and the like).
When R ¹¹ and R ¹¹ ′ are tertiary alkyl groups and R ¹² and R ¹² ′ are alkyl groups other than methyl groups, R ¹³ is preferably a hydrogen atom.
When R ¹¹ and R ¹¹ ′ are not a tertiary alkyl group, R ¹³ is preferably a hydrogen atom or a secondary alkyl group, and particularly preferably a secondary alkyl group. Preferred groups as the secondary alkyl group for R ¹³ are isopropyl group and 2,4-dimethyl-3-cyclohexenyl group.
The reducing agent has different heat developability and developed silver tone depending on the combination of R ¹¹ , R ¹¹ ′, R ¹² , R ¹² ′ and R ¹³ . Since these can be prepared by combining two or more reducing agents, it is preferable to use a combination of two or more depending on the purpose.

  Although the specific example of the reducing agent in this invention including the compound represented by general formula (R) below is shown, this invention is not limited to these.

Examples of preferable reducing agents in the present invention other than those described above are compounds described in JP-A Nos. 2001-188314, 2001-209145, 2001-350235, 2002-156727, and EP1278101A2.
In the present invention, the addition amount of the reducing agent is preferably 0.1 g / m ² or more and 3.0 g / m ² or less, more preferably 0.2 g / m ² or more and 2.0 g / m ² or less, and still more preferably. Is 0.3 g / m ² or more and 1.0 g / m ² or less. 5 mol% or more and 50 mol% or less is preferably contained with respect to 1 mol of silver on the surface having the image forming layer, more preferably 8 mol% or more and 30 mol% or less, and 10 mol% or more and 20 mol% or less. More preferably, it is contained. The reducing agent is preferably contained in the image forming layer.

The reducing agent may be contained in the coating solution by any method such as a solution form, an emulsified dispersion form, or a solid fine particle dispersion form, and may be contained in the photosensitive material.
Well-known emulsification and dispersion methods include oils such as dibutyl phthalate, tricresyl phosphate, dioctyl sebacate or tri (2-ethylhexyl) phosphate, and an auxiliary solvent such as ethyl acetate and cyclohexanone, and dodecylbenzene. Examples include a method of mechanically preparing an emulsified dispersion by adding a surfactant such as sodium sulfonate, sodium N-oleyl-N-methyltaurate, sodium di (2-ethylhexyl) sulfosuccinate. At this time, it is also preferable to add a polymer such as α-methylstyrene oligomer or poly (t-butylacrylamide) for the purpose of adjusting the viscosity and refractive index of the oil droplets.

In addition, as a solid fine particle dispersion method, a reducing agent powder is dispersed in an appropriate solvent such as water by a ball mill, a colloid mill, a vibration ball mill, a sand mill, a jet mill, a roller mill, or an ultrasonic wave to produce a solid dispersion. A method is mentioned. In this case, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, an anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three isopropyl groups having different substitution positions)) may be used. Good. In the mills, beads such as zirconia are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1 ppm to 1000 ppm. If the Zr content in the light-sensitive material is 0.5 mg or less per 1 g of silver, there is no practical problem.
The aqueous dispersion preferably contains a preservative (for example, benzoisothiazolinone sodium salt).
Particularly preferred is a solid particle dispersion method of a reducing agent, in which fine particles having an average particle size of 0.01 μm to 10 μm, preferably 0.05 μm to 5 μm, more preferably 0.1 μm to 2 μm are added. Is preferred. In the present application, it is preferable to use other solid dispersions dispersed in a particle size within this range.

(Description of development accelerator)
In the photothermographic material of the present invention, a sulfonamide phenol compound represented by the general formula (A) described in JP-A-2000-267222, JP-A-2000-330234, or the like as a development accelerator, Hindered phenol compounds represented by general formula (II) described in JP-A-2001-92075, general formula (I) described in JP-A-10-62895, JP-A-11-15116, and the like, A hydrazine-based compound represented by the general formula (D) of JP-A No. 2002-156727 or the general formula (1) described in JP-A No. 2002-278017, and described in the specification of JP-A No. 2001-264929 Phenol-based or naphthol-based compounds represented by the general formula (2) are preferably used. Moreover, the phenol type compound described in Unexamined-Japanese-Patent No. 2002-311533 and Unexamined-Japanese-Patent No. 2002-341484 is also preferable. In particular, naphthol compounds described in JP-A No. 2003-66558 are preferable. These development accelerators are used in the range of 0.1 mol% or more and 20 mol% or less, preferably 0.5 mol% or more and 10 mol% or less, more preferably 1 mol% or more with respect to the reducing agent. The range is 5 mol% or less. The introduction method to the light-sensitive material includes the same method as the reducing agent, but it is particularly preferable to add as a solid dispersion or an emulsified dispersion. When added as an emulsified dispersion, it is added as an emulsified dispersion dispersed using a high-boiling solvent that is solid at room temperature and a low-boiling auxiliary solvent, or as a so-called oilless emulsified dispersion that does not use a high-boiling solvent. It is preferable to add.
In the present invention, among the above development accelerators, hydrazine compounds described in JP-A Nos. 2002-156727 and 2002-278017 and naphthol compounds described in JP-A No. 2003-66558 are used. Is more preferable.

Particularly preferred development accelerators in the invention are compounds represented by the following general formulas (A-1) and (A-2).
Formula (A-1)
Q ₁ -NHNH-Q ₂
(Wherein Q ₁ represents an aromatic group or a heterocyclic group bonded to —NHNH—Q ₂ at a carbon atom, and Q ₂ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, Or represents a sulfamoyl group.)

In the general formula (A-1), the aromatic group or heterocyclic group represented by Q ₁ is preferably a 5- to 7-membered unsaturated ring. Preferred examples include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, pyrrole ring, imidazole ring, pyrazole ring, 1,2 , 3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4 -Oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, thiophene ring, etc. are preferable, and these Also preferred are fused rings in which the rings are fused together.

  These rings may have a substituent, and when they have two or more substituents, these substituents may be the same or different. Examples of substituents include halogen atoms, alkyl groups, aryl groups, carbonamido groups, alkylsulfonamido groups, arylsulfonamido groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, carbamoyl groups, sulfamoyl groups, cyano Groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyl groups. When these substituents are substitutable groups, they may further have substituents. Examples of preferred substituents include halogen atoms, alkyl groups, aryl groups, carbonamido groups, alkylsulfonamido groups, aryls. Sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, and acyloxy group Can be mentioned.

The carbamoyl group represented by Q ₂ is preferably a carbamoyl group having 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. For example, unsubstituted carbamoyl, methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl N-sec-butylcarbamoyl, N-octylcarbamoyl, N-cyclohexylcarbamoyl, N-tert-butylcarbamoyl, N-dodecylcarbamoyl, N- (3-dodecyloxypropyl) carbamoyl, N-octadecylcarbamoyl, N- {3 -(2,4-tert-pentylphenoxy) propyl} carbamoyl, N- (2-hexyldecyl) carbamoyl, N-phenylcarbamoyl, N- (4-dodecyloxyphenyl) carbamoyl, N- (2-chloro-5 Dodecyloxycarbo Butylphenyl) carbamoyl, N- naphthylcarbamoyl, N-3- pyridylcarbamoyl include N- benzylcarbamoyl.

The acyl group represented by Q ₂ is preferably an acyl group having 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, such as formyl, acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, octanoyl, 2 -Hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl, 2-hydroxymethylbenzoyl. The alkoxycarbonyl group represented by Q2 is preferably an alkoxycarbonyl group having 2 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl, dodecyl. Examples include oxycarbonyl and benzyloxycarbonyl.

The aryloxycarbonyl group represented by Q ₂ is preferably an aryloxycarbonyl group having 7 to 50 carbon atoms, more preferably 7 to 40 carbon atoms, such as phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxy Examples thereof include methylphenoxycarbonyl and 4-dodecyloxyphenoxycarbonyl. The sulfonyl group represented by Q2 is preferably a sulfonyl group having 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, such as methylsulfonyl, butylsulfonyl, octylsulfonyl, 2-hexadecylsulfonyl, 3-dodecyl. Examples include oxypropylsulfonyl, 2-octyloxy-5-tert-octylphenylsulfonyl, and 4-dodecyloxyphenylsulfonyl.

The sulfamoyl group represented by Q ₂ is preferably a sulfamoyl group having 0 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, such as an unsubstituted sulfamoyl group, an N-ethylsulfamoyl group, N- (2- Ethylhexyl) sulfamoyl, N-decylsulfamoyl, N-hexadecylsulfamoyl, N- {3- (2-ethylhexyloxy) propyl} sulfamoyl, N- (2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl, N- (2-tetradecyloxyphenyl) sulfamoyl is mentioned. The group represented by Q ₂ may further have the group exemplified as the substituent of the 5- to 7-membered unsaturated ring represented by Q ₁ at a substitutable position. When it has two or more substituents, these substituents may be the same or different.

Next, a preferable range of the compound represented by formula (A-1) is described. Q ₁ is preferably a 5- to 6-membered unsaturated ring, such as a benzene ring, pyrimidine ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring. 1,2,4-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, and these rings Is more preferably a ring fused with a benzene ring or an unsaturated heterocycle. Q ₂ is preferably a carbamoyl group, particularly preferably a carbamoyl group having a hydrogen atom on a nitrogen atom.

  Formula (A-2)

In the general formula (A-2), R ₁ represents an alkyl group, an acyl group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, or a carbamoyl group. R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, or a carbonate group. R ₃ and R ₄ each represents a group that can be substituted on the benzene ring mentioned in the example of the substituent of formula (A-1). R ₃ and R ₄ may be connected to each other to form a condensed ring.
R ₁ is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, isopropyl group, butyl group, tert-octyl group, cyclohexyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, methyl group). Ureido group, 4-cyanophenylureido group, etc.), carbamoyl group (n-butylcarbamoyl group, N, N-diethylcarbamoyl group, phenylcarbamoyl group, 2-chlorophenylcarbamoyl group, 2,4-dichlorophenylcarbamoyl group, etc.) acylamino Groups (including ureido groups and urethane groups) are more preferred. R2 is preferably a halogen atom (more preferably a chlorine atom or a bromine atom), an alkoxy group (for example, methoxy group, butoxy group, n-hexyloxy group, n-decyloxy group, cyclohexyloxy group, benzyloxy group, etc.), aryloxy A group (phenoxy group, naphthoxy group, etc.).
R ₃ is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, and most preferably a halogen atom. R ₄ is preferably a hydrogen atom, an alkyl group or an acylamino group, more preferably an alkyl group or an acylamino group. Examples of these preferable substituents are the same as those for R ₁ . When R ₄ is an acylamino group, R ₄ is preferably linked to R ₃ to form a carbostyryl ring.

In the general formula (A-2), when R ₃ and R ₄ are connected to each other to form a condensed ring, a naphthalene ring is particularly preferable as the condensed ring. The same substituent as the example of a substituent quoted by general formula (A-1) may couple | bond with the naphthalene ring. When general formula (A-2) is a naphthol-based compound, R ₁ is preferably a carbamoyl group. Of these, a benzoyl group is particularly preferable. R ₂ is preferably an alkoxy group or an aryloxy group, and particularly preferably an alkoxy group.

  Hereinafter, preferred specific examples of the development accelerator in the invention will be given. The present invention is not limited to these.

(Description of hydrogen bonding compound)
When the reducing agent in the present invention has an aromatic hydroxyl group (—OH) or amino group (—NHR, R is a hydrogen atom or an alkyl group), particularly in the case of the bisphenols described above, these groups and hydrogen bonds It is preferable to use together a non-reducing compound having a group capable of forming.
Examples of the group that forms a hydrogen bond with a hydroxyl group or an amino group include a phosphoryl group, a sulfoxide group, a sulfonyl group, a carbonyl group, an amide group, an ester group, a urethane group, a ureido group, a tertiary amino group, and a nitrogen-containing aromatic group. Can be mentioned. Among them, preferred are a phosphoryl group, a sulfoxide group, an amide group (however, it has no> N—H group and is blocked like> N—Ra (Ra is a substituent other than H)), a urethane group. (However, it has no> N—H group and is blocked like> N—Ra (Ra is a substituent other than H)), a ureido group (however, it has no> N—H group,> N-Ra (Ra is a substituent other than H).)
In the present invention, a particularly preferred hydrogen bonding compound is a compound represented by the following general formula (D).
Formula (D)

In the general formula (D), R ²¹ to R ²³ each independently represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these groups may be substituted even if they are unsubstituted. You may have.
When R ²¹ to R ²³ have a substituent, examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an alkylthio group, an arylthio group, a sulfonamide group, an acyloxy group, Examples thereof include an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, and a phosphoryl group. Preferred examples of the substituent include an alkyl group or an aryl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a t-octyl group. Group, phenyl group, 4-alkoxyphenyl group, 4-acyloxyphenyl group and the like.
Specific examples of the alkyl group represented by R ²¹ to R ²³ include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, an isopropyl group, a t-butyl group, a t-amyl group, a t-octyl group, a cyclohexyl group, Examples include 1-methylcyclohexyl group, benzyl group, phenethyl group, 2-phenoxypropyl group and the like.
Examples of the aryl group include phenyl group, cresyl group, xylyl group, naphthyl group, 4-t-butylphenyl group, 4-t-octylphenyl group, 4-anisidyl group, and 3,5-dichlorophenyl group.
Alkoxy groups include methoxy, ethoxy, butoxy, octyloxy, 2-ethylhexyloxy, 3,5,5-trimethylhexyloxy, dodecyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, benzyl An oxy group etc. are mentioned.
Examples of the aryloxy group include a phenoxy group, a cresyloxy group, an isopropylphenoxy group, a 4-t-butylphenoxy group, a naphthoxy group, and a biphenyloxy group.
Examples of the amino group include a dimethylamino group, a diethylamino group, a dibutylamino group, a dioctylamino group, an N-methyl-N-hexylamino group, a dicyclohexylamino group, a diphenylamino group, and an N-methyl-N-phenylamino group. .

R ²¹ to R ²³ are preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. In view of the effects of the present invention, at least one of R ²¹ to R ²³ is preferably an alkyl group or an aryl group, and more preferably two or more are an alkyl group or an aryl group. In addition, it is preferable that R ²¹ to R ²³ are the same group in that they can be obtained at low cost.
Specific examples of the hydrogen bonding compound including the compound of the general formula (D) in the present invention are shown below, but the present invention is not limited thereto.

Specific examples of the hydrogen bonding compound include those described in European Patent No. 1096310, JP-A No. 2002-156727, and JP-A No. 2002-318431 in addition to the above.
The compound represented by the general formula (D) in the present invention can be used in a light-sensitive material by being incorporated in a coating solution in the form of a solution, an emulsified dispersion, or a solid dispersion fine particle dispersion in the same manner as the reducing agent. It is preferable to use it as a product. These compounds form a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state, and depending on the combination of the reducing agent and the compound of the general formula (D) in the present invention, the compound may be crystallized as a complex. It can be isolated in the state.
The use of the crystal powder isolated in this way as a solid dispersed fine particle dispersion is particularly preferable for obtaining stable performance. Further, a method in which the reducing agent and the compound of the general formula (D) in the present invention are mixed in a powder and complexed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can be preferably used.
The compound of the general formula (D) in the present invention is preferably used in the range of 1 mol% to 200 mol%, more preferably in the range of 10 mol% to 150 mol%, based on the reducing agent. More preferably, it is the range of 20 mol% or more and 100 mol%.

(Description of silver halide)
1) Halogen composition The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and is silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, silver iodide. Can be used. Of these, silver bromide, silver iodobromide and silver iodide are preferred. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be continuously changed. Further, silver halide grains having a core / shell structure can be preferably used. A preferable structure is a 2- to 5-fold structure, more preferably 2- to 4-fold core / shell particles. A technique for localizing silver bromide or silver iodide on the surface of silver chloride, silver bromide or silver chlorobromide grains can also be preferably used.

2) Grain Forming Methods Methods for forming photosensitive silver halide are well known in the art and are described, for example, in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. In particular, a photosensitive silver halide is prepared by adding a silver supply compound and a halogen supply compound into gelatin or another polymer solution, and then mixed with an organic silver salt. Use the method. Further, the method described in paragraph Nos. 0217 to 0224 of JP-A No. 11-119374, and the methods described in JP-A Nos. 11-352627 and 2000-347335 are also preferable.

3) Grain size The grain size of the photosensitive silver halide is preferably small for the purpose of keeping the cloudiness after image formation low, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less. More preferably, it is 0.02 μm or more and 0.12 μm or less. The grain size here means the diameter when converted into a circular image having the same area as the projected area of silver halide grains (in the case of tabular grains, the projected area of the main plane).

4) Grain shape Examples of the shape of the silver halide grains include cubes, octahedrons, tabular grains, spherical grains, rod-like grains, and potato grains. In the present invention, cubic grains are particularly preferred. Grains with rounded corners of silver halide grains can also be preferably used. The surface index (Miller index) on the outer surface of the photosensitive silver halide grain is not particularly limited, but the ratio of the {100} plane, which has high spectral sensitizing efficiency when adsorbed by the spectral sensitizing dye, is high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more. The ratio of the Miller index {100} plane is determined by T.sub. Tani; Imaging Sci. 29, 165 (1985).

5) Heavy Metal The photosensitive silver halide grain in the invention can contain a metal or metal complex of Group 8 to Group 10 of the Periodic Table (showing Groups 1 to 18). As the central metal of the group 8 to group 10 metal or metal complex of the periodic table, rhodium, ruthenium and iridium are preferable. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol with ^respect to 1 mol of silver. These heavy metals and metal complexes and methods for adding them are described in JP-A-7-225449, JP-A-11-65021, paragraphs 0018 to 0024, and JP-A-11-119374, paragraphs 0227 to 0240.

In the present invention, silver halide grains in which a hexacyano metal complex is present on the outermost surface of the grains are preferred. The hexacyano metal complexes include [Fe (CN) ₆ ] ⁴⁻ , [Fe (CN) ₆ ] ³⁻ , [Ru (CN) ₆ ] ⁴⁻ , [Os (CN) ₆ ] ⁴⁻ , [Co ( CN) ₆ ] ³⁻ , [Rh (CN) ₆ ] ³⁻ , [Ir (CN) ₆ ] ³⁻ , [Cr (CN) ₆ ] ³⁻ , [Re (CN) ₆ ] ^{3− and the} like. . In the present invention, a hexacyano Fe complex is preferred.

  The hexacyano metal complex is present in the form of ions in aqueous solution, so the counter cation is not important, but it is easy to mix with water and is suitable for precipitation of silver halide emulsions. Sodium ion, potassium ion, rubidium It is preferable to use alkali metal ions such as ions, cesium ions, and lithium ions, ammonium ions, and alkylammonium ions (for example, tetramethylammonium ions, tetraethylammonium ions, tetrapropylammonium ions, tetra (n-butyl) ammonium ions).

  In addition to water, the hexacyano metal complex is miscible with a mixed solvent or gelatin with an appropriate organic solvent miscible with water (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be added.

The addition amount of the hexacyano metal complex is preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less, more preferably 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻³ mol or less per mol of silver.

  In order for the hexacyano metal complex to be present on the outermost surface of the silver halide grain, the chalcogen sensitization of sulfur sensitization, selenium sensitization and tellurium sensitization is completed after the addition of the aqueous silver nitrate solution used for grain formation. It is added directly before the completion of the preparation step before the chemical sensitization step for performing noble metal sensitization such as sensitization and gold sensitization, during the washing step, during the dispersion step, or before the chemical sensitization step. In order to prevent the silver halide fine grains from growing, it is preferable to add the hexacyano metal complex immediately after the grain formation, and it is preferable to add it before the completion of the preparation step.

  The addition of the hexacyano metal complex may be started after adding 96% by mass of the total amount of silver nitrate to be added to form grains, more preferably starting after adding 98% by mass, The addition of 99% by mass is particularly preferable.

  When these hexacyanometal complexes are added after the addition of the aqueous silver nitrate solution just before the completion of grain formation, they can be adsorbed on the outermost surface of the silver halide grains, and most of them form slightly soluble salts with silver ions on the grain surface. To do. This silver salt of hexacyanoiron (II) is a less soluble salt than AgI, so that re-dissolution by fine particles can be prevented and silver halide fine particles having a small particle size can be produced. .

Further, regarding a metal atom (for example, [Fe (CN) ₆ ] ⁴⁻ ), a silver halide emulsion desalting method and a chemical sensitization method which can be contained in the silver halide grains used in the present invention, JP-A No. 11-101. No. 84574, paragraph numbers 0046 to 0050, JP-A No. 11-65021, paragraph numbers 0025 to 0031, and JP-A No. 11-119374, paragraph numbers 0242 to 0250.

6) Gelatin As the gelatin contained in the photosensitive silver halide emulsion used in the present invention, various gelatins can be used. It is necessary to maintain a good dispersion state of the photosensitive silver halide emulsion in the coating solution containing an organic silver salt, and gelatin having a molecular weight of 10,000 to 1,000,000 is preferably used. It is also preferable to phthalate the gelatin substituent. These gelatins may be used at the time of grain formation or at the time of dispersion after desalting, but are preferably used at the time of grain formation.

7) Sensitizing Dye Sensitizing dyes applicable to the present invention are those that can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and are suitable for the spectral characteristics of the exposure light source. Sensitizing dyes with sensitivity can be advantageously selected. Regarding the sensitizing dye and the addition method, paragraphs 0103 to 0109 of JP-A-11-65021, compounds represented by the general formula (II) of JP-A-10-186572, and general formulas (I) of JP-A-11-119374 ) And the dye described in Example 5 of U.S. Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131, JP-A-59-48753. No. 19, page 38 to line 20, page 35 of European Patent Publication No. 0803764A1, JP 2001-272747, JP 2001-290238, JP 2002-23306, etc. It is described in. These sensitizing dyes may be used alone or in combination of two or more. In the present invention, the time when the sensitizing dye is added to the silver halide emulsion is preferably the time from the desalting step to the coating, and more preferably the time from desalting to the end of chemical ripening.
The addition amount of the sensitizing dye in the present invention can be set to a desired amount according to the sensitivity and fogging performance, but is preferably 10 ⁻⁶ to 1 mol, more preferably 1 mol per mol of silver halide in the image forming layer. Is 10 ⁻⁴ to 10 ⁻¹ mol.

  In the present invention, a supersensitizer can be used to improve spectral sensitization efficiency. As the supersensitizer used in the present invention, European Patent Publication No. 587,338, US Pat. Nos. 3,877,943, 4,873,184, JP-A-5-341432, 11- 109547, 10-111543, etc. are mentioned.

8) Chemical Sensitization The photosensitive silver halide grain in the invention is preferably chemically sensitized by sulfur sensitization, selenium sensitization or tellurium sensitization. As the compound preferably used in the sulfur sensitization method, selenium sensitization method, and tellurium sensitization method, known compounds such as compounds described in JP-A-7-128768 can be used. In the present invention, tellurium sensitization is particularly preferred, and compounds described in the literature described in paragraph No. 0030 of JP-A-11-65021, general formulas (II), (III), (IV) in JP-A-5-313284 The compound shown by is more preferable.

  The photosensitive silver halide grains in the present invention are preferably chemically sensitized by gold sensitization alone or in combination with the chalcogen sensitization described above. As the gold sensitizer, the valence of gold is preferably +1 or +3, and the gold sensitizer is preferably a commonly used gold compound. Typical examples include chloroauric acid, bromoauric acid, potassium chloroaurate, potassium bromoaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold. Etc. are preferable. Further, gold sensitizers described in US Pat. No. 5,858,637 and Japanese Patent Application No. 2001-79450 are also preferably used.

In the present invention, chemical sensitization can be performed at any time after particle formation and before coating. After desalting, (1) before spectral sensitization, (2) simultaneously with spectral sensitization, (3) spectral After sensitization, there may be (4) immediately before application.
The amount of sulfur, selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is 10 ⁻⁸ mol or more and 10 ⁻² mol or less per mol of silver halide, Preferably, about 10 ⁻⁷ mol or more and 10 ⁻³ mol or less is used.
The amount of the gold sensitizer added varies depending on various conditions, but as a guideline, it is 10 ⁻⁷ mol or more and 10 ⁻³ mol or less, more preferably 10 ⁻⁶ mol or more and 5 × 10 ⁻⁴ mol or less per mol of silver halide. It is.
The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, and the temperature is about 40 to 95 ° C.
A thiosulfonic acid compound may be added to the silver halide emulsion used in the present invention by the method described in European Patent Publication No. 293,917.

    A reducing agent is preferably used for the photosensitive silver halide grains in the present invention. As specific compounds of the reduction sensitization method, ascorbic acid and aminoiminomethanesulfinic acid are preferable. In addition, it is preferable to use stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like. The reduction sensitizer may be added at any stage in the photosensitive emulsion production process from crystal growth to the preparation process immediately before coating. Further, reduction sensitization is preferable by ripening while maintaining the pH of the emulsion at 7 or more or pAg at 8.3 or less, and reduction sensitization is achieved by introducing a single addition portion of silver ions during grain formation. It is also preferable to do.

9) Compound in which 1-electron oxidant produced by 1-electron oxidation can emit 1 electron or more electrons In the photothermographic material of the present invention, 1-electron oxidant produced by 1-electron oxidation is 1 electron or 1 electron or more. It is preferable to contain a compound capable of emitting more electrons. The compound can be used alone or in combination with the above-described various chemical sensitizers, and can increase the sensitivity of silver halide.

The one-electron oxidant produced by one-electron oxidation contained in the light-sensitive material of the present invention is a compound selected from the following types 1 and 2 that can emit one or more electrons.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) is a compound that is a type 1 compound, and a one-electron oxidant produced by one-electron oxidation can further emit one electron with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786692A1 (Specific examples: Compounds INV 1-35), “One-photon two-electron sensitizer” or “deprotonated electron donation” described in patents such as European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. No. 5,994,051 Compound called sensitive agent "and the like. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

  In addition, as a compound of type 1 that can be emitted by one-electron oxidant produced by one-electron oxidation and further releasing one electron or more with a subsequent bond cleavage reaction, a compound represented by the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in JP-A-2003-75950), and general formula (7) (JP-A-2003-75950). Synonymous with general formula (2) described in , General formula (8) (synonymous with general formula (1) described in Japanese Patent Application No. 2003-25886), or chemical reaction formula (1) (chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) And the compound represented by the general formula (9) (synonymous with the general formula (3) described in Japanese Patent Application No. 2003-33446). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the formula, RED ₁ and RED ₂ represent a reducing group. R ₁ represents a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form of a 5-membered or 6-membered aromatic ring (including an aromatic heterocycle) or an octahydro form together with carbon atom (C) and RED _1. Represent. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. L ₁ represents a leaving group. ED represents an electron donating group. Z ₁ represents an atomic group capable of forming a 6-membered ring with a nitrogen atom and two carbon atoms of a benzene ring. X ₁ represents a substituent, and m ₁ represents an integer of 0 to 3. Z ₂ represents —CR ₁₁ R ₁₂ —, —NR ₁₃ —, or —O—. R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a substituent. R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. X ₁ represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. L ₂ represents a carboxy group or a salt thereof, or a hydrogen atom. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

Next, the type 2 compound will be described.
As a compound that can be emitted by one-electron oxidant generated by one-electron oxidation with a type 2 compound and further with one subsequent bond formation reaction, a compound represented by the general formula (10) is disclosed. The reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) may occur. And a compound represented by the general formula (11) (synonymous with the general formula (2) described in Japanese Patent Application No. 2003-33446). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the formula, X represents a reducing group that is one-electron oxidized. Y reacts with a one-electron oxidant produced by one-electron oxidation of X to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or a benzo The reactive group containing the non-aromatic heterocyclic part of a condensed ring is represented. L ₂ represents a linking group for linking X and Y. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide include those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are a 5-mercaptotetrazole group, a 3-mercapto-1,2,4-triazole group, and a benzotriazole group, and most preferred are a 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing heterocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Is mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As a counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

  A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

Formula (X) (PQ ₁ −) _i −R (−Q ₂ −S) _j

In the general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group. Specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (= O) —, —SO ₂ —, —SO—, —P (═O) — each independently represents a group consisting of a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and i + j is selected from the range of 2-6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

  The compounds of type 1 and type 2 in the present invention may be used at any time during the preparation of the photosensitive silver halide emulsion and during the process of producing the photothermographic material. For example, at the time of photosensitive silver halide grain formation, desalting step, chemical sensitization, before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of formation of the photosensitive silver halide grains to before the desalting step, at the time of chemical sensitization (immediately after the start of chemical sensitization to immediately after completion), and before coating, more preferably from the time of chemical sensitization Until before mixing with the non-photosensitive organic silver salt.

  The compounds of type 1 and type 2 in the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is raised or lowered may be dissolved at a higher or lower pH and added.

The compounds of type 1 and type 2 in the present invention are preferably used in an image forming layer containing a photosensitive silver halide and a non-photosensitive organic silver salt, but the photosensitive silver halide and the non-photosensitive organic silver salt are used. It may be added to the protective layer or intermediate layer together with the image forming layer containing, and diffused during coating. The addition timing of these compounds is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻¹ mol, more preferably 1 × 10 ^{−8 to} 5 mol, per mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-2 mol of silver halide emulsion layer (image forming layer).

10) Adsorbing redox compound having an adsorbing group and a reducing group In the present invention, an adsorbing redox compound having an adsorbing group and a reducing group for silver halide is preferably contained in the molecule. The adsorptive redox compound is preferably a compound represented by the following formula (I).

Formula (I) A- (W) n-B
In formula (I), A represents a group that can be adsorbed to silver halide (hereinafter referred to as an adsorbing group), W represents a divalent linking group, n represents 0 or 1, and B represents a reducing group. Represent.

  In the formula (I), the adsorption group represented by A is a group that directly adsorbs to silver halide, or a group that promotes adsorption to silver halide, and specifically, a mercapto group (or a salt thereof). , A thione group (—C (═S) —), a heterocyclic group, a sulfide group, a disulfide group, a cationic group, or an ethynyl group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom Etc.

The mercapto group (or salt thereof) as the adsorptive group means the mercapto group (or salt thereof) itself, and more preferably a heterocyclic group or aryl group substituted with at least one mercapto group (or salt thereof) or Represents an alkyl group. Here, the heterocyclic group is at least a 5- to 7-membered monocyclic or condensed aromatic or non-aromatic heterocyclic group such as an imidazole ring group, a thiazole ring group, an oxazole ring group, or a benzimidazole ring. Group, benzothiazole ring group, benzoxazole ring group, triazole ring group, thiadiazole ring group, oxadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyrimidine ring group, And triazine ring group. Moreover, the heterocyclic group containing the quaternized nitrogen atom may be sufficient, and in this case, the substituted mercapto group may dissociate and it may become a meso ion. When the mercapto group forms a salt, the counter ion is a cation such as an alkali metal, alkaline earth metal or heavy metal (Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ag ⁺ , Zn ²⁺ etc.), ammonium ion Examples thereof include a heterocyclic group containing a quaternized nitrogen atom, a phosphonium ion, and the like.
Further, the mercapto group as the adsorptive group may be tautomerized into a thione group.
The thione group as an adsorbing group also includes a chain or cyclic thioamide group, thioureido group, thiourethane group, or dithiocarbamate group.
A heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as the adsorptive group is a -NH- group capable of forming imino silver (> NAg) as a partial structure of the heterocyclic ring. A nitrogen-containing heterocyclic group, or a “—S—” group, a “—Se—” group, a “—Te—” group or a “═N—” group which can be coordinated to a silver ion by a coordination bond A heterocyclic group having a partial structure of benzotriazole group, triazole group, indazole group, pyrazole group, tetrazole group, benzimidazole group, imidazole group, purine group and the like as thiophene group as the latter example , Thiazole group, oxazole group, benzothiophene group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole group, triazine group, Renoazoru group, benzoselenazole group, tellurium azole group, such as benzo tellurium azole group.
Examples of the sulfide group or disulfide group as the adsorptive group include all groups having a partial structure of -S- or -SS-.
The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, specifically, an ammonio group or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, an imidazolio group, and the like.
An ethynyl group as an adsorptive group means a —C≡CH group, and the hydrogen atom may be substituted.
The adsorbing group may have an arbitrary substituent.

  Further, specific examples of the adsorbing group include those described in the specifications p4 to p7 of JP-A No. 11-95355.

  In the formula (I), preferred as the adsorptive group represented by A is a mercapto-substituted heterocyclic group (for example, 2-mercaptothiadiazole group, 2-mercapto-5-aminothiadiazole group, 3-mercapto-1,2,4). -Triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzimidazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5-dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3-thiazole group), or Nitrogen-containing heterocyclic group having —NH— group capable of forming imino silver (> NAg) as a partial structure of heterocyclic ring (for example, benzotriazo Group, benzimidazole group, an indazole group), more preferable as an adsorptive group is a 2-mercaptobenzimidazole group, a 3,5-dimercapto-1,2,4-triazole group.

In formula (I), W represents a divalent linking group. Any linking group may be used as long as it does not adversely affect photographic properties. For example, a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom can be used. Specifically, an alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, etc.), an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. , An arylene group having 6 to 20 carbon atoms (eg, phenylene group, naphthylene group, etc.), —CO—, —SO ₂ —, —O—, —S—, —NR ₁ —, combinations of these linking groups, and the like. It is done. Here, R ₁ represents a hydrogen atom, an alkyl group, a heterocyclic group, or an aryl group.
The linking group represented by W may have an arbitrary substituent.

  In formula (I), the reducing group represented by B represents a group capable of reducing silver ions. For example, a triple bond group such as formyl group, amino group, acetylene group or propargyl group, mercapto group, hydroxylamines. Hydroxamic acids, hydroxyureas, hydroxyurethanes, hydroxysemicarbazides, reductones (including reductone derivatives), anilines, phenols (chroman-6-ols, 2,3-dihydrobenzofuran-5-ols, (Including aminophenols, sulfonamidophenols, and hydroquinones, catechols, resorcinols, polyphenols such as benzenetriols, bisphenols), acylhydrazines, carbamoylhydrazines, 3-pyrazolidones, etc. Residue with one removed And the like. Of course, these may have an arbitrary substituent.

In the formula (I), the reducing group represented by B shows its oxidation potential by Akira Fujishima “Electrochemical measurement method” (pages 150-208, published by Gihodo) or “The Experimental Chemistry Course” edited by the Chemical Society of Japan, 4th edition ( 9 pages 282-344, Maruzen). For example, by a rotating disk voltammetry technique, specifically, a sample is dissolved in a solution of methanol: pH 6.5 Briton-Robinson buffer = 10%: 90% (volume%), and nitrogen gas is used for 10 minutes. , A glassy carbon rotating disk electrode (RDE) is used as a working electrode, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 25 ° C., 1000 rev / min, 20 mV / sec. Can be measured at sweep speed. A half-wave potential (E1 / 2) can be obtained from the obtained voltammogram.
In the present invention, the reducing group represented by B preferably has an oxidation potential in the range of about -0.3 V to about 1.0 V when measured by the above measurement method. More preferably, it is in the range of about -0.1V to about 0.8V, and particularly preferably in the range of about 0 to about 0.7V.

  In the formula (I), the reducing group represented by B is preferably selected from hydroxylamines, hydroxamic acids, hydroxyureas, hydroxysemicarbazides, reductones, phenols, acylhydrazines, carbamoylhydrazines, and 3-pyrazolidones. A residue obtained by removing one hydrogen atom.

  The compound of the formula (I) in the present invention may be one in which a ballast group or polymer chain commonly used in an immobile photographic additive such as a coupler is incorporated. Examples of the polymer include those described in JP-A-1-100530.

  The compound of the formula (I) in the present invention may be a bis form or a tris form. The molecular weight of the compound of formula (I) in the present invention is preferably between 100 and 10000, more preferably between 120 and 1000, particularly preferably between 150 and 500.

  Examples of the compound of formula (I) in the present invention are shown below, but the present invention is not limited thereto.

  Further, specific compounds 1 to 30 and 1 ″ -1 to 1 ″ -77 described in European Patent No. 1308776A2 P73 to P87 are also preferable examples of the compound having an adsorbing group and a reducing group in the present invention. .

  These compounds can be easily synthesized according to known methods. As the compound of the formula (I) in the present invention, one kind of compound may be used alone, but it is also preferred to use two or more kinds of compounds at the same time. When two or more kinds of compounds are used, they may be added in the same layer or in different layers, and the addition methods may be different.

The compound of formula (I) in the present invention is preferably added to the silver halide emulsion layer, and more preferably added during preparation of the emulsion. When added at the time of emulsion preparation, it can be added at any time during the process. For example, silver halide grain formation process, before the start of desalting process, desalting process, chemical ripening Examples include a step before starting, a chemical ripening step, and a step before preparing a finished emulsion. Moreover, it can also be added in several steps in these processes. Although it is preferably used for the image forming layer, it may be added to the adjacent protective layer or intermediate layer together with the image forming layer and diffused during coating.
The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but generally 1 × 10 ⁻⁶ mol to 1 mol, preferably 1 × 10 ⁻⁵ mol, per mol of photosensitive silver halide. The amount is 5 × 10 ⁻¹ mol or less, more preferably 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻¹ mol or less.

  The compound of the formula (I) in the present invention can be added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. At this time, the pH may be appropriately adjusted with an acid or a base, and a surfactant may be allowed to coexist. Furthermore, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion. It can also be added as a solid dispersion.

11) Multiple silver halides in combination The photosensitive 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 having different average grain sizes, those having different halogen compositions, Those having different crystal habits and different chemical sensitization conditions may be used in combination. The gradation can be adjusted by using a plurality of types of photosensitive silver halides having different sensitivities. Examples of these technologies include JP-A-57-119341, 53-106125, 47-3929, 48-55730, 46-5187, 50-73627, 57-150841 and the like. Can be mentioned. The sensitivity difference is preferably 0.2 log E or more for each emulsion.

12) Application amount The addition amount of photosensitive silver halide is preferably 0.03 g / m ² or more and 0.6 g / m ² or less, expressed as the amount of silver applied per 1 m ² of the light-sensitive material. / M ² or more and 0.4 g / m ² or less is more preferable, and 0.07 g / m ² or more and 0.3 g / m ² or less is most preferable. The functional silver halide is preferably from 0.01 mol to 0.5 mol, more preferably from 0.02 mol to 0.3 mol, and still more preferably from 0.03 mol to 0.2 mol.

13) Mixing of photosensitive silver halide and organic silver salt Regarding the mixing method and mixing conditions of separately prepared photosensitive silver halide and organic silver salt, the silver halide grains and the organic silver salt that were prepared respectively were stirred at high speed. Prepare an organic silver salt by mixing with a machine, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc., or by mixing photosensitive silver halide that has been prepared at any time during the preparation of the organic silver salt However, there is no particular limitation as long as the effects of the present invention are sufficiently exhibited. Moreover, mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions when mixing is a preferred method for adjusting photographic characteristics.

14) Mixing of silver halide into coating solution The preferred addition time of silver halide into the image forming layer coating solution is from 180 minutes before application, preferably from 60 minutes to 10 seconds before application. The method and mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid fed to the coater is a desired time, and N.I. Harnby, M.M. F. Edwards, A.D. W. There is a method using a static mixer described in Chapter 8 of Nienow's “Liquid Mixing Technology” (Nikkan Kogyo Shimbun, 1989), translated by Koji Takahashi.

(Description of binder)
Any polymer may be used as the binder of the image-forming layer in the present invention. Suitable binders are transparent or translucent and generally colorless, and are natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other films. Forming media such as gelatins, gums, poly (vinyl alcohol) s, hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrates, poly (vinyl pyrrolidone) s, casein, starch, poly (acrylic acid) , Poly (methyl methacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, Poly (vinyl acetal) s (for example, poly (vinyl acetal) (Formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resins, poly (vinylidene chloride) s, poly (epoxides), poly (carbonates), poly (vinyl acetate) s , Poly (olefin) s, cellulose esters, and poly (amides). The binder may be formed from water, an organic solvent or an emulsion.

  In the present invention, the glass transition temperature of the binder that can be used in combination with the layer containing the organic silver salt is preferably 0 ° C. or higher and 80 ° C. or lower (hereinafter sometimes referred to as a high Tg binder), and preferably 10 ° C. to 70 ° C. Is more preferable, and it is still more preferable that it is 15 to 60 degreeC.

In this specification, Tg was calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature (Tgi) of each monomer was the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)).

  Two or more binders may be used in combination as required. Further, a glass transition temperature of 20 ° C. or higher and a glass transition temperature of less than 20 ° C. may be used in combination. When two or more kinds of polymers having different Tg are blended, the weight average Tg is preferably within the above range.

In the present invention, it is preferable that the image forming layer is coated and dried using a coating solution in which 30% by mass or more of the solvent is water to form a film.
In the present invention, when the image forming layer is formed using a coating solution in which 30% by mass or more of the solvent is water and dried, the binder of the image forming layer is further added to an aqueous solvent (aqueous solvent). When it is soluble or dispersible, the performance is improved particularly when it is made of a latex of a polymer having an equilibrium water content of 2% by mass or less at 25 ° C. and 60% RH. The most preferable form is one prepared so that the ionic conductivity is 2.5 mS / cm or less, and as such a preparation method, there is a method of performing purification treatment using a separation functional membrane after polymer synthesis.

  The aqueous solvent in which the polymer is soluble or dispersible here is a mixture of water or water and 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol, cellosolvs such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, ethyl acetate, and dimethylformamide.

  In the case of a system in which the polymer is not dissolved thermodynamically and exists in a so-called dispersed state, the term aqueous solvent is used here.

The “equilibrium moisture content at 25 ° C. and 60% RH” is the following using the weight W1 of the polymer in the humidity-controlled equilibrium under the atmosphere of 25 ° C. and 60% RH and the weight W0 of the polymer in the absolutely dry state at 25 ° C. It can be expressed as
Equilibrium moisture content at 25 ° C. and 60% RH = {(W1−W0) / W0} × 100 (mass%)

  For the definition and measurement method of moisture content, for example, Polymer Engineering Course 14, Polymer Material Testing Method (Edited by Society of Polymer Sciences, Jinshokan) can be referred to.

  The equilibrium water content at 25 ° C. and 60% RH of the binder polymer in the present invention is preferably 2% by mass or less, more preferably 0.01% by mass or more and 1.5% by mass or less, and further preferably 0.02 Desirably, the content is from 1% by mass to 1% by mass.

  In the present invention, a polymer dispersible in an aqueous solvent is particularly preferred. Examples of the dispersed state may be either latex in which fine particles of water-insoluble hydrophobic polymer are dispersed or polymer molecules dispersed in a molecular state or forming micelles. preferable. The average particle size of the dispersed particles is 1 nm or more and 50000 nm or less, preferably 5 nm or more and 1000 nm or less, more preferably 10 nm or more and 500 nm or less, and further preferably 50 nm or more and 200 nm or less. 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. Mixing two or more types having a monodispersed particle size distribution is also a preferable method for controlling the physical properties of the coating solution.

  In the present invention, preferred embodiments of the polymer that can be dispersed in an aqueous solvent include acrylic polymers, poly (esters), rubbers (eg, SBR resin), poly (urethanes), poly (vinyl chloride) s, poly (acetic acid). Hydrophobic polymers such as vinyl), poly (vinylidene chloride) and poly (olefin) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of these polymers is 5,000 to 1,000,000, preferably 10,000 to 200,000 in terms of number average molecular weight. When the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and when the molecular weight is too large, the film formability is poor, which is not preferable. A crosslinkable polymer latex is particularly preferably used.

(Specific examples of latex)
Specific examples of preferable polymer latex include the following. Below, it represents using a raw material monomer, the numerical value in a parenthesis is the mass%, and molecular weight is a number average molecular weight. When a polyfunctional monomer was used, the concept of molecular weight was not applicable because a crosslinked structure was formed, so it was described as crosslinkability, and the description of molecular weight was omitted. Tg represents the glass transition temperature.

-P-1; latex of -MMA (70) -EA (27) -MAA (3)-(molecular weight 37000, Tg 61 ° C.)
-Latex of P-2; -MMA (70) -2EHA (20) -St (5) -AA (5)-(molecular weight 40000, Tg 59 ° C.)
-P-3; Latex of -St (50) -Bu (47) -MAA (3)-(crosslinkability, Tg-17 ° C)
-P-4; Latex of -St (68) -Bu (29) -AA (3)-(crosslinkability, Tg 17 ° C)
-P-5; Latex of -St (71) -Bu (26) -AA (3)-(crosslinkability, Tg 24 ° C)
-P-6; -St (70) -Bu (27) -IA (3)-latex (crosslinkable)
-P-7; Latex of -St (75) -Bu (24) -AA (1)-(crosslinkability, Tg 29 ° C.)
-P-8; Latex (crosslinkability) of -St (60) -Bu (35) -DVB (3) -MAA (2)-
-Latex (crosslinkable) of P-9; -St (70) -Bu (25) -DVB (2) -AA (3)-
-Latex (molecular weight 80,000) of P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-
-P-11; latex of -VDC (85) -MMA (5) -EA (5) -MAA (5)-(molecular weight 67000)
-P-12; -Et (90) -MAA (10)-latex (molecular weight 12000)
-P-13; Latex of -St (70) -2EHA (27) -AA (3) (molecular weight 130,000, Tg 43 ° C)
-P-14; -MMA (63) -EA (35) -AA (2) latex (molecular weight 33000, Tg 47 ° C.)
-P-15; Latex of -St (70.5) -Bu (26.5) -AA (3)-(crosslinkability, Tg 23 ° C.)
-P-16; Latex of -St (69.5) -Bu (27.5) -AA (3)-(crosslinkability, Tg 20.5 ° C)

  The abbreviations for the above structures represent the following monomers. MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2-ethylhexyl acrylate, St; styrene, Bu; butadiene, AA; acrylic acid, DVB; divinylbenzene, VC; vinyl chloride, AN; Vinylidene chloride, Et; ethylene, IA; itaconic acid.

  The polymer latex described above is also commercially available, and the following polymers can be used. Examples of the acrylic polymer include Sebian A-4635, 4718, 4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820, 857 (manufactured by Nippon Zeon Co., Ltd.), etc. Examples of poly (esters) include poly (urethane) such as FINETEX ES650, 611, 675, 850 (above, Dainippon Ink Chemical Co., Ltd.), WD-size, WMS (above, Eastman Chemical). Examples of rubbers include HYDRAN AP10, 20, 30, 40 (above, manufactured by Dainippon Ink Chemical Co., Ltd.), and examples of rubbers include LACSTAR 7310K, 3307B, 4700H, 7132C (above, Dainippon Ink Chemical Co., Ltd.). (Made by Co., Ltd.), Nipol Lx416, 410, 438C, 2507 As examples of poly (vinyl chloride) such as G351 and G576 (above, manufactured by Nippon Zeon Co., Ltd.), examples of poly (vinylidene chloride) such as L502, L513 (above Examples of poly (olefin) s such as Asahi Kasei Kogyo Co., Ltd. include Chemipearl S120 and SA100 (above Mitsui Petrochemical Co., Ltd.).

  These polymer latexes may be used alone or in combination of two or more as required.

(Preferred latex)
As the polymer latex used in the present invention, a styrene-butadiene copolymer latex is particularly preferable. The weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably 40:60 to 95: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by mass. Moreover, it is preferable that the polymer latex in this invention contains 1-6 mass% of acrylic acid or methacrylic acid with respect to the sum of styrene and butadiene, More preferably, it contains 2-5 mass%. The polymer latex in the present invention preferably contains acrylic acid. The preferred molecular weight range is the same as described above.

  Examples of latexes of styrene-butadiene acid copolymer that are preferably used in the present invention include the aforementioned P-3 to P-8,15, commercially available LACSTAR-3307B, 7132C, Nipol Lx416, and the like.

  If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose may be added to the image forming layer of the light-sensitive material of the present invention. The amount of these hydrophilic polymers added is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total binder of the image forming layer.

  The organic silver salt-containing layer (that is, the image forming layer) in the present invention is preferably formed using a polymer latex. The amount of binder in the image forming layer is such that the weight ratio of total binder / organic silver salt is 1/10 to 10/1, more preferably 1/3 to 5/1, and still more preferably 1/1 to 3/1. Range.

  Further, such an organic silver salt-containing layer is usually a photosensitive layer (image forming layer) containing a photosensitive silver halide which is a photosensitive silver salt. The weight ratio of silver halide is in the range of 400-5, more preferably 200-10.

The total binder amount of the image forming layer in the present invention is preferably 0.2 g / m ² or more and 30 g / m ² or less, more preferably 1 g / m ² or more and 15 g / m ² or less, and further preferably 2 g / m ² or more and 10 g. / M ² or less. In the image forming layer of the present invention, a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added.

(Preferable solvent for coating solution)
In the present invention, the solvent of the image forming layer coating solution of the light-sensitive material (for simplicity, the solvent and the dispersion medium are collectively referred to as a solvent) is preferably an aqueous solvent containing 30% by mass or more of water. As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate may be used. The water content of the solvent of the coating solution is preferably 50% by mass or more, more preferably 70% by mass or more. Examples of preferred solvent compositions include water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / Ethyl cellosolve = 85/10/5, water / methyl alcohol / isopropyl alcohol = 85/10/5, etc. (numerical values are mass%).

(Description of antifogging agent)
Antifoggants, stabilizers and stabilizer precursors which can be used in the present invention are disclosed in paragraph No. 0070 of JP-A-10-62899, page 20, line 57 to page 21, line 7 of European Patent Publication No. 0803764A1. And the compounds described in JP-A-9-281737 and JP-A-9-329864, and the compounds described in US Pat. No. 6,083,681 and European Patent 1048875.

(Description of polyhalogen compounds)
Hereinafter, preferred organic polyhalogen compounds that can be used in the present invention will be specifically described. A preferred polyhalogen compound in the present invention is a compound represented by the following general formula (H).
General formula (H)
Q- (Y) n-C (Z ₁ ) (Z ₂ ) X
In general formula (H), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 to ₁ , Z ₁ and Z ₂ represent a halogen atom, X represents a hydrogen atom or an electron withdrawing group.
In the general formula (H), Q is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heterocyclic group containing at least one nitrogen atom (pyridine, quinoline group, etc.).
In the general formula (H), when Q is an aryl group, Q preferably represents a phenyl group substituted with an electron-attracting group having a positive Hammett's substituent constant σp. For Hammett's substituent constants, see Journal of Medicinal Chemistry, 1973, Vol. 16, no. 11, 1207-1216 etc. can be referred to. Examples of such an electron withdrawing group include a halogen atom, an alkyl group substituted with an electron withdrawing group, an aryl group substituted with an electron withdrawing group, a heterocyclic group, an alkyl or arylsulfonyl group, acyl Group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group and the like. Particularly preferred as the electron withdrawing group are a halogen atom, a carbamoyl group and an arylsulfonyl group, and a carbamoyl group is particularly preferred.
X is preferably an electron withdrawing group. Preferred electron withdrawing groups are halogen atoms, aliphatic / aryl or heterocyclic sulfonyl groups, aliphatic / aryl or heterocyclic acyl groups, aliphatic / aryl or heterocyclic oxycarbonyl groups, carbamoyl groups, sulfamoyl groups, More preferred are a halogen atom and a carbamoyl group, and particularly preferred is a bromine atom.
Z ₁ and Z ₂ are preferably a bromine atom or an iodine atom, and more preferably a bromine atom.
Y preferably represents -C (= O) -, - SO -, - SO 2 -, - C (= O) N (R) -, - SO 2 N (R) - , more preferably -C ( ═O) —, —SO ₂ —, —C (═O) N (R) —, and particularly preferably —SO ₂ —, —C (═O) N (R) —. R here represents a hydrogen atom, an aryl group or an alkyl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
n represents 0 or 1, and is preferably 1.
In the general formula (H), when Q is an alkyl group, preferred Y is —C (═O) N (R) —, and when Q is an aryl group or heterocyclic group, preferred Y is —SO ₂ —. is there.
In the general formula (H), a form in which residues obtained by removing a hydrogen atom from the compound are bonded to each other (generally referred to as bis type, tris type, tetrakis type) can also be preferably used.
In the general formula (H), a dissociable group (for example, a COOH group or a salt thereof, a SO ₃ H group or a salt thereof, a PO ₃ H group or a salt thereof), a group containing a quaternary nitrogen cation (for example, an ammonium group or a pyridinium group) Etc.), those having a polyethyleneoxy group, a hydroxyl group or the like as a substituent are also preferred forms.

  Specific examples of the compound represented by formula (H) in the present invention are shown below.

As polyhalogen compounds that can be used in the present invention other than the above, US Pat. No. 3,874,946, US Pat. No. 4,756,999, US Pat. No. 5,340,712, US Pat. 119624, 59-57234, JP-A-7-2781, 7-5621, 9-160164, 9-244177, 9-244178, 9-160167, 9- 319022, 9-258367, 9-265150, 9-319022, 10-197988, 10-197989, 11-242304, JP 2000-2963, JP 2000-11270 , JP2000-284410, JP2 The compounds listed as exemplary compounds of the invention in 00-284212, JP-A-2001-33911, JP-A-2001-31644, JP-A-2001-312027, and JP-A-2003-50441 are preferably used. In particular, compounds specifically exemplified in JP-A-7-2781, JP-A-2001-33911, and JP-A-2001-312027 are preferred.
The compound represented by formula (H) in the present invention is preferably used in the range of 10 ⁻⁴ mol to 1 mol, more preferably 10 ⁻³ , per mol of the non-photosensitive silver salt in the image forming layer. It is preferable to use in the range of from 1 to 10 mol, more preferably from 1 × 10 ⁻² mol to 0.2 mol.
In the present invention, the antifoggant is added to the light-sensitive material by the method described in the method for containing a reducing agent, and the organic polyhalogen compound is also preferably added as a solid fine particle dispersion.

(Other antifoggants)
Examples of other antifoggants include mercury (II) salts described in paragraph No. 0113 of JP-A No. 11-65021, benzoic acids of paragraph No. 0114 of the same, salicylic acid derivatives disclosed in JP-A No. 2000-206642, and formulas described in JP-A No. 2000-221634. A formalin scavenger compound represented by (S), a triazine compound according to claim 9 of JP-A-11-352624, a compound represented by formula (III) of JP-A-6-11791, 4-hydroxy-6-6 And methyl-1,3,3a, 7-tetrazaindene and the like.

The photothermographic material in the invention may contain an azolium salt for the purpose of fog prevention. Examples of the azolium salt include compounds represented by general formula (XI) described in JP-A-59-193447, compounds described in JP-B-55-12581, and general formula (II) described in JP-A-60-153039. And the compounds represented. The azolium salt may be added to any part of the light-sensitive material, but the addition layer is preferably added to the layer having the image forming layer, and more preferably added to the image forming layer. The azolium salt may be added at any step during the preparation of the coating solution, and when added to the image forming layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be used. Immediately before is preferable. The azolium salt may be added by any method such as powder, solution, fine particle dispersion. Moreover, you may add as a solution mixed with other additives, such as a sensitizing dye, a reducing agent, and a color toning agent. In the present invention, the azolium salt may be added in any amount, but it is preferably 1 × 10 ⁻⁶ mol or more and 2 mol or less, more preferably 1 × 10 ⁻³ mol or more and 0.5 mol or less per 1 mol of silver.

(Other additives)
1) Mercapto, disulfide, and thiones In the present invention, mercapto compounds and disulfide compounds are used for the purpose of controlling development by suppressing or promoting development, improving spectral sensitization efficiency, and improving storage stability before and after development. And thione compounds, paragraphs 0067 to 0069 of JP-A-10-62899, compounds represented by formula (I) of JP-A-10-186572, and specific examples thereof include paragraph numbers 0033 to 0052. , European Patent Publication No. 0803764A1, page 20, lines 36-56. Of these, mercapto-substituted heteroaromatic compounds described in JP-A-9-297367, JP-A-9-304875, JP-A-2001-100388, JP-A-2002-303955, JP-A-2002-303951, and the like are preferable. .

2) Toning agent In the photothermographic material of the invention, it is preferable to add a toning agent. For the toning agent, paragraph numbers 0054 to 0055 of JP-A-10-62899, page 21 to 23 of European Patent Publication No. 0803764A1. Line 48, described in JP-A No. 2000-356317 and JP-A No. 2000-187298, and in particular, phthalazinones (phthalazinone, phthalazinone derivatives or metal salts; for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone. 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione); phthalazinones and phthalic acids (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, diammonium phthalate) , Sodium phthalate, potassium phthalate and tetrachlorophthalic anhydride) Combinations; phthalazines (phthalazine, phthalazine derivatives or metal salts; for example, 4- (1-naphthyl) phthalazine, 6-isopropylphthalazine, 6-t-butylphthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine And 2,3-dihydrophthalazine); a combination of phthalazines and phthalic acids is preferable, and a combination of phthalazines and phthalic acids is particularly preferable. Among them, a particularly preferable combination is a combination of 6-isopropylphthalazine and phthalic acid or 4-methylphthalic acid.

3) Plasticizers and lubricants In the present invention, known plasticizers and lubricants can be used to improve film physical properties. In particular, it is preferable to use a lubricant such as liquid paraffin, long chain fatty acid, fatty acid amide, fatty acid ester, etc., in order to improve handling at the time of manufacture and scratch resistance at the time of heat development. In particular, liquid paraffin from which low-boiling components have been removed and fatty acid esters having a branched structure and having a molecular weight of 1000 or more are preferred.
Regarding the plasticizer and lubricant that can be used in the image forming layer and the non-photosensitive layer, JP-A No. 11-65021, paragraph No. 0117, JP-A No. 2000-5137, Japanese Patent Application No. 2003-8015, Japanese Patent Application No. 2003-8071, The compounds described in Japanese Patent Application No. 2003-132815 are preferred.

4) Dye and Pigment In the image forming layer of the present invention, various dyes and pigments (for example, CI Pigment Blue 60, CI, etc.) are used from the viewpoints of color tone improvement, prevention of interference fringes during laser exposure, and prevention of irradiation. Pigment Blue 64, CI Pigment Blue 15: 6) can be used. These are described in detail in WO98 / 36322, JP-A-10-268465, JP-A-11-338098 and the like.

5) Super-high contrast agent For the formation of a super-high contrast image suitable for printing plate making, it is preferable to add a super-high contrast agent to the image forming layer. As for the super-high contrast agent and its addition method and addition amount, the formula (H ), Formulas (1) to (3), compounds of formulas (A) and (B), compounds of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652 (specific compounds: 21 to 24) and the high contrast accelerator are described in paragraph No. 0102 of JP-A No. 11-65021 and paragraph Nos. 0194 to 0195 of JP-A No. 11-223898.

  In order to use formic acid or formate as a strong fogging substance, it is preferably contained in an amount of 5 mmol or less, more preferably 1 mmol or less per mol of silver on the side having an image forming layer containing photosensitive silver halide.

When the ultrahigh contrast agent is used in the photothermographic material of the present invention, it is preferable to use an acid formed by hydrating diphosphorus pentoxide or a salt thereof in combination. 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), hexametalin An acid (salt) etc. can be mentioned. Examples of the acid or salt thereof formed by hydrating diphosphorus pentoxide particularly preferably include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific examples of the salt include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, and ammonium hexametaphosphate.
The amount of acid or salt thereof formed by hydration of diphosphorus pentoxide (the coating amount per 1 m ^{2 of} photosensitive material) may be a desired amount according to the performance such as sensitivity and fog, but is 0.1 mg / m ^2. It is preferably 500 mg / m ² or less, more preferably 0.5 mg / m ² or more and 100 mg / m ² or less.
The reducing agent, hydrogen bonding compound, development accelerator and polyhalogen compound in the present invention are preferably used as a solid dispersion, and a preferred method for producing these solid dispersions is described in JP-A-2002-55405. .

(Preparation and application of coating solution)
The preparation temperature of the image forming layer coating solution in the invention is preferably from 30 ° C. to 65 ° C., more preferably from 35 ° C. to less than 60 ° C., and more preferably from 35 ° C. to 55 ° C. Moreover, it is preferable that the temperature of the image forming layer coating liquid immediately after the addition of the polymer latex is maintained at 30 ° C. or higher and 65 ° C. or lower.

(Layer structure and components)
The image forming layer in the invention is composed of one or more layers on a support. In the case of a single layer, it consists of an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, and optionally contains additional materials such as toning agents, coating aids and other auxiliary agents. In the case of two or more layers, the first image forming layer (usually a layer adjacent to the support) contains an organic silver salt and a light-sensitive silver halide, and some of the second image forming layer or both layers include Must contain other ingredients. The construction of a multicolor photosensitive photothermographic material may include a combination of these two layers for each color and all components in a single layer as described in US Pat. No. 4,708,928. May be included. In the case of multi-dye multicolor photosensitive photothermographic materials, each image-forming layer is generally functional or non-functional between each image-forming layer as described in US Pat. No. 4,460,681. By using a sex barrier layer, they are kept distinct from each other.
The photothermographic material of the present invention can have a non-photosensitive layer in addition to the image forming layer. The non-photosensitive layer includes (a) a surface protective layer provided on the image forming layer (on the side farther than the support), (b) between the plurality of image forming layers and between the image forming layer and the protective layer. It can be classified into an intermediate layer provided therebetween, (c) an undercoat layer provided between the image forming layer and the support, and (d) a back layer provided on the opposite side of the image forming layer.

  In addition, although a layer acting as an optical filter can be provided, it is provided as the layer (a) or (b). The antihalation layer is provided on the photosensitive material as the layer (c) or (d).

1) Surface protective layer The photothermographic material according to the invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer. The surface protective layer may be a single layer or a plurality of layers.
The surface protective layer is described in JP-A No. 11-65021, paragraph numbers 0119 to 0120 and JP-A No. 2000-171936.
As the binder for the surface protective layer in the present invention, gelatin is preferable, but it is also preferable to use polyvinyl alcohol (PVA) or a combination thereof. As gelatin, inert gelatin (for example, Nitta gelatin 750), phthalated gelatin (for example, Nitta gelatin 801), and the like can be used. Examples of PVA include those described in paragraph Nos. 0009 to 0020 of JP-A No. 2000-171936. Completely saponified PVA-105, partially saponified PVA-205, PVA-335, and modified polyvinyl alcohol MP- Preferred is 203 (trade name, manufactured by Kuraray Co., Ltd.). Preferably 0.3 to 4.0 g / m ² of polyvinyl alcohol coating amount as (per support 1 m ²⁾ is the protective layer (per one layer), 0.3 to 2.0 g / m ² is more preferable.

The total coating amount (including water-soluble polymer and latex polymer) of the surface protective layer (per layer) is preferably 0.3 g / m ² or more and 5.0 g / m ² or less as the coating amount (per 1 m ^{2 of the} support). .3g / m ² or more 2.0 g / m ² or less is more preferable.
In addition, it is preferable to use a lubricant such as liquid paraffin and aliphatic ester for the surface protective layer. The amount of the lubricant used is in the range of 1 mg / m ^{2 to} 200 mg / m ² , preferably 10 mg / m ^{2 to} 150 mg / m ² , more preferably 20 mg / m ^{2 to} 100 mg / m ^2. .

2) Antihalation layer In the photothermographic material of the invention, the antihalation layer can be provided on the side farther from the light source than the image forming layer.

As for the antihalation layer, paragraphs 0123 to 0124 of JP-A-11-65021, JP-A-11-223898, 9-230531, 10-36695, 10-104779, 11-231457, 11 -352625, 11-352626 and the like.
The antihalation layer contains an antihalation dye having absorption at the exposure wavelength. When the exposure wavelength is in the infrared region, an infrared absorbing dye may be used, and in that case, a dye having no absorption in the visible region is preferable.
When antihalation is performed using a dye having absorption in the visible range, it is preferable that substantially no dye color remains after image formation, and a means for decoloring by the heat of heat development is used. In particular, it is preferable to add a thermally decolorable dye and a base precursor to the non-photosensitive layer to function as an antihalation layer. These techniques are described in JP-A-11-231457 and the like.
The compound represented by the general formula (1) used in the present invention is useful as a heat decoloring dye used in the non-photosensitive layer. In particular, by containing it in the antihalation layer, the dye of the raw storage The stability can be improved and the residual salt component after image processing can be reduced, whereby an excellent photothermographic material can be obtained.

The amount of the decolorizable dye that is the compound of the general formula (1) is determined depending on the use of the dye. In general, the optical density (absorbance) measured at the target wavelength is used in an amount exceeding 0.1. The optical density is preferably 0.15 to 2, and more preferably 0.2 to 1. The amount of dye used to obtain such an optical density is generally about 0.001 to 1 g / m ² .

  In addition, when the dye which is the compound of the general formula (1) is decolored in this way, the optical density after heat development can be lowered to 0.1 or less. Two or more kinds of decoloring dyes may be used in combination in a heat decoloring type recording material or a photothermographic material. Similarly, two or more kinds of base precursors may be used in combination.

  There are various types of base precursors that can be used in the present invention. Since the decoloring reaction is carried out under heating conditions, it is preferable to use a type of precursor that generates (or releases) a base by heating. A typical base precursor that generates a base by heating is a thermal decomposition (decarboxylation type) base precursor comprising a salt of a carboxylic acid and a base. When the decarboxylated base precursor is heated, the carboxyl group of the carboxylic acid undergoes a decarboxylation reaction, and the organic base is released. As the carboxylic acid, sulfonylacetic acid or propiolic acid which is easily decarboxylated is used. The sulfonylacetic acid and propiolic acid preferably have, as a substituent, a group having an aromaticity that promotes decarboxylation (an aryl group or an unsaturated heterocyclic group). The base precursor of sulfonyl acetate is described in JP-A-59-168441, and the base precursor of propiolate is described in JP-A-59-180537.

  The base side component of the decarboxylation type base precursor is preferably an organic base, more preferably amidine, guanidine or a derivative thereof. The organic base is preferably a diacid base, a triacid base or a tetraacid base, more preferably a diacid base, and most preferably a diacid base of an amidine derivative or a guanidine derivative.

  A diacid base, a triacid base or a tetraacid base precursor of an amidine derivative is described in JP-B-7-59545. The diacid base, triacid base or tetraacid base precursor of the guanidine derivative is described in JP-B-8-10321.

  The diacid base of the amidine derivative or guanidine derivative comprises (A) two amidine or guanidine moieties, (B) a substituent of the amidine or guanidine moiety and (C) a divalent linking two amidine or guanidine moieties. Consists of a linking group. Examples of the substituent of (B) include an alkyl group (including a cycloalkyl group), an alkenyl group, an alkynyl group, an aralkyl group, and a heterocyclic residue. Two or more substituents may combine to form a nitrogen-containing heterocycle. The linking group of (C) is preferably an alkylene group or a phenylene group.

  Examples of diacid base precursors (BP-1 to BP-39) of amidine derivatives or guanidine derivatives are shown below.

The base precursor may be contained in the coating liquid by any method such as a solution form, an emulsified dispersion form, a solid fine particle dispersion form, etc., but is preferably contained in the coating liquid in a solid fine particle dispersion form. The solid fine particle dispersion method is the same as that in the case of a dye that can be bleached with a base.
The coating amount of the base precursor is 0.001 g / m ² or more and 0.25 g / m ² or less, preferably 0.001 g / m ² or more and 0.21 g / m ² or less, more preferably 0. .001g / m ² or more 0.17 g / m ² or less. When the amount is less than 0.001 g / m ² , the decoloring property is deteriorated. When the amount is more than 0.25 g / m ² , devitrification occurs during storage.
The amount (mole) of the base precursor used in the present invention is preferably 1 to 100 times, more preferably 3 to 30 times the amount (mole) of the dye that can be bleached by the base. preferable.

  Furthermore, in the thermal decoloration using the decoloring dye which is the compound of the general formula (1) and a base precursor, the melting point is 3 ° C. (deg) when mixed with a base precursor as described in JP-A-11-352626. It is preferable from the viewpoint of thermal decoloring property, etc., to use together the substances to be lowered (for example, diphenylsulfone, 4-chlorophenyl (phenyl) sulfone), 2-naphthylbenzoate and the like.

3) Back Layer Back layers that can be applied to the present invention are described in paragraph Nos. 0128 to 0130 of JP-A No. 11-65021.

In the present invention, a colorant having an absorption maximum at 300 to 450 nm can be added for the purpose of improving the silver color tone and the temporal change of the image. Such colorants are disclosed in JP-A-62-210458, JP-A-63-104046, JP-A-63-103235, JP-A-63-208846, JP-A-63-306436, JP-A-63-141435, and JP-A-01-61745. No. 1, Japanese Patent Laid-Open No. 2001-100363, and the like.
Such a colorant is usually added in a range of 0.1 mg / m ² or more and 1 g / m ² or less, and the layer to be added is preferably a back layer provided on the opposite side of the image forming layer.
In order to adjust the base color tone, it is preferable to use a dye having an absorption peak at 580 to 680 nm. As the dye for this purpose, azomethine oil-soluble dyes described in JP-A-4-359967 and JP-A-4-359968, which have a small absorption intensity on the short wavelength side, and phthalocyanine water-soluble dyes described in Japanese Patent Application No. 2002-96797 are preferable. The dye for this purpose may be added to any layer, but is more preferably added to the non-photosensitive layer on the emulsion surface side or the back surface side.

  The photothermographic material of the present invention is a so-called single-sided photosensitive material having an image forming layer containing at least one silver halide emulsion on one side of a support and a back layer on the other side. preferable.

4) Matting Agent In the present invention, it is preferable to add a matting agent for improving transportability, and the matting agent is described in paragraph Nos. 0126 to 0127 of JP-A No. 11-65021. The matting agent is preferably 1 mg / m ² or more and 400 mg / m ² or less, more preferably 5 mg / m ² or more and 300 mg / m ² or less when expressed in terms of the coating amount per 1 m ² of the photosensitive material.
In the present invention, the shape of the matting agent may be either a regular shape or an irregular shape, but is preferably a regular shape, and a spherical shape is preferably used.
The volume weighted average of the equivalent sphere diameters of the matting agent used on the emulsion surface is preferably from 0.3 μm to 10 μm, and more preferably from 0.5 μm to 7 μm. The variation coefficient of the size distribution of the matting agent is preferably 5% or more and 80% or less, and more preferably 20% or more and 80% or less. Here, the coefficient of variation is a value represented by (standard deviation of particle size) / (average value of particle size) × 100. Further, two or more kinds of matting agents having different average grain sizes can be used as the matting agent on the emulsion surface. In that case, the difference in particle size between the matting agent having the largest average particle size and the smallest matting agent is preferably 2 μm or more and 8 μm or less, and more preferably 2 μm or more and 6 μm or less.
The volume weighted average of the equivalent sphere diameters of the matting agent used for the back surface is preferably 1 μm or more and 15 μm or less, and more preferably 3 μm or more and 10 μm or less. The variation coefficient of the size distribution of the matting agent is preferably 3% or more and 50% or less, and more preferably 5% or more and 30% or less. Further, two or more types of matting agents having different average particle sizes can be used as the matting agent for the back surface. In this case, the difference in particle size between the matting agent having the largest average particle size and the smallest matting agent is preferably 2 μm or more and 14 μm or less, and more preferably 2 μm or more and 9 μm or less.

  The emulsion surface may have any matte degree as long as no stardust failure occurs, but the Beck smoothness is preferably 30 seconds or more and 2000 seconds or less, and particularly preferably 40 seconds or more and 1500 seconds or less. The Beck smoothness can be easily determined by Japanese Industrial Standard (JIS) P8119 “Smoothness test method using Beck tester for paper and paperboard” and TAPPI standard method T479.

  In the present invention, the matte degree of the back layer is preferably a Beck smoothness of 1200 seconds or less and 10 seconds or more, preferably 800 seconds or less and 20 seconds or more, and more preferably 500 seconds or less and 40 seconds or more.

  In the present invention, the matting agent is preferably contained in the outermost surface layer of the photosensitive material, the layer functioning as the outermost surface layer, or a layer close to the outer surface, and also contained in a layer acting as a so-called protective layer. It is preferable.

5) Polymer Latex When the photothermographic material of the present invention is used for printing applications in which dimensional change is a problem, it is preferable to use a polymer latex for the surface protective layer or the back layer. For such polymer latex, “Synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Publishing (1978))”, “Application of synthetic latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, Takashi "Molecular Publications (1993))" and "Synthetic Latex Chemistry (Muroichi Muroi, published by High Polymers Publication (1970))", specifically, methyl methacrylate (33.5% by mass) / Ethyl acrylate (50 wt%) / methacrylic acid (16.5 wt%) copolymer latex, methyl methacrylate (47.5 wt%) / butadiene (47.5 wt%) / itaconic acid (5 wt%) copolymer Latex, latex of ethyl acrylate / methacrylic acid copolymer, methyl methacrylate (58.9% by mass) / 2-ethyl Latex of xyl acrylate (25.4 mass%) / styrene (8.6 mass%) / 2-hydroxyethyl methacrylate (5.1 mass%) / acrylic acid (2.0 mass%) copolymer, methyl methacrylate (64. 0 mass%) / styrene (9.0 mass%) / butyl acrylate (20.0 mass%) / 2-hydroxyethyl methacrylate (5.0 mass%) / acrylic acid (2.0 mass%) copolymer latex, etc. Is mentioned. Furthermore, as a binder for the surface protective layer, a combination of polymer latex described in Japanese Patent Application No. 11-6872 and a technique described in Paragraph Nos. 0021 to 0025 of Japanese Patent Application Laid-Open No. 2000-267226, Japanese Patent Application No. 11-6872 The technology described in paragraph numbers 0027 to 0028 of the specification and the technology described in paragraph numbers 0023 to 0041 of JP 2000-19678 may be applied. The ratio of the polymer latex in the surface protective layer is preferably 10% by mass or more and 90% by mass or less, and particularly preferably 20% by mass or more and 80% by mass or less of the total binder.

6) Membrane pH
The photothermographic material of the present invention preferably has a film surface pH of 7.0 or less, more preferably 6.6 or less before heat development. The lower limit is not particularly limited, but is about 3. The most preferred pH range is in the range of 4 to 6.2. For the adjustment of the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, and a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is volatile and is preferable for achieving a low film surface pH because it can be removed before the coating process or heat development.
In addition, it is also preferable to use ammonia in combination with a nonvolatile base such as sodium hydroxide, potassium hydroxide, or lithium hydroxide. In addition, the measuring method of film surface pH is described in paragraph number 0123 of Unexamined-Japanese-Patent No. 2000-284399.

7) Hardener A hardener may be used in each layer such as the image forming layer, protective layer, and back layer in the present invention. Examples of hardeners include T.W. H. There are various methods described in "THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION" written by James (published by Macmillan Publishing Co., Inc., published in 1977), pages 77 to 87. -S-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N, N-propylenebis (vinylsulfoneacetamide), polyvalent metal ions described on page 78 of the same, U.S. Pat. No. 4,281, Polyisocyanates such as 060 and JP-A-6-208193, epoxy compounds such as US Pat. No. 4,791,042, and vinyl sulfone compounds such as JP-A 62-89048 are preferably used.

  The hardening agent is added as a solution, and the addition time of this solution into the protective layer coating solution is from 180 minutes before to immediately before application, preferably from 60 minutes to 10 seconds before application. As long as the effects of the present invention are sufficiently exhibited, there is no particular limitation. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid fed to the coater is a desired time, and N.I. Harnby, M.M. F. Edwards, A.D. W. There is a method using a static mixer described in Chapter 8 of Nienow's “Liquid Mixing Technology” (Nikkan Kogyo Shimbun, 1989), translated by Koji Takahashi.

8) Surfactant As for the surfactant applicable to the present invention, paragraph No. 0132 of JP-A No. 11-65021, paragraph No. 0133 of the solvent, paragraph No. 0134 of the support, antistatic or conductive layer Are described in paragraph No. 0135 of the same number, paragraph No. 0136 of the same number about the method of obtaining a color image, paragraph Nos. 0061 to 0064 of JP-A No. 11-84573 and paragraph Nos. 0049 to 0062 of JP-A No. 2001-83679 about the slip agent. ing.
In the present invention, it is preferable to use a fluorosurfactant. Specific examples of the fluorosurfactant include compounds described in JP-A Nos. 10-197985, 2000-19680, 2000-214554 and the like. Further, a polymeric fluorine-based surfactant described in JP-A-9-281636 is also preferably used. In the photothermographic material of the present invention, it is preferable to use a fluorosurfactant described in JP-A No. 2002-82411, JP-A No. 2003-057780, and Japanese Patent Application No. 2002-074564. In particular, the fluorosurfactants described in JP-A No. 2003-057780 and Japanese Patent Application No. 2001-264110 are preferable in terms of charge adjustment ability, stability of the coated surface, and smoothness when coating and production is performed with an aqueous coating solution. The fluorine-containing surfactant described in Japanese Patent Application No. 2001-264110 is most preferable in that it has a high charge adjustment capability and requires a small amount of use.
In the present invention, the fluorosurfactant can be used on either the emulsion surface or the back surface, and is preferably used on both surfaces. Further, it is particularly preferable to use in combination with a conductive layer containing the above-described metal oxide. In this case, sufficient performance can be obtained even if the amount of the fluorosurfactant used on the surface having the conductive layer is reduced or removed.
The preferred amount of the fluorocarbon surfactant is emulsion surface, ranging back surface each ^{0.1mg / m 2 ~100mg / m 2} , more preferably 0.3mg / m ² ~30mg / m ² range, further preferably in the range of ^{1mg / m 2 ~10mg / m 2} . Especially, the fluorocarbon surfactant described in Japanese Patent Application No. 2001-264110 is effective, and preferably in the range of 0.01 to 10 mg / m ^2, the range of 0.1 to 5 mg / m ² is more preferable.

9) Antistatic agent In this invention, it is preferable to have a conductive layer containing a metal oxide or a conductive polymer. The antistatic layer may serve as an undercoat layer, a back layer surface protective layer, or the like, or may be provided separately. As the conductive material for the antistatic layer, a metal oxide in which conductivity is improved by introducing oxygen defects or different metal atoms into the metal oxide is preferably used. Examples of metal oxides are preferably ZnO, TiO ₂ and SnO _2. Addition of Al and In to ZnO, addition of Sb, Nb, P and halogen elements to SnO ₂ , and addition to TiO _2. For example, addition of Nb, Ta or the like is preferable. In particular, SnO ₂ added with Sb is preferable. The amount of different atoms added is preferably in the range of 0.01 to 30 mol%, more preferably in the range of 0.1 to 10 mol%. The shape of the metal oxide may be spherical, needle-like, or plate-like, but the long axis / uniaxial ratio is 2.0 or more, preferably 3.0 to 50 in terms of the effect of imparting conductivity. Good. Range amount preferably of 1mg / m ² ~1000mg / m ² of metal oxide, more preferably 10mg / m ² ~500mg / m ² range, more preferably at 20mg / m ² ~200mg / m ² It is a range. The antistatic layer in the present invention may be disposed on either the emulsion surface side or the back surface side, but is preferably disposed between the support and the back layer. Specific examples of the antistatic layer include those described in paragraph No. 0135 of JP-A No. 11-65021, JP-A Nos. 56-143430, 56-143431, 58-62646, No. 56-120519, and JP-A No. 11-84573. Paragraph Nos. 0040 to 0051, US Pat. No. 5,575,957, and paragraph Nos. 0078 to 0084 of JP-A-11-223898.

10) Support The transparent support was subjected to a heat treatment in a temperature range of 130 to 185 ° C. in order to relieve internal strain remaining in the film during biaxial stretching and to eliminate heat shrinkage strain generated during heat development processing. Polyester, particularly polyethylene terephthalate is preferably used. In the case of a photothermographic material for medical use, the transparent support may be colored with a blue dye (for example, dye-1 described in Examples of JP-A-8-240877) or may be uncolored. Examples of the support include water-soluble polyesters disclosed in JP-A-11-84574, styrene-butadiene copolymers described in JP-A-10-186565, and vinylidene chloride described in JP-A-2000-39684 and Japanese Patent Application No. 11-106881, paragraphs 0063-0080. It is preferable to apply an undercoating technique such as a copolymer. When the image forming layer or the back layer is applied to the support, the moisture content of the support is preferably 0.5% by mass or less.

11) Other additives An antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber or a coating aid may be further added to the photothermographic material. Various additives are added to either the image forming layer or the non-photosensitive layer. With respect to these, WO 98/36322, EP 803764A1, JP-A-10-186567, 10-18568 and the like can be referred to.

12) Coating method The photothermographic material in the invention may be coated by any method. Specifically, various coating operations including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. And Stephen F. Kistler, Peter M. et al. Extrusion coating or slide coating described in pages 399 to 536 of “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) by Schweizer is preferably used, and slide coating is particularly preferably used. An example of the shape of a slide coater used for slide coating is shown in FIG. 11b. 1 If desired, two or more layers can be coated simultaneously by the method described on pages 399 to 536 of the same document, the method described in US Pat. No. 2,761,791 and British Patent No. 837,095. . In the present invention, particularly preferred coating methods are those described in JP-A Nos. 2001-194748, 2002-153808, 2002-153803, and 2002-182333.

The image forming layer coating solution in the present invention is preferably a so-called thixotropic fluid. Regarding this technique, JP-A-11-52509 can be referred to. In the image forming layer coating solution of the present invention, the viscosity at a shear rate of 0.1 S ⁻¹ is preferably 400 mPa · s or more and 100,000 mPa · s or less, more preferably 500 mPa · s or more and 20,000 mPa · s or less. Further, at a shear rate of 1000 S ⁻¹ , 1 mPa · s to 200 mPa · s is preferable, and 5 mPa · s to 80 mPa · s is more preferable.

In the case of preparing a coating liquid, a known in-line mixer or implant mixer is preferably used when mixing two kinds of liquids. A preferable in-line mixer in the present invention is described in JP-A No. 2002-85948, and an implant mixer is described in JP-A No. 2002-90940.
The coating solution in the present invention is preferably subjected to defoaming treatment in order to keep the coated surface state good. A preferable defoaming treatment method in the present invention is the method described in JP-A No. 2002-66431.
When applying the coating solution, it is preferable to perform static elimination in order to prevent adhesion of dust, dust, and the like due to electric resistance of the support. An example of a preferable static elimination method in the present invention is described in JP-A No. 2002-143747.
In the present invention, it is important to precisely control the drying air and the drying temperature in order to dry the non-setting image forming layer coating solution. Preferred drying methods in the present invention are described in detail in JP-A Nos. 2001-194749 and 2002-139814.
The photothermographic material of the present invention is preferably subjected to a heat treatment immediately after coating and drying in order to improve film formability. The temperature of the heat treatment is preferably in the range of 60 ° C. to 100 ° C. as the film surface temperature, and the heating time is preferably in the range of 1 second to 60 seconds. A more preferable range is a film surface temperature of 70 to 90 ° C. and a heating time of 2 to 10 seconds. A preferable heat treatment method in the present invention is described in JP-A No. 2002-107872.
In order to stably and continuously produce the photothermographic material of the present invention, the production methods described in JP-A Nos. 2002-156728 and 2002-182333 are preferably used.

  The photothermographic material is preferably a mono-sheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material).

13) Packaging material The photosensitive material of the present invention is packaged with a packaging material having a low oxygen permeability and / or moisture permeability in order to suppress fluctuations in photographic performance during raw storage or to improve curling, curling, etc. It is preferable. The oxygen permeability is preferably 50 ml / atm · m ² · day or less at 25 ° C., more preferably 10 ml / atm · m ² · day or less, more preferably 1.0 ml / atm · m ² · day or less. is there. The moisture permeability is preferably 10 g / atm · m ² · day or less, more preferably 5 g / atm · m ² · day or less, and still more preferably 1 g / atm · m ² · day or less.
Specific examples of the packaging material having low oxygen permeability and / or moisture permeability are disclosed in, for example, JP-A-8-254793. This is a packaging material described in JP-A-2000-206653.
14) Other available technologies

  Techniques that can be used for the photothermographic material of the present invention include EP80364A1, EP883022A1, WO98 / 36322, JP56-62648, 58-62644, JP9-43766, and 9-. 281637, 9-297367, 9-304869, 9-311405, 9-329865, 10-10669, 10-62899, 10-69023, 10-186568, 10-90823, 10-171106, 10-186565, 10-186567, 10-186567 to 10-186572, 10-197974, 10-197982, 10 -197983, 10-197985 to 10-197987, 10- 07001, 10-207004, 10-221807, 10-282601, 10-288823, 10-288824, 10-307365, 10-312038, 10-339934 11-7100, 11-15105, 11-24200, 11-24201, 11-30201, 11-30832, 11-84574, 11-65021, 11-109547, 11-125880, 11-129629, 11-133536 to 11-133539, 11-133542, 11-133543, 11-223898, 11-352627, 11- 305377, 11-305378, 11-305384, 11-30538 11-316435, 11-327076, 11-338096, 11-338098, 11-338099, 11-343420, 2000-187298, 2001-200414, 2001-234635, 2002-020699, 2001-275471, 2001-275461, 2000-313204, 2001-292844, 2000-324888, 2001-293864, 2001 -348546 is also mentioned.

In the case of multicolor color photothermographic materials, each image-forming layer is generally a functional or non-functional barrier between each photosensitive layer as described in US Pat. No. 4,460,681. By using layers, they are kept distinct from each other.
The construction in the case of a multicolor color photothermographic material may include a combination of these two layers for each color and all within a single layer as described in US Pat. No. 4,708,928. Ingredients may be included.

(Image forming method)
1) Exposure Red to infrared emission He—Ne laser, red semiconductor laser, blue to green emission Ar ⁺ , He—Ne, He—Cd laser, blue semiconductor laser. Preferred is a red to infrared semiconductor laser, and the peak wavelength of the laser light is 600 nm to 900 nm, preferably 620 nm to 850 nm.
On the other hand, in recent years, in particular, a module in which an SHG (Second Harmonic Generator) element and a semiconductor laser are integrated and a blue semiconductor laser have been developed, and a laser output device in a short wavelength region has been closed up. The blue semiconductor laser is expected to increase in demand in the future because high-definition image recording is possible, the recording density is increased, and a stable output is obtained with a long lifetime. The peak wavelength of the blue laser light is preferably 300 nm to 500 nm, particularly preferably 400 nm to 500 nm.
It is also preferable that the laser light is oscillated in a vertical multi by a method such as high frequency superposition.

2) Photothermographic development The photothermographic material of the present invention may be developed by any method, but is usually developed by raising the temperature of the photothermographic material exposed imagewise. The preferred development temperature is 80 to 250 ° C, preferably 100 to 140 ° C, more preferably 110 to 130 ° C. The development time is preferably 1 to 60 seconds, more preferably 3 to 30 seconds, still more preferably 5 to 25 seconds, and 7 to 15 seconds.

  Either a drum type heater or a plate type heater may be used as the thermal development method, but the plate type heater method is more preferable. The heat development method using the plate type heater method is preferably a method described in JP-A-11-133572, and a visible image is obtained by bringing a photothermographic material having a latent image formed thereon into contact with a heating means in a heat developing unit. In the heat development apparatus, the heating unit includes a plate heater, and a plurality of press rollers are disposed to face each other along one surface of the plate heater, and the press roller is disposed between the press roller and the plate heater. A heat development apparatus characterized in that heat development is performed by passing a photothermographic material. It is preferable to divide the plate heater into 2 to 6 stages and lower the temperature about 1 to 10 ° C. at the tip. For example, there are examples in which four sets of plate heaters that can be independently controlled are used and controlled so as to be 112 ° C., 119 ° C., 121 ° C., and 120 ° C. Such a method is also described in JP-A-54-30032, which can exclude moisture and organic solvents contained in the photothermographic material out of the system, and rapidly develop the photothermographic material. It is also possible to suppress a change in the shape of the support of the photothermographic material due to the heating.

  In order to reduce the size of the heat developing machine and shorten the heat development time, it is preferable to be able to control the heater more stably. In addition, the exposure of one sheet of photosensitive material is started from the top and the exposure is finished to the back end. It is desirable to start the heat development before the time. Imagers capable of rapid processing preferred in the present invention are described in, for example, Japanese Patent Application Nos. 2001-088832 and 091114. If this imager is used, for example, heat development can be performed in 14 seconds with a three-stage plate heater controlled at 107 ° C.-121 ° C.-121 ° C., and the output time of the first sheet is reduced to about 60 seconds. be able to. For such rapid development processing, it is preferable to use the photothermographic material-2 of the present invention in combination with high sensitivity and less susceptible to environmental temperature.

3) System As a medical laser imager provided with an exposure part and a heat development part, Fuji Medical Dry Laser Imager FM-DPL and DRYPIX7000 can be exemplified. Regarding FM-DPL, Fuji Medical Review No. 8, pages 39 to 55, and it goes without saying that those techniques are applied as a laser imager of the photothermographic material of the present invention. Further, it can also be applied as a photothermographic material for a laser imager in “AD network” proposed by Fuji Film Medical Co., Ltd. as a network system adapted to the DICOM standard.

(Use of the present invention)
The silver halide photographic light-sensitive material and heat-developable light-sensitive material of the present invention form a black-and-white image with a silver image, and are used for medical diagnosis, heat-developable light-sensitive material for industrial photography, heat-developable light-sensitive material for printing, COM It is preferably used as a photothermographic material.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
(Example 1)

(Preparation of PET support)
1) Film formation Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) is obtained. It was. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled to prepare an unstretched film.

This was longitudinally stretched 3.3 times using rolls with different peripheral speeds, and then stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit and then knurled at both ends, and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

2) Surface corona treatment Both surfaces of the support were treated at room temperature at 20 m / min using a solid state corona treatment machine 6KVA model manufactured by Pillar. From the current and voltage readings at this time, it was found that the support was processed at 0.375 kV · A · min / m ² . The treatment frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

3) Undercoat 1) Preparation formulation of undercoat layer coating solution (1) (for image forming layer side undercoat layer)
・ Pesresin A-520 (30% by mass solution) manufactured by Takamatsu Yushi Co., Ltd. 46.8 g
・ Toyobo Co., Ltd. Bironal MD-1200 10.4 g
Polyethylene glycol monononyl phenyl ether (average ethylene oxide number = 8.5) 1% by weight solution 11.0 g
・ MP-1000 (PMMA polymer fine particles, average particle size 0.4 μm) 0.91 g manufactured by Soken Chemical Co., Ltd.
・ 931 ml of distilled water

Formula (2) (for back layer 1st layer)
・ Styrene-butadiene copolymer latex 130.8 g
(Solid content 40% by mass, styrene / butadiene weight ratio = 68/32)
2,4-dichloro-6-hydroxy-S-triazine sodium salt
8% by weight aqueous solution 5.2g
・ 10% 1% by weight aqueous solution of sodium laurylbenzenesulfonate
・ Polystyrene particle dispersion (average particle size 2 μm, 20 mass%) 0.5 g
-854 ml of distilled water

Formula (3) (for back side second layer)
SnO ₂ / SbO (9/1 mass ratio, average particle size 0.5 μm, 17 mass% dispersion)
84g
・ Gelatin 7.9g
・ Shin-Etsu Chemical Co., Ltd. Metros TC-5 (2 mass% aqueous solution) 10g
・ 10% 1% aqueous solution of sodium dodecylbenzenesulfonate
・ NaOH (1% by mass) 7 g
・ Proxel (Abyssia) 0.5g
・ Distilled water 881ml

After both surfaces of the biaxially stretched polyethylene terephthalate support having a thickness of 175 μm are subjected to the corona discharge treatment, the undercoat coating solution formulation (1) is applied on one side (image forming layer surface) with a wire bar with a wet coating amount of 6. .6ml / m ² was applied (per one side) and dried for 5 minutes at 180 ° C., then the amount of wet coating the coating solution for the undercoat was coated (2) by a wire bar on the rear surface (back surface) 5. Apply to 7 ml / m ² , dry at 180 ° C. for 5 minutes, and further wet coat amount of 8.4 ml / m ² with the above-mentioned undercoat coating liquid formulation (3) on the back surface (back surface) with a wire bar. It was applied as described above and dried at 180 ° C. for 6 minutes to prepare an undercoat support.

(Back layer)
1) Preparation of back layer coating solution (preparation of solid fine particle dispersion (a) of base precursor)
Add 2.5 kg of Base Precursor Compound 1 and 300 g of a surfactant (trade name: Demol N, manufactured by Kao Corporation), 800 g of diphenylsulfone, 1.0 g of benzoisothiazolinone sodium salt and distilled water to make a total amount. The mixture was mixed to 8.0 kg, and the mixed solution was dispersed with beads using a horizontal sand mill (UVM-2: manufactured by Imex Corporation). In the dispersion method, the mixed solution was fed to UVM-2 filled with zirconia beads having an average diameter of 0.5 mm by a diaphragm pump, and dispersed at an internal pressure of 50 hPa or more until a desired average particle size was obtained.
The dispersion was subjected to spectral absorption measurement, and the ratio of absorbance at 450 nm to absorbance at 650 nm (D450 / D650) in the spectral absorption of the dispersion was dispersed to 3.0. The obtained dispersion was diluted with distilled water so that the concentration of the base precursor was 25% by weight, and was filtered for removal of dust (polypropylene filter having an average pore size of 3 μm) for practical use.

(Preparation of solid dispersion <dye solid fine particle dispersion>)
<< Preparation of Solid Dispersion-1 >>
6.0 kg of a cyanine dye having a cation part and an anion part in Table 1, 3.0 kg of a surfactant Demol SNB manufactured by Kao Corporation, and an antifoaming agent (trade names: Surfynol 104E, manufactured by Nisshin Chemical Co., Ltd.) ) 0.08 kg was mixed with distilled water to make a total liquid volume of 60 kg. Using a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with 0.5 mm zirconia beads, the mixture was dispersed at 20 ° C. for 7.5 hours per kg of cyanine dye. The ratio of the absorbance at 650 nm to the absorbance at 750 nm (D650 / D750) was calculated by measuring the spectral absorption of this dispersion and found to be 4.2. The obtained dispersion was diluted with distilled water so that the concentration of the cyanine dye was 6% by mass, filtered to remove dust (average pore size: 1 μm), and then solid dispersion (hereinafter referred to as “dye fine particles”). Also referred to as “dispersion”.

<< Preparation of solid dispersions 2 to 11 >>
In the preparation of the solid dispersion-1, except that the general formula (2) described in Table 1, the dispersant, the water-soluble polymer dispersion, the dispersion time, the dispersion temperature and the dye concentration were as shown in Table 1, A solid dispersion was prepared in the same manner.

<< Preparation of Solid Dispersion-12 >>
6.0 kg of the general formula (2) cyanine dye in Table 1, 3.0 kg of the compound of the general formula (3) as BM, and an antifoaming agent (trade name: Surfynol 104E, manufactured by Nissin Chemical Co., Ltd.) 08 kg was mixed with distilled water to make a total liquid volume of 60 kg. Using a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with 0.5 mm zirconia beads, the mixture was dispersed at 20 ° C. for 7.5 hours per kg of cyanine dye. The dispersion was measured for spectral absorption, and the ratio of the absorbance at 650 nm to the absorbance at 750 nm (D650 / D750) was calculated to be 5.0. The obtained dispersion was diluted with distilled water so that the concentration of the cyanine dye was 6% by mass, filtered to remove dust (average pore size: 1 μm), and then solid dispersion (hereinafter referred to as “dye fine particles”). Also referred to as “dispersion”.

<< Preparation of Solid Dispersions-13-29 >>
In the preparation of Solid Dispersion-12, the same applies except that the general formula (2), the general formula (3), the water-soluble polymer dispersant, the dispersion time, and the dye concentration are changed as shown in Table 1. A solid dispersion was obtained.

<< Preparation of Solid Dispersion-30 >>
6.0 kg of the compound of the general formula (1) in Table 2, 15 kg of a 10% by mass solution of a water-soluble polymer dispersant (trade name: MP-203, manufactured by Kuraray Co., Ltd.), and an antifoaming agent (trade name) : Surfinol 104E, manufactured by Nissin Chemical Co., Ltd.) was mixed with distilled water to make a total liquid volume of 60 kg. The mixed solution was dispersed using a horizontal sand mill (UVM-2: manufactured by Imex Corporation) filled with 0.5 mm zirconia beads. The absorbance ratio (D650 / D750) was calculated by measuring the spectral absorption of the dispersion and found to be 5.2. Then, it diluted with distilled water so that it might become 6 mass% in the density | concentration of a cyanine dye, and filter filtration (average pore diameter: 1 micrometer) was performed for dust removal, and the solid dispersion was obtained.

<< Preparation of solid dispersions 31-45 >>
In the preparation of Solid Dispersion-30, it was prepared in the same manner except that the general formula (1), the general formula (3), the water-soluble polymer dispersant, the dispersion time, and the dye concentration were changed as shown in Table 2. A solid dispersion was obtained.

(Preparation of antihalation layer coating solution-1)
The container is kept at 40 ° C., and gelatin is dissolved by adding 40 g of gelatin, 20 g of monodisperse polymethyl methacrylate fine particles (average particle size 8 μm, particle size standard deviation 0.4), 0.1 g of benzoisothiazolinone, and 490 ml of water. It was. Further, 2.3 ml of 1 mol / l sodium hydroxide aqueous solution, 40 g of the above solid dispersion-1, 90 g of the solid fine particle dispersion (a) of the above base precursor, 12 ml of 3% by weight aqueous solution of sodium polystyrenesulfonate, 10 mass of SBR latex % Liquid 180 g was mixed. Immediately before coating, 80 ml of a 4% by weight aqueous solution of N, N-ethylenebis (vinylsulfonacetamide) was mixed to prepare a coating solution for preventing halation.

(Preparation of antihalation layer coating solution-2 to 45)
An antihalation layer coating solution was obtained in the same manner as in the antihalation layer coating solution-1, except that solid dispersions 2 to 45 were used instead of the solid dispersion-1.

2) Preparation of back surface protective layer coating solution The container was kept at 40 ° C., and gelatin was dissolved by adding 40 g of gelatin, 35 mg of benzoisothiazolinone, and 840 ml of water. Further, 5.8 ml of 1 mol / l sodium hydroxide aqueous solution, 5 g of 10% by weight emulsion of liquid paraffin, 5 g of 10% by weight emulsion of trimethylolpropane triisostearate, di (2-ethylhexyl) sodium sulfosuccinate 5 10 ml of a mass% aqueous solution, 20 ml of a 3 mass% aqueous solution of sodium polystyrene sulfonate, 2.4 ml of a 2 mass% solution of a fluorosurfactant (F-1), and 2 of a 2 mass% solution of a fluorosurfactant (F-2) .4 ml of methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 57/8/28/5/2) latex 19% by mass 32 g was mixed. Immediately before coating, 25 ml of a 4% by weight aqueous solution of N, N-ethylenebis (vinylsulfonacetamide) was mixed to prepare a coating solution for the back surface protective layer.

3) Application of back layer (production of supports 1 to 45 having a back layer)
On the back surface side of the undercoat support, an antihalation layer coating solution-1 to 45 is applied so that the gelatin coating amount is 0.52 g / m ^2, and the back surface protective layer coating solution is 1.7 g in gelatin coating amount. / M ² was applied simultaneously and dried to prepare a back layer.

<Performance Evaluation of Solid Dispersion of Cyanine Dye>
1. Analysis of production rate of general formula (A) in solid dispersion The solid dispersions 1 to 45 were centrifuged at 40000 rpm for 4 hours, and the anion species contained in the supernatant was analyzed by ion chromatography. The ratio of the analytical amount to the theoretical amount was defined as the dye production rate (also referred to as “salt exchange rate”) of the general formula (A). The results are shown in Tables 1 and 2.

2. Evaluation of the dispersibility of the solid dispersion After diluting the dispersion with the value of the ratio of the absorbance and the dispersion 100 times, the presence or absence of aggregation was observed with an optical microscope. Dispersibility was evaluated in the following five stages. The results are shown in Tables 1 and 2.
(Evaluation criteria)
1: Aggregation occurs at the time of solid dispersion and is not practical.
2: A level at which agglomeration occurs in the dispersion and is unstable and not yet practical.
3: Some dispersions have a slightly larger particle size and are practically possible.
4: Level that can be dispersed relatively finely and can be manufactured almost stably.
5: A level at which no aggregation is observed in the dispersion and it can be stably produced.

3. Evaluation of sedimentation property of solid dispersion After placing the sedimentation property in the solid dispersions 1 to 45 in a glass tube and standing for one month at room temperature, the presence and state of sediment at the bottom were confirmed, and Evaluation was performed based on evaluation criteria (5 levels). The evaluation results are shown in Tables 1 and 2 below.
(Evaluation criteria)
1: A level in which a hard precipitate is generated during storage and cannot be uniformly mixed with simple stirring, and the concentration of the liquid part decreases.
2: The amount of sediment is less than 1, but it cannot be mixed uniformly with simple stirring.
3: A slight amount of sediment is formed, but it can be mixed uniformly with simple stirring, which is a practically acceptable level.
4: Level where almost no sediment is generated during storage.
5: Good level with very little stabilization over time and very stabilized.

From the results of Tables 1 and 2, the dispersion No. From 1 to 11, the salt exchange rate is low, and the dispersibility and sedimentation stability are also poor.
Dispersion No. In 12-45, dispersibility is good and sedimentation stability is also good.
In particular, when the dye concentration is 10% by mass or more and the production rate of the general formula (1) is 60 mol% or more using a water-soluble polymer dispersant, both dispersibility and sedimentation are even better.

(Image forming layer, intermediate layer, and surface protective layer)
1. Preparation of coating materials 1) Silver halide emulsion << Preparation of silver halide emulsion 1 >>
A solution prepared by adding 3.1 ml of 1% by mass potassium bromide solution to 1421 ml of distilled water and further adding 3.5 ml of 0.5 mol / L sulfuric acid and 31.7 g of phthalated gelatin was stirred in a stainless steel reaction vessel. While maintaining the liquid temperature at 30 ° C., the solution A diluted with 92.2 ml of distilled water added to 22.22 g of silver nitrate, 15.3 g of potassium bromide and 0.8 g of potassium iodide in a distilled water volume of 97.4 ml. Solution B diluted in a total amount was added at a constant flow rate over 45 seconds. Thereafter, 10 ml of a 3.5% by mass aqueous hydrogen peroxide solution was added, and 10.8 ml of a 10% by mass aqueous solution of benzimidazole was further added. Further, a solution C in which distilled water was added to 51.86 g of silver nitrate to be diluted to 317.5 ml, a solution D in which 44.2 g of potassium bromide and 2.2 g of potassium iodide were diluted with distilled water to a volume of 400 ml was added to solution C. Was added at a constant flow rate over 20 minutes, and solution D was added by the controlled double jet method while maintaining pAg at 8.1. The total amount of potassium hexachloroiridium (III) was added 10 minutes after the start of the addition of Solution C and Solution D so that it would be 1 × 10 ⁻⁴ mole per mole of silver. Further, 5 seconds after the completion of the addition of the solution C, an aqueous solution of potassium iron (II) hexacyanide was added in an amount of 3 × 10 ⁻⁴ mol per mol of silver. The pH was adjusted to 3.8 using 0.5 mol / L sulfuric acid, stirring was stopped, and a precipitation / desalting / water washing step was performed. The pH was adjusted to 5.9 with 1 mol / L sodium hydroxide to prepare a silver halide dispersion having a pAg of 8.0.

The silver halide dispersion was maintained at 38 ° C. with stirring, 5 ml of a 0.34 mass% 1,2-benzisothiazolin-3-one methanol solution was added, and the temperature was raised to 47 ° C. after 40 minutes. 20 minutes after the temperature increase, sodium benzenethiosulfonate was added in a methanol solution to 7.6 × 10 ⁻⁵ moles per 1 mole of silver, and 5 minutes later, tellurium sensitizer C was added in a methanol solution at a rate of 2. per mol of silver. 9 × 10 ⁻⁴ mol was added and aged for 91 minutes. Thereafter, a methanol solution having a molar ratio of the spectral sensitizing dye A and the sensitizing dye B of 3: 1 was added in a total amount of 1.2 × 10 ⁻³ moles of the sensitizing dyes A and B per mole of silver. , N'-dihydroxy-N "-diethylmelamine in 1.3 ml of a 0.8 wt% methanol solution was added, and after another 4 minutes, 5-methyl-2-mercaptobenzimidazole was added to the methanol solution at a rate of 4.8 per mole of silver. × 10 ⁻³ mol, 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in methanol solution is 5.4 × 10 ⁻³ mol and 1- (3-methyl) with respect to 1 mol of silver. A silver halide emulsion 1 was prepared by adding 8.5 × 10 ⁻³ mol of ureidophenyl) -5-mercaptotetrazole in an aqueous solution to 1 mol of silver.

  The grains in the prepared silver halide emulsion were silver iodobromide grains containing 3.5 mol% of iodine having an average sphere equivalent diameter of 0.042 μm and a sphere equivalent diameter variation coefficient of 20%. The particle size and the like were determined from an average of 1000 particles using an electron microscope. The {100} face ratio of the particles was determined to be 80% using the Kubelka-Munk method.

<< Preparation of silver halide emulsion 2 >>
In the preparation of silver halide emulsion 1, the liquid temperature at the time of grain formation was changed from 30 ° C. to 47 ° C., and solution B was changed to diluting 15.9 g of potassium bromide with distilled water to a volume of 97.4 ml, Solution D was changed to diluting 45.8 g of potassium bromide with distilled water to a volume of 400 ml, and the addition time of solution C was changed to 30 minutes to remove potassium hexacyanoiron (II) in the same manner. A silver halide emulsion 2 was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as silver halide emulsion 1. Furthermore, the addition amount of tellurium sensitizer C is 1.1 × 10 ⁻⁴ mol per mol of silver, and the addition amount of methanol solution of 3: 1 in the molar ratio of spectral sensitizing dye A and spectral sensitizing dye B is silver. The total of sensitizing dye A and sensitizing dye B per mole is 7.0 × 10 ⁻⁴ mol, and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole is added to 1 mol of silver. Same as Emulsion 1 except that 3.3 × 10 ⁻³ mol and 1- (3-methylureidophenyl) -5-mercaptotetrazole were changed to 4.7 × 10 ⁻³ mol added to 1 mol of silver. Spectral sensitization, chemical sensitization, and addition of 5-methyl-2-mercaptobenzimidazole and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole were performed to obtain silver halide emulsion 2. . The emulsion grains of the silver halide emulsion 2 were pure silver bromide cubic grains having an average sphere equivalent diameter of 0.080 μm and a sphere equivalent diameter variation coefficient of 20%.

<< Preparation of silver halide emulsion 3 >>
In the preparation of silver halide emulsion 1, silver halide emulsion 3 was prepared in the same manner except that the liquid temperature at the time of grain formation was changed from 30 ° C. to 27 ° C. Further, precipitation / desalting / washing / dispersion was performed in the same manner as silver halide emulsion 1. The molar ratio of spectral sensitizing dye A and spectral sensitizing dye B is 1: 1 as a solid dispersion (gelatin aqueous solution), and the addition amount is 6 × 10 ⁻ as the total of sensitizing dye A and sensitizing dye B per mole of silver. ³ mol, the amount of tellurium sensitizer C added was changed to 5.2 × 10 ⁻⁴ mol per mol of silver, and 3 minutes after the addition of tellurium sensitizer, bromoauric acid was changed to 5 × 10 ⁻⁴ per mol of silver. A silver halide emulsion 3 was obtained in the same manner as Emulsion 1 except that 2 × 10 ⁻³ mol of mol and potassium thiocyanate were added per mol of silver. The emulsion grains of the silver halide emulsion 3 were silver iodobromide grains containing 3.5 mol% of iodine having an average sphere equivalent diameter of 0.034 μm and a sphere equivalent diameter variation coefficient of 20%.

<< Preparation of mixed emulsion A for coating solution >>
70% by weight of silver halide emulsion 1, 15% by weight of silver halide emulsion 2 and 15% by weight of silver halide emulsion 3 were dissolved, and benzothiazolium iodide was dissolved in a 1% by weight aqueous solution of 7% per mole of silver. × 10 ^-3 mol was added.
Further, the amount of the one-electron oxidant produced by one-electron oxidation is 2 × 10 ⁻³ moles per mole of silver halide, each of compounds 1, 2, and 3 capable of emitting one electron or more. Added.
The adsorbing redox compounds 1 and 2 having an adsorbing group and a reducing group were added in an amount of 5 × 10 ⁻³ mol per mol of silver halide.
Further, water was added so that the content of silver halide per 1 kg of the mixed emulsion for coating solution was 38.2 g as silver. 1- (3-Methylureidophenyl) -5-mercaptotetrazole was added so as to be 0.34 g per kg of the mixed emulsion for coating solution.

2) Preparation of fatty acid silver dispersion <Preparation of recrystallized behenic acid>
100 kg of behenic acid (product name Edenor C22-85R) manufactured by Henkel was mixed in 1200 kg of isopropyl alcohol, dissolved at 50 ° C., filtered through a 10 μm filter, cooled to 30 ° C., and recrystallized. The cooling speed during recrystallization was controlled at 3 ° C./hour. The obtained crystals were centrifugally filtered, washed with 100 kg of isopropyl alcohol, and then dried. When the obtained crystals were esterified and subjected to GC-FID measurement, the behenic acid content was 96 mol%, and in addition, lignoceric acid was 2 mol%, arachidic acid was 2 mol%, and erucic acid was 0.001 mol%. It was.

<Preparation of fatty acid silver dispersion>
Recrystallized behenic acid 88 kg, distilled water 422 L, 5 mol / L NaOH aqueous solution 49.2 L and t-butyl alcohol 120 L were mixed and stirred at 75 ° C. for 1 hour to react to obtain sodium behenate solution B. Separately, 206.2 L (pH 4.0) of an aqueous solution containing 40.4 kg of silver nitrate was prepared and kept warm at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of t-butyl alcohol was kept at 30 ° C., and with sufficient stirring, the total amount of the previous sodium behenate solution B and the total amount of silver nitrate aqueous solution were kept at a constant flow rate for 93 minutes 15 Added over seconds and 90 minutes. At this time, only the silver nitrate aqueous solution is added for 11 minutes after the start of the addition of the silver nitrate aqueous solution, and then the addition of the sodium behenate solution B is started. After the addition of the silver nitrate aqueous solution, only the sodium behenate solution B is added for 14 minutes and 15 seconds Was added. At this time, the temperature in the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The pipe of the addition system for the sodium behenate solution B was kept warm by circulating hot water outside the double pipe so that the liquid temperature at the outlet at the tip of the addition nozzle was 75 ° C. Moreover, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution B and the addition position of the silver nitrate aqueous solution were symmetrically arranged around the stirring axis, and were adjusted so as not to contact the reaction solution.

After completion of the addition of the sodium behenate solution B, the mixture was left stirring for 20 minutes at the same temperature, heated to 35 ° C. over 30 minutes, and then aged for 210 minutes. Immediately after completion of aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of filtered water reached 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying.
When the morphology of the obtained silver behenate particles was evaluated by electron microscope photography, the average values were a = 0.21 μm, b = 0.4 μm, c = 0.4 μm, average aspect ratio 2.1, and equivalent sphere diameter. The crystal had a coefficient of variation of 11%. (A, b, and c are the text provisions)

  19.3 kg of polyvinyl alcohol (trade name: PVA-217) and water are added to a wet cake corresponding to a dry solid content of 260 kg to make a total amount of 1000 kg, and then slurried with a dissolver blade, and a pipeline mixer (manufactured by Mizuho Kogyo) : PM-10 type).

Next, the pre-dispersed stock solution is adjusted to a pressure of 1150 kg / cm ² in a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidics International Corporation, using a Z-type interaction chamber) three times. Treatment gave a silver behenate dispersion. The cooling operation was carried out by installing a serpentine heat exchanger before and after the interaction chamber, and adjusting the temperature of the refrigerant to a dispersion temperature of 18 ° C.

3) Preparation of reducing agent dispersion << Preparation of reducing agent-2 dispersion >>
10 mass of reducing agent-1 (6,6′-di-t-butyl-4,4′-dimethyl-2,2′-butylidenediphenol) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10 kg of water was added to 16 kg of% aqueous solution and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a reducing agent concentration of 25% by mass. This dispersion was heated at 40 ° C. for 1 hour, and then further heated at 80 ° C. for 1 hour to obtain a reducing agent-2 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.50 μm and a maximum particle diameter of 1.6 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

4) Preparation of Hydrogen Bonding Compound-1 Dispersion 10 kg of hydrogen bonding compound-1 (tri (4-t-butylphenyl) phosphine oxide) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10 kg of water was added to 16 kg of the aqueous solution and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump, and dispersed for 4 hours in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm. 2 g and water were added to prepare a hydrogen bonding compound concentration of 25% by mass. This dispersion was heated at 40 ° C. for 1 hour and then further heated at 80 ° C. for 1 hour to obtain a hydrogen bonding compound-1 dispersion. The hydrogen bonding compound particles contained in the hydrogen bonding compound dispersion thus obtained had a median diameter of 0.45 μm and a maximum particle diameter of 1.3 μm or less. The obtained hydrogen bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

5) Preparation of Development Accelerator-1 Dispersion 10 kg of Development Accelerator-1 and 20 kg of 10% by weight aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) were added with 10 kg of water and mixed well. To make a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to adjust the concentration of the development accelerator to 20% by mass to obtain a development accelerator-1 dispersion. The development accelerator particles contained in the development accelerator dispersion thus obtained had a median diameter of 0.48 μm and a maximum particle diameter of 1.4 μm or less. The obtained development accelerator dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
6) Preparation of Dispersion of Development Accelerator-2 and Color Adjuster-1 The solid dispersion of Development Accelerator-2 and Color Adjuster-1 was also dispersed by the same method as Development Accelerator-1, each having 20 mass. % And 15% by mass dispersion liquid were obtained.

7) Preparation of polyhalogen compound << Preparation of organic polyhalogen compound-1 dispersion >>
10 kg of organic polyhalogen compound-1 (tribromomethanesulfonylbenzene), 10 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), 0.4 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate, Then, 14 kg of water was added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm. 2 g and water were added to prepare an organic polyhalogen compound concentration of 26% by mass to obtain an organic polyhalogen compound-1 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.41 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust and stored.

<< Preparation of organic polyhalogen compound-2 dispersion >>
10 kg of an organic polyhalogen compound-2 (N-butyl-3-tribromomethanesulfonylbenzoamide), 20 kg of a 10% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), and 20 of sodium triisopropylnaphthalenesulfonate 0.4 kg of a mass% aqueous solution was added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm. 2 g and water were added to prepare an organic polyhalogen compound concentration of 30% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-2 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 1.3 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

8) Preparation of phthalazine compound-1 solution >>
8 kg of modified polyvinyl alcohol MP203 manufactured by Kuraray Co., Ltd. was dissolved in 174.57 kg of water, and then 3.15 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate and 70 mass of phthalazine compound-1 (6-isopropylphthalazine). 14.28 kg of a% aqueous solution was added to prepare a 5% by mass solution of phthalazine compound-1.

9) Preparation of mercapto compound << Preparation of aqueous solution of mercapto compound-1 >>
7 g of mercapto compound-1 (1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt) was dissolved in 993 g of water to obtain a 0.7% by mass aqueous solution.

<< Preparation of Mercapto Compound-2 Aqueous Solution >>
20 g of mercapto compound-2 (1- (3-methylureidophenyl) -5-mercaptotetrazole) was dissolved in 980 g of water to obtain a 2.0 mass% aqueous solution.

10) Preparation of Pigment-1 Dispersion To 64 g of Pigment-1 (CI Pigment Blue 60) and 6.4 g of Kamol Co., Ltd. Demol N, 250 g of water was added and mixed well to obtain a slurry. Prepare 800 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and disperse with a disperser (1/4 G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours. A pigment-1 dispersion was obtained by adjusting the concentration to 5% by mass. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

11) Preparation of SBR latex solution SBR latex was prepared as follows.
In a polymerization kettle of a gas monomer reactor (TAS-2J type manufactured by Pressure Glass Industrial Co., Ltd.), 287 g of distilled water and a surfactant (Pionin A-43-S (manufactured by Takemoto Yushi Co., Ltd.)): solid content 48.5 (Mass%) 7.73 g, 1 mol / liter NaOH 14.06 ml, ethylenediaminetetraacetic acid tetrasodium salt 0.15 g, styrene 255 g, acrylic acid 11.25 g, tert-dodecyl mercaptan 3.0 g were put, the reaction vessel was sealed and the stirring speed was Stir at 200 rpm. After degassing with a vacuum pump and repeating nitrogen gas replacement several times, 108.75 g of 1,3-butadiene was injected and the internal temperature was raised to 60 ° C. A solution obtained by dissolving 1.875 g of ammonium persulfate in 50 ml of water was added thereto, and the mixture was stirred as it was for 5 hours. The temperature was further raised to 90 ° C. and stirred for 3 hours. After the reaction was completed, the internal temperature was lowered to room temperature, and then Na ⁺ ion: NH ₄ ⁺ ion = 1: 1 using 1 mol / liter NaOH and NH ₄ OH. Addition treatment was performed so that the molar ratio was 5.3 (molar ratio), and the pH was adjusted to 8.4. Thereafter, the mixture was filtered through a polypropylene filter having a pore size of 1.0 μm to remove foreign substances such as dust and stored to obtain 774.7 g of SBR latex. When the halogen ions were measured by ion chromatography, the chloride ion concentration was 3 ppm. As a result of measuring the concentration of the chelating agent by high performance liquid chromatography, it was 145 ppm.

  The latex has an average particle size of 90 nm, Tg = 17 ° C., solid content concentration of 44 mass%, equilibrium moisture content at 25 ° C. and 60% RH, 0.6 mass%, ion conductivity of 4.80 mS / cm (measurement of ion conductivity is A latex stock solution (44 mass%) was measured at 25 ° C. using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd.).

  SBR latexes having different Tg can be prepared in the same manner by appropriately changing the ratio of styrene and butadiene.

2. Preparation of coating solution 1) Preparation of coating solution for image forming layer 1000 g of fatty acid silver dispersion obtained above, 135 ml of water, 36 g of pigment-1 dispersion, 25 g of organic polyhalogen compound-1 dispersion, and dispersion of organic polyhalogen compound-2 39 g, phthalazine compound-1 solution 171 g, SBR latex (Tg: 17 ° C.) liquid 1060 g, reducing agent-2 dispersion 153 g, hydrogen bonding compound-1 dispersion 55 g, development accelerator-1 dispersion 4.8 g, Development accelerator-2 dispersion 5.2g, color tone modifier-1 dispersion 2.1g, mercapto compound-2 aqueous solution 8ml was added in order, and silver halide mixed emulsion A140g was added immediately before coating and mixed well. The forming layer coating solution was directly fed to the coating die and applied.
The viscosity of the image forming layer coating solution was 40 [mPa · s] at 40 ° C. (No. 1 rotor, 60 rpm) as measured with a B-type viscometer of Tokyo Keiki.
The viscosity of the coating solution at 38 ° C. using a Haake RheoStress RS150 is 30, 43, 41, 28, 20 [mPa · s] at shear rates of 0.1, 1, 10, 100, 1000 [1 / second], respectively. s].

  The amount of zirconium in the coating solution was 0.30 mg per 1 g of silver.

3) Preparation of intermediate layer coating solution 1000 g of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), 163 g of pigment-1 dispersion, blue dye compound-1 (manufactured by Nippon Kayaku Co., Ltd .: Kayafect Turquoise RN Liquid 150) 18.5% by weight aqueous solution 33 g, sulfosuccinic acid di (2-ethylhexyl) sodium salt 5% by weight aqueous solution 27 ml, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 57/8 / 28/5/2) 27% of 5% aqueous solution of aerosol OT (manufactured by American Cyanamid Co., Ltd.) in 4200 ml of 19% by weight latex, 135 ml of 20% by weight aqueous solution of diammonium phthalate, total amount 10000g Water is added to the NaO so that the pH is 7.5. The intermediate layer coating solution was adjusted with H and fed to the coating die so as to be 8.9 ml / m ² .
The viscosity of the coating solution was 58 [mPa · s] at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).

4) Preparation of surface protective layer first layer coating solution 100 g of inert gelatin and 10 mg of benzoisothiazolinone were dissolved in 840 ml of water, and a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio). 57/8/28/5/2) Latex 19% by weight solution 180g, phthalic acid 15% by weight methanol solution 46ml, sulfosuccinic acid di (2-ethylhexyl) sodium salt 5% by weight aqueous solution 5.4ml was added. The mixture was mixed, and immediately before coating, 40 ml of 4% by weight chromium alum was mixed with a static mixer and fed to the coating die so that the amount of the coating solution was 26.1 ml / m ² .
The viscosity of the coating solution was 20 [mPa · s] at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).

5) Preparation of surface protective layer second layer coating solution 100 g of inert gelatin and 10 mg of benzoisothiazolinone are dissolved in 800 ml of water, 40 g of 10% by mass of liquid paraffin and 10% by mass of dipentaerythrityl hexaisostearate are mixed. 40 g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 57/8/28/5/2) latex 19% by weight solution 180 g, phthalic acid 15% by weight methanol solution 40 ml, 5.5 ml of a 1% by weight solution of a fluorosurfactant (F-1), 5.5 ml of a 1% by weight aqueous solution of a fluorosurfactant (F-2), and di (2-ethylhexyl) sodium sulfosuccinate 28 ml of 5% by weight aqueous solution of polymethyl methacrylate fine particles (average A mixture of 4 g of particle size 0.7 μm, volume weighted average distribution 30%) and 21 g of polymethyl methacrylate fine particles (average particle size 3.6 μm, volume weighted average distribution 60%) is used as a surface protective layer coating solution. The solution was fed to the coating die so as to be 3 ml / m ² .
The viscosity of the coating solution was 19 [mPa · s] at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).

3. Production of photothermographic material 1) Production of photothermographic material-1 to 45 In the support 1 to 45 having the back layer, an image-forming layer coating solution from the undercoat surface to the surface opposite to the back surface of each support, The intermediate layer coating solution, the surface protective layer first layer coating solution, and the surface protective layer second layer coating solution are simultaneously applied in the order of the slide bead coating method, and heat development is performed on the supports 1 to 45 having the back layer. Photosensitive material samples 1 to 45 were prepared. At this time, the coating solution for the image forming layer and the intermediate layer was adjusted to 31 ° C., the coating solution for the first surface protective layer was adjusted to 36 ° C., and the coating solution for the second surface protective layer was adjusted to 37 ° C.
The coating amount (g / m ² ) of each compound in the image forming layer is as follows.

Fatty acid silver 5.27
Pigment (C.I. Pigment Blue 60) 0.036
Polyhalogen compound-1 0.14
Polyhalogen compound-2 0.28
Phthalazine Compound-1 0.18
SBR latex 9.43
Reducing agent-2 0.77
Hydrogen bonding compound-1 0.28
Development accelerator-1 0.019
Development accelerator-2 0.016
Color tone adjusting agent-1 0.006
Mercapto compound-2 0.003
Silver halide (as Ag) 0.13

The coating and drying conditions are as follows.
The coating was performed at a speed of 160 m / min, the gap between the coating die tip and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set to be 196 to 882 Pa lower than the atmospheric pressure. The support was neutralized with an ion wind before coating.
In the subsequent chilling zone, after cooling the coating solution with a wind at a dry bulb temperature of 10 to 20 ° C., it is transported in a non-contact type, and is dried at a dry bulb temperature of 23 to 45 ° C. It dried with the dry wind of the wet bulb temperature 15-21 degreeC.
After drying, the humidity was adjusted at 25 ° C. and humidity of 40 to 60% RH, and then the film surface was heated to 70 to 90 ° C. After heating, the film surface was cooled to 25 ° C.
The photothermographic material thus prepared had a Beck smoothness of 550 seconds on the image forming layer surface side and 130 seconds on the back surface. Further, the pH of the film surface on the image forming layer surface side was measured and found to be 6.0.

  The chemical structures of the compounds used in the examples of the present invention are shown below.

4). Evaluation of stability over time of the dye of the present invention in the coating film 1) Preparation The obtained sample was cut into half-cut size (43 cm length x 35 cm width) and packaged in the following packaging materials in an environment of 25 ° C. and 50% RH. Stored at room temperature for a week. Thereafter, in order to confirm the temporal stability of the dye of the present invention in the coating film, each photothermographic material was stored at 60 ° C. and 40% RH for 3 days as forced aging.
<Packaging materials>
PET 10 μm / PE 12 μm / aluminum foil 9 μm / Ny 15 μm / polyethylene 50 μm containing 3% by mass of carbon
Oxygen permeability: 0.02 ml / atm · m ² · 25 ° C · day, moisture permeability: 0.10 g / atm · m ² · 25 ° C · day

2) <Evaluation of storage stability in coating film>
In order to evaluate the storage stability of the dye of the present invention, the photothermographic material was not forcedly aged and the coating film on the image forming surface of a sample was removed using water and acetone, and then the spectral absorption of the back surface was measured. The concentration value of the maximum absorption wavelength of the dye of each sample was read, the residual ratio of the dye before and after forced aging was calculated based on the following formula, and the temporal stability of the dye in the coating film was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3.
Residual rate = (concentration value of maximum absorption wavelength of dye after forced aging) / (concentration value of maximum absorption wavelength of dye without forced aging)
(Evaluation criteria)
1: The residual rate is less than 70% and the stability is very bad.
2: The residual ratio is 70% or more and less than 80%, and the level of photographic performance degradation is clearly evident.
3: Residual rate is 80% or more and less than 85%, which is an acceptable level for photographic performance.
4: The residual rate is 85% or more and less than 90%, and the photographic performance is hardly deteriorated.
5: Residual rate is 90% or more and has no effect on photographic performance degradation.

上記表３から明らかな通り、本発明の熱現像感光材料は比較例に比べて生保存中の染料の残存率が高く、写真性能の点で極めて優れていることが分かった。

As apparent from Table 3 above, it was found that the photothermographic material of the present invention has a higher residual ratio of the dye during raw storage than the comparative examples, and is extremely excellent in terms of photographic performance.

2) Exposure and development of photosensitive materials

Photothermographic materials-1 to 45 were exposed and heat-developed (107 ° C.-121 ° C.-121 ° C.) using a dry laser imager DRYPIX7000 (equipped with a 660 nm semiconductor laser with a maximum output of 50 mW (IIIB)). (Total 14 seconds with 3 panel heaters).
In all the samples of the present invention, the residual color of the cyanine dye related to the present invention was hardly seen, and good image performance (photographic performance) was obtained.

Claims (9)

In the silver halide light-sensitive material having an image forming layer containing a photosensitive silver halide on a support, it contains a compound represented by the following general formula (1) on at least one surface of the support. A characteristic silver halide photographic light-sensitive material.
General formula (1) DM
[Wherein, D represents a cation moiety of the following general formula (A). M represents an anion moiety of the following general formula (A). ]

[In General Formula (A), R ¹ is a hydrogen atom, an aliphatic group, an aromatic group, —NR ²¹ R ²⁴ , —OR ²¹ or —SR ²¹ , and R ²¹ and R ²⁴ are each independently hydrogen. It is an atom, an aliphatic group or an aromatic group, or R ²¹ and R ²⁴ are combined to form a nitrogen-containing heterocycle. R ² is a hydrogen atom, an aliphatic group or an aromatic group. Z ¹ is an atomic group forming a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring, and the nitrogen-containing heterocycle and its condensed ring May have a substituent. Q ₁ represents a group necessary for forming a cyanine dye, a styryl dye, a hemicyanine dye, a rhodacyanine dye, a complex cyanine dye, an allopolar dye, a squalium dye, a croconium dye, or an azamethine dye. M represents a charge balance counter anion having 8 or more carbon atoms. However, M has 3 or less sulfonic acid groups. ] The silver halide photographic light-sensitive material according to claim 1 further has an image forming layer containing a non-photosensitive organic silver salt, a reducing agent and a binder on the surface of the support having the photosensitive silver halide. A photothermographic material having a non-photosensitive layer on at least one surface of the support, wherein the non-photosensitive layer contains a compound represented by the general formula (1). material. 3. The photothermographic material according to claim 2, wherein the non-photosensitive layer is formed using the compound represented by the general formula (1) as a solid dispersion. The heat represented by the compound represented by the general formula (1) in the solid dispersion according to claim 3 formed by mixing and dispersing the following general formula (2) and the following general formula (3) Development photosensitive material.
General formula (2) DA
General formula (3) BM
[In General Formula (2), D represents the cation part of the said General formula (1), and A represents the anion part which does not contain M of General formula (1). In the general formula (3), B represents a cation moiety not containing D in the general formula (1), and M represents an anion moiety in the general formula (1). ] The photothermographic material according to claim 4, wherein the production rate of the general formula (1) in the solid dispersion is 60 mol% or more based on the total molar amount of the general formula (2). 6. The photothermographic material according to claim 3, wherein the concentration of the compound represented by the general formula (1) in the solid dispersion is 10% by mass or more. The photothermographic material according to claim 3, wherein the solid dispersion contains a water-soluble polymer dispersant. 8. The photothermographic material according to claim 7, wherein the solid dispersion contains 10 to 40% by weight of a water-soluble polymer dispersant based on the compound represented by the general formula (1). The water-soluble polymer dispersant is at least one member selected from the group consisting of polyvinyl alcohols, modified polyvinyl alcohols, hydroxyalkyl celluloses, carboxymethyl celluloses, polyacrylamides and polyvinyl pyrrolidones. The photothermographic material according to claim 7 or 8.