JP2002244243A - Heat developable photosensitive material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material excellent in photographic performance, image preserving performance and blocking property. SOLUTION: In the heat developable photosensitive material having at least one photosensitive silver halide-containing photosensitive layer and a non- photosensitive protective layer on one face of the base and containing at least one photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a toning agent and a binder in the photosensitive layer, a latex reactive with gelatin is contained on the side with the photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material excellent in photographic performance, image storability and blocking property.

[0002]

2. Description of the Related Art In recent years, in the field of medical diagnostic films and photoengraving films, there has been a strong demand for reducing the amount of processing waste liquid from the viewpoint of environmental protection and space saving. Therefore, as a film for medical diagnosis and a film for photoengraving, which can be efficiently exposed by a laser imagesetter or a laser imager and can form a clear black image having high resolution and sharpness, heat There is a need for a technique for developing photosensitive materials. According to these photothermographic materials, a photothermographic processing system that does not require solution-based processing chemicals and is simpler and does not damage the environment can be supplied to customers.

[0003] In the field of general image forming materials, there is a similar requirement, but in particular, medical diagnostic images require high-quality images with excellent sharpness and granularity due to the need for fine description.
From the viewpoint of easiness of diagnosis, there is a characteristic that a cool black image is preferred. At present, various hard copy systems using pigments and dyes, such as ink jet printers and electrophotographs, are distributed as general image forming systems, but none of them is satisfactory as a medical image output system.

On the other hand, a thermal image forming system using an organic silver salt is disclosed in, for example, US Pat. Nos. 3,152,904 and 345.
No. 7075 and D.C. Crosta Bohr (Kloste
rboer) "Thermal Processed Silver System (Thermall)
y Processed Silver Systems) "(Imaging Processes and Materials
and Materials) Neblette 8th edition, J. Sturg
e), V. Walworth, A. Shepp
Compilation, Chapter 9, p. 279, 1989). In particular, the photothermographic material generally contains a catalytically active amount of a photocatalyst (for example, silver halide), a reducing agent, a reducible silver salt (for example, an organic silver salt), and if necessary, a color tone agent for controlling the color tone of silver. And a photosensitive layer dispersed in a binder matrix. After the image exposure, the photothermographic material is heated to a high temperature (for example, 80 ° C. or higher), and a black silver image is formed by a redox reaction between a reducible silver salt (which functions as an oxidizing agent) and a reducing agent. Form. The oxidation-reduction reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, a black silver image is formed in the exposed area. U.S. Pat. No. 2,910,377, JP-B-43-
It is disclosed in many documents including 4924.

However, in these photothermographic materials, there is no fixing step after the heat development, so that there is a problem of image deterioration in image preservability due to an increase in density of an undeveloped portion. In addition, since the photothermographic materials described above do not require wet processing, a crosslinking agent is often not used, and there is a problem in performing special handling in which water or an organic solvent may adhere. was there.

[0006]

SUMMARY OF THE INVENTION In view of these problems of the prior art, an object of the present invention is to provide a photothermographic material excellent in photographic performance, image storability and blocking property, and a method for producing the same.

[0007]

The present invention has been achieved by the following means.

<Embodiment (1)> On one surface of a support, there is provided at least one photosensitive layer containing photosensitive silver halide and a non-photosensitive protective layer, wherein the photosensitive layer comprises at least one kind of photosensitive layer. In a photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, a latex which reacts with gelatin is contained on the side having the photosensitive layer. A photothermographic material comprising:

<Embodiment (2)> On one surface of a support, there is provided at least one photosensitive layer containing a photosensitive silver halide and a non-photosensitive gelatin-containing layer. In a photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, the non-photosensitive gelatin-containing layer on the side having the photosensitive layer A photothermographic material containing a latex that reacts with gelatin.

<Embodiment (3)> On one surface of a support, there is provided at least one photosensitive layer containing a photosensitive silver halide and a non-photosensitive protective layer, wherein the photosensitive layer comprises at least one kind of photosensitive layer. In a photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, a latex which reacts with gelatin is contained on the side having the photosensitive layer. And adding the latex in a closed mixing container (inline).

<Embodiment (4)> On one surface of a support, there is provided at least one photosensitive layer containing a photosensitive silver halide and a non-photosensitive gelatin-containing layer. In a photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, the non-photosensitive gelatin-containing layer on the side having the photosensitive layer Contains a latex that reacts with gelatin, and in a closed mixing container (inline)
A method for producing a photothermographic material, wherein

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The photothermographic material of the present invention has at least one photosensitive layer containing a photosensitive silver halide on one surface of a support, and a non-photosensitive protective layer.
A photothermographic material comprising a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a toning agent and a binder, which reacts with gelatin on the side having the photosensitive layer. It is characterized by containing latex.

The above-mentioned photosensitive layer (image forming layer) is composed of one or more layers, and when it is composed of one layer, a photosensitive silver halide, a non-photosensitive organic silver salt and a silver ion A reducing agent, a color tone agent and a binder are contained in the layer, and if necessary, a coating auxiliary and other auxiliary agents are optionally contained. On the other hand, when it is composed of two layers, the first layer (usually a layer adjacent to the support) contains a photosensitive silver halide and a non-photosensitive organic silver salt, and the second layer or both layers contain Some other components are included.

The non-photosensitive protective layer is a protective layer provided on the photosensitive layer (image forming layer), that is, on the side far from the support. An intermediate layer or the like may be provided between the layer and the protective layer, and an undercoat layer or the like may be provided between the image forming layer and the support. It is preferable to provide a back layer on the other surface of the support (the side opposite to the side on which the photosensitive layer is provided).

The heat-developable material of the present invention can solve the problems of the present invention by including at least one layer on the side having the photosensitive layer (image forming layer) with a latex which reacts with gelatin. However, among the sides having the photosensitive layer, it is preferable that the non-photosensitive gelatin-containing layer contains a latex which reacts with the gelatin, particularly for improving the performance. When there are a plurality of non-photosensitive gelatin-containing layers, it is preferable to include them in the protective layer,
When it has two or more protective layers, it is most preferable to include it in the outermost protective layer (the layer farthest from the support).

Further, as a method of adding the latex which reacts with the gelatin, it is preferable to add the latex in a closed mixing vessel (in-line) because the reactivity of the latex is less likely to be impaired, so that the above performance is surely improved. Is preferred.

(Gelatin-Reactive Latex) First, the latex which reacts with gelatin used in the present invention will be described. In the present specification, the latex that reacts with gelatin is a latex containing a group that directly reacts with gelatin in an amount of 0.1 mol% or more, and other than that, there is no particular limitation. Examples of such groups that directly react with gelatin include aldehyde groups, epoxy groups, active halide groups, active vinyl groups, active ester groups, oxazoline groups, ethyleneimine groups, and active methylene groups.

Among these, an active vinyl group and an active methylene group are preferable, and among the active vinyl groups, a vinyl sulfone group or a group derived from the vinyl sulfone group is particularly preferable.

In the latex which reacts with gelatin of the present invention, the group which reacts with gelatin may be at least 0.1 mol%, preferably 0.1 mol% to 40 mol%, more preferably 0.5 mol% or less. Mol% or more and 20 mol% or less,
More preferably, it is 1 mol% or more and 10 mol% or less.

The following is an example of a latex that is preferably used in the present invention and reacts with the above gelatin. In the examples, Core (shell) and Shell (shell)
Shell around the core (polymer) mass forming the core
This is a latex coated with a polymer forming a (shell), and this Core / Shell type latex is preferable in the present invention. The present invention is not limited to these examples.

[0021]

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[0023]

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[0024]

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[0029]

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[0030]

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[0031]

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[0032]

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The amount of the latex which reacts with the gelatin of the present invention is not particularly limited, but is preferably 1 m.
g / m ² or more and 1,000 mg / m ² or less, more preferably 50 mg / m ² or more and 800 mg / m ² or less, still more preferably 100 mg / m ² or more and 500 mg / m ² or less.
The latex that reacts with the gelatin of the present invention is preferably in a gelatin-containing layer.

(In-line Addition) The latex which reacts with the above gelatin of the present invention can be contained in any layer having a photosensitive layer, and the addition method is as follows. There are a method of adding to the liquid surface, a method of adding to the liquid, and a method of adding in a closed mixing vessel (in-line) described later. Either method may be used, but adding in a closed mixing vessel (in-line) This method is preferred because the risk of impairing the reaction activity of the latex is minimized.

(Non-photosensitive Organic Silver Salt) The non-photosensitive organic silver salt (hereinafter sometimes simply referred to as “organic silver salt”) which can be used in the present invention is relatively stable to light. Are silver salts which form a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Such a non-photosensitive organic silver salt is described in paragraphs [0048 to 004] of JP-A-10-62899.
9], EP-A-0803764A1, page 18, line 24 to page 19, line 37, EP-A-0962.
812A1, JP-A-11-34991, JP-A-20
Nos. 00-7683 and 2000-72711.

The organic silver salt is preferably a silver salt of an organic acid, particularly a silver salt of a long-chain aliphatic carboxylic acid having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms. Preferred examples of such organic silver salts include silver behenate, silver arachidate,
Examples thereof include silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, and mixtures thereof. In the present invention,
Among these organic silver salts, a silver behenate content of 75 mol%
It is preferable to use the above-mentioned organic acid silver.

The shape of the organic silver salt used in the present invention is not particularly limited, and may be needle-like, rod-like, flat-plate-like, scaly, or the like. Organic silver salts are preferred.

In the present specification, the scaly organic silver salt is defined as follows. The organic silver salt was observed with an electron microscope, and the shape of the organic silver salt particles was approximated to a rectangular parallelepiped.
May be the same as ) Then, calculation is performed using the shorter two numerical values a and b, and x is obtained as follows. x = b / a

As described above, x is obtained for about 200 particles, and when the average value is x (average), x
Those satisfying the relationship of (average) ≧ 1.5 are defined as scaly.
As the flaky organic silver salt of the present invention, 1.5 ≦ x (average)
≦ 30 is preferable, and 2.0 ≦ x (average) ≦ 20 is more preferable. Incidentally, the needle shape is a shape of 1 ≦ x (average) <1.5.

In the scaly particles, a can be regarded as the thickness of tabular particles having a main plane with b and c as sides. A (average) as the thickness is preferably 0.01 μm or more and 0.23 μm, and more preferably 0.1 μm or more and 0.20 μm.
m or less is more preferable. c / b (average) is preferably 1 or more and 6 or less, more preferably 1.05 or more and 4 or less,
It is more preferably 1.1 or more and 3 or less, particularly preferably 1.
It is 1 or more and 2 or less.

The particle size distribution of the organic silver salt used in the present invention is preferably monodispersed. Monodispersion means that the percentage of the value obtained by dividing the standard deviation of the length of each of the minor axis and major axis by the minor axis and major axis is preferably 100% or less, more preferably 80% or less, and still more preferably 50% or less. is there. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion.

As another method for measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) of the value divided by the volume-weighted average diameter is known.
However, it is preferably 100% or less, more preferably 80% or less, and still more preferably 50% or less. As a measurement method, for example, the organic silver salt dispersed in a liquid is irradiated with laser light, and the particle size (volume weighted average diameter) obtained by obtaining an autocorrelation function with respect to the time change of the fluctuation of the scattered light is calculated. can do.

Known methods and the like can be applied to the production of the organic acid silver used in the present invention and the dispersion method thereof. For example, JP-A-10-62899, European Patent Publication No. 0803763A1, and European Patent Publication No. 0962812A described above.
No. 1, JP-A-11-34991, JP-A-2000-7
No. 683, No. 2000-72711, Japanese Patent Application No. 11-3
No. 48228-30, No. 11-203413, Japanese Patent Application No. 2
000-90093, 2000-195621,
Nos. 2000-191226 and 2000-21381
No. 3, 2000-214155, 2000-19
No. 1226 can be referred to.

In addition, when a photosensitive silver salt is present at the time of dispersing the organic silver salt, fog may increase and the sensitivity may be remarkably lowered. Is more preferred. In the present invention, the amount of the photosensitive silver salt in the aqueous dispersion to be dispersed is 0.1 mol% or less based on 1 mol of the organic silver salt in the liquid. Don't do it.

In the present invention, it is possible to produce a photosensitive material by mixing an aqueous dispersion of an organic silver salt and an aqueous dispersion of a photosensitive silver salt, but the mixing ratio of the organic silver salt to the photosensitive silver salt depends on the purpose. You can choose, but the ratio of photosensitive silver salt to organic silver salt is 1
~ 30 mol% is preferable, and further 3 ~ 20 mol%,
Particularly, a range of 5 to 15 mol% is preferable. When mixing
Mixing two or more aqueous dispersions of organic silver salts with two or more aqueous dispersions of photosensitive silver salts is a method preferably used for adjusting photographic characteristics.

The organic silver salt of the present invention can be used in a desired amount.
However, the amount of silver is 0.1 to 5 g / m ^TwoIs preferred, and
Preferably 1-3 g / m^TwoIt is.

(Reducing Agent) The photothermographic material of the present invention preferably contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, but an organic substance is preferred. Such reducing agents are described in, for example, paragraphs [0043 to 0045] of JP-A-11-65021 and European Patent Publication No. 08
No. 03764A1, page 7, line 34 to page 18, line 12.

In the present invention, the reducing agent is preferably a hindered phenol reducing agent or a bisphenol reducing agent, and more preferably a compound represented by the following formula (I).

Embedded image In the general formula (I), R ¹¹ and R ^{11 ′} each independently represent an alkyl group having 1 to 20 carbon atoms. R ¹² and R
^{12 ′} each independently represents a hydrogen atom or a substituent that can be substituted on a benzene ring. L represents an -S- group or a -CHR ¹³ -
Represents a group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ and X ^{1 ′} each independently represent a hydrogen atom or a group that can be substituted on a benzene ring.

The general formula (I) will be described in detail. R
¹¹ and R ^{11 ′} are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the substituent of the alkyl group is not particularly limited, but is preferably an aryl group or a hydroxy group. , An alkoxy group, an aryloxy group,
Examples thereof include an alkylthio group, an arylthio group, an acylamino group, a sulfonamide group, a sulfonyl group, a phosphoryl group, an acyl group, a carbamoyl group, an ester group, and a halogen atom.

R ¹² and R ^{12 ′} are each independently a hydrogen atom or a substituent that can be substituted on a benzene ring, and X ¹ and X ^{1 ′} are each independently a hydrogen atom or a substituent that can be substituted on a benzene ring. Represents Preferred examples of the group that can be substituted on a benzene ring include an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acylamino group.

L represents a —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. R
Specific examples of the unsubstituted alkyl group represented by ¹³ include methyl, ethyl, propyl, butyl, heptyl, undecyl, isopropyl, 1-ethylpentyl, 2,4,4-trimethyl And a pentyl group. Examples of the substituent for the alkyl group can include, similar to substituent of R ^11, halogen atom, alkoxy group, alkylthio group, aryloxy group, arylthio group, an acylamino group, a sulfonamido group, a sulfonyl group, a phosphoryl group, an oxycarbonyl group, Examples include a carbamoyl group and a sulfamoyl group.

R ¹¹ and R ^{11 ′} are preferably a secondary or tertiary alkyl group having 3 to 15 carbon atoms, specifically, isopropyl, isobutyl, t-butyl,
Examples thereof include a t-amyl group, a t-octyl group, a cyclohexyl group, a cyclopentyl group, a 1-methylcyclohexyl group, and a 1-methylcyclopropyl group. R ¹¹ and R
^{11 ′} is more preferably a tertiary alkyl group having 4 to 12 carbon atoms, and among them, t-butyl group, t-amyl group,
A -methylcyclohexyl group is more preferred, and a t-butyl group is most preferred.

R ¹² and R ^{12 ′} are preferably an alkyl group having 1 to 20 carbon atoms, specifically, a methyl group,
Ethyl group, propyl group, butyl group, isopropyl group, t
-Butyl group, t-amyl group, cyclohexyl group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group, methoxyethyl group and the like. More preferably methyl group, ethyl group, propyl group, isopropyl group,
t-butyl 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.
Methyl group, ethyl group, propyl group, isopropyl group,
A 2,4,4-trimethylpentyl group is preferred. Particularly preferred as R ¹³ are a hydrogen atom, a methyl group, a propyl group and an isopropyl group.

When R ¹³ is a hydrogen atom, R ¹² and R
^{12 ′} is preferably an alkyl group having 2 to 5 carbon atoms,
An ethyl group and a propyl group are more preferred, and an ethyl group is most preferred.

R¹³Is a primary or secondary C 1 -C 8
When it is a alkyl group, R¹²And R ^{12 '}Is preferably a methyl group
Good. R¹³Primary or secondary having 1 to 8 carbon atoms represented by
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl
Group, isopropyl group is more preferable, methyl group, ethyl group
And propyl groups are more preferred.

When R ¹¹ , R ^{11 ′} , R ¹² and R ^{12 ′} are all methyl groups, R ¹³ is preferably a secondary alkyl group. In this case, the secondary alkyl group represented by R ¹³ includes an isopropyl group, an isobutyl group,
An ethylpentyl group is preferred, and an isopropyl group is more preferred.

Hereinafter, specific examples of the reducing agent used in the present invention, including the compound represented by the general formula (I), are shown, but the present invention is not limited to these.

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In the present invention, the amount of the reducing agent added is 0.1.
It is preferably 0.1 to 5.0 g / m ² , and 0.1 to 5.0 g / m ^2.
It is more preferably 3.0 g / m ² , and it is contained in an amount of 5 to 50% by mol with respect to 1 mol of silver on the surface having a photosensitive layer (hereinafter sometimes referred to as “image forming layer”). , And more preferably 10 to 40 mol%. 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, and a solid fine particle dispersion form, and may be contained in the photosensitive material. Well-known emulsification dispersion methods include oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and dissolution using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically dispersing the emulsified dispersion. There is a method of manufacturing.

In the solid fine particle dispersion method, a reducing agent powder is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves to obtain a solid dispersion. The method of making is mentioned. In this case, a protective colloid (for example, polyvinyl alcohol) and 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. The aqueous dispersion can contain a preservative (eg, benzoisothiazolinone sodium salt).

In the photothermographic material of the present invention, a phenol derivative represented by the formula (A) described in Japanese Patent Application No. 11-73951 is preferably used as a development accelerator.

(Hydrogen Bonding Compound) When the reducing agent in the present invention has an aromatic hydroxyl group (—OH), particularly in the case of the above-mentioned bisphenols, it is possible to form a hydrogen bond with these groups. It is preferable to use a non-reducing compound having a suitable group in combination. 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. No. Among them, preferred are a phosphoryl group, a sulfoxide group and an amide group (provided that> N
Having no -H group,> N-Ra (Ra is a substituent other than H)
It is blocked like. ), Urethane group (however,
It has no> NH group and is blocked as in> N-Ra (Ra is a substituent other than H). ), And a ureido group (provided that it has no> NH group and is blocked like> N—Ra (Ra is a substituent other than H)).

In the present invention, a particularly preferred compound having a hydrogen bonding property is a compound represented by the following formula (II).

Embedded image In the general formula (II), R ^{21 to} R ²³ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these groups may be unsubstituted or substituted. It may have a group. R ^{21 to} R ²³
When a substituent has a substituent, 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, an oxycarbonyl group, Carbamoyl group, sulfamoyl group,
A sulfonyl group, a phosphoryl group and the like are exemplified, and a preferable substituent is an alkyl group or an aryl group. For example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a t-octyl group, a phenyl group, a 4-alkoxyphenyl And 4-acyloxyphenyl groups.

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 and a t-butyl group.
-Amyl group, t-octyl group, cyclohexyl group, 1-
Methylcyclohexyl group, benzyl group, phenethyl group,
2-phenoxypropyl group and the like.

Examples of the aryl group include a phenyl group, a cresyl group, a xylyl group, a naphthyl group, a 4-t-butylphenyl group, a 4-t-octylphenyl group, a 4-anisidyl group and a 3,5-dichlorophenyl group. Can be

Examples of the alkoxy group include methoxy, ethoxy, butoxy, octyloxy, 2-ethylhexyloxy, 3,5,5-trimethylhexyloxy, dodecyloxy, cyclohexyloxy,
-Methylcyclohexyloxy group, benzyloxy group and the like.

Examples of the aryloxy group include a phenoxy group, a cresyloxy group, an isopropylphenoxy group,
-T-butylphenoxy group, naphthoxy group, biphenyloxy group and the like.

Examples of the amino group include dimethylamino, diethylamino, dibutylamino, dioctylamino, N-methyl-N-hexylamino, dicyclohexylamino, diphenylamino, N-methyl-N-
And a phenylamino group.

As R ^{21 to} R ²³ , an alkyl group, an aryl group, an alkoxy group and an aryloxy group are preferred. From the viewpoint of the effect 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.

Hereinafter, the general formula (II) used in the present invention will be described.
Specific examples of the hydrogen bonding compound including the compound of the following are shown, but the present invention is not limited thereto.

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[0077]

Embedded image Specific examples of the hydrogen-bonding compound are described in Japanese Patent Application No. 200-200
Nos. 0-192191 and 2000-194811.

The compound of the general formula (II) of the present invention can be contained in a coating solution in the form of a solution, an emulsified dispersion, or a solid-dispersed fine particle dispersion as in the case of the reducing agent, and used in a photosensitive material. The compound of the present invention forms a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state. Depending on the combination of the reducing agent and the compound of the general formula (II) of the present invention, the compound may form a complex. It can be isolated in crystalline form. It is particularly preferable to use the crystal powder isolated in this way as a solid dispersion fine particle dispersion in order to obtain stable performance. Further, a method in which the reducing agent and the compound of the general formula (II) of the present invention are mixed in a powder form, and a complex is formed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can also be preferably used.

The compound of the general formula (II) of the present invention is preferably used in a range of 1 to 200 mol%, more preferably in a range of 10 to 150 mol%, further preferably 30 to 150 mol%, based on the reducing agent. １００100 mol%.

(Photosensitive Silver Halide) The photosensitive silver halide used in the present invention is not particularly limited in terms of the halogen composition. Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, chloroiodide Silver halide can be used. Among them, silver bromide and silver iodobromide are preferred. The distribution of the halogen composition in the grains may be uniform, the halogen composition may change stepwise, or may change continuously. Further, silver halide grains having a core / shell structure can also be preferably used. Preferred as the structure is a 2- to 5-fold structure, more preferably 2 to 4
Heavy core / shell particles can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods for forming photosensitive silver halide are well known in the art, and include, for example, those described in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. Specifically, a method of preparing a photosensitive silver halide by adding a silver-supplying compound and a halogen-supplying compound into gelatin or another polymer solution, and thereafter mixing with an organic silver salt can be used. . Also, the paragraph numbers [0217 to 02] of JP-A-11-119374 are used.
24], Japanese Patent Application No. 11-98708.
And Japanese Patent Application No. 2000-42336 are also preferable.

The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically, 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less. , More preferably 0.1.
It is preferably from 02 μm to 0.12 μm. The grain size as used herein means a diameter when converted into a circular image having an area equal to the projected area of a silver halide grain (in the case of a tabular grain, the projected area of a main plane).

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles are particularly preferable. Silver halide grains having rounded corners can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited, but the ratio of the [100] plane, which has high spectral sensitization efficiency when the spectral sensitizing dye is adsorbed, is high. Is preferred. The ratio is preferably at least 50%, more preferably at least 65%, even more preferably at least 80%. The ratio of the Miller index [100] plane is determined by T. Tani; J. Imaging Sci., <29>, 165 (1985) using the adsorption dependence of the [111] plane and the [100] plane in the adsorption of the sensitizing dye.
Year).

In the present invention, silver halide grains having a hexacyano metal complex present on the outermost surface of the grains are preferred. 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 more preferable.

Since the hexacyano metal complex exists in the form of ions in an aqueous solution, the counter cation is not important, but it is easily miscible with water and is suitable for sodium ion, which is suitable for the precipitation operation of a silver halide emulsion. Use of alkali metal ions such as potassium ion, rubidium ion, cesium ion, and lithium ion, ammonium ion, and alkylammonium ion (for example, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, and tetra (n-butyl) ammonium ion) Is preferred.

The hexacyano metal complex can be obtained by mixing a water-miscible organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) or gelatin with water. And can be added as a mixture. 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 1 mol of silver.

In order for the hexacyano metal complex to be present on the outermost surface of the silver halide grains, the addition of the hexacyano metal complex to the aqueous silver nitrate solution used for grain formation is followed by sulfur sensitization, selenium sensitization and tellurium sensitization. Is added directly before the completion of the charging step before the chemical sensitization step for precious metal sensitization such as chalcogen sensitization or gold sensitization, during the water washing step, during the dispersion step, or before the chemical sensitization step. In order not to grow the silver halide fine grains, it is preferable to add the hexacyano metal complex immediately after the grain formation, and it is preferable to add the hexacyano metal complex before the completion of the charging step.

Incidentally, the addition of the hexacyano metal complex may be started after 96% by mass of the total amount of silver nitrate added for grain formation is added, or started after 98% by mass is added. More preferably, it is particularly preferable after adding 99% by mass.

When these hexacyano metal complexes are added after the addition of an aqueous silver nitrate solution immediately before the completion of grain formation, they can be adsorbed on the outermost surface of silver halide grains, and most of them are hardly soluble in silver ions on the grain surface. Forms salt. Since the silver salt of hexacyanoiron (II) is a salt that is less soluble than AgI, it can be prevented from being redissolved by fine particles, and silver halide fine particles having a small particle size can be produced.

The photosensitive silver halide grains of the present invention can contain a metal or a metal complex of Group 8 to Group 10 of the periodic table (showing Groups 1 to 18). Rhodium, ruthenium, and iridium are preferably the metals of Group 8 to Group 10 of the periodic table or the central metal of the metal complex. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per mol of silver. Regarding these heavy metals and metal complexes and methods for adding them, JP-A-7-225449,
JP-A-11-65021, paragraph number [0018 to 002]
4], paragraph number [0227] of JP-A-11-119374.
０２0240].

Further, metal atoms (for example, [Fe (CN) ₆ ]) which can be contained in the silver halide grains used in the present invention.
^4- ), desalting and chemical sensitization of silver halide emulsions are described in paragraphs [0046 to 0] of JP-A-11-84574.
050], JP-A-11-65021, paragraph [002]
5-0031] and JP-A-11-119374, paragraph numbers [0242 to 0250].

(Gelatin) As the gelatin contained in the photosensitive silver halide emulsion used in the present invention, various gelatins can be used. In order to maintain a good dispersion state of the photosensitive silver halide emulsion in the coating solution containing the organic silver salt, it is preferable to use low molecular weight gelatin having a molecular weight of 500 to 60,000. These low molecular weight gelatins may be used at the time of particle formation or at the time of dispersion after desalting, but are preferably used at the time of dispersion after desalting.

(Sensitizing Dye) The sensitizing dye applicable to the present invention is a sensitizing dye capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains. A sensitizing dye having a spectral sensitivity suitable for the above can be advantageously selected. The sensitizing dye and the method of addition are described in paragraph [0103] of JP-A-11-65021.
To 0109], and the general formula (I) disclosed in JP-A-10-186572.
A compound represented by the formula (I), a dye represented by the general formula (I) in JP-A-11-119374, and a dye described in Example 5 of paragraphs [0106], US Pat. Nos. 5,510,236 and 3,871,887. Dyes disclosed in JP-A-2-96131 and JP-A-59-48753, page 19, line 38 to column 20 of EP-A-0803764A1.
Page 35 line, Japanese Patent Application No. 2000-86865, Japanese Patent Application 200
No. 0-102560 and Japanese Patent Application No. 2000-205399. 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 after the desalting step and before coating, and more preferably after desalting and before the start of chemical ripening.

The addition amount of the sensitizing dye in the present invention can be adjusted to a desired amount according to the sensitivity and the performance of fogging, but is preferably from 10 ^-6 to 1 mol per mol of silver halide in the photosensitive layer. And more preferably 10 ^-4 to 10 ^-1 mol.

According to the present invention, in order to improve the spectral sensitization efficiency,
Supersensitizers can be used. Examples of the supersensitizer used in the present invention include EP 587338, US Pat. Nos. 3,877,943 and 4,873,184, JP-A-5-341432, JP-A-11-109547, and JP-A-10-10947.
And the compounds described in JP-A-111543.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized by a sulfur sensitization method, a selenium sensitization method or a tellurium sensitization method. Known compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method include, for example, JP-A-7-12876.
Compounds described in No. 8, etc. can be used. Particularly in the present invention, tellurium sensitization is preferable.
No. 65021, a compound described in the document described in paragraph [0030], a compound represented by the general formula (I) described in JP-A-5-313284.
Compounds represented by I), (III) and (IV) are more preferred.

In the present invention, chemical sensitization can be performed at any time after grain formation and before coating, and after desalting, (1) before spectral sensitization, (2) simultaneously with spectral sensitization, ( 3) After spectral sensitization, (4) immediately before coating, and the like. In particular, it is preferably performed after spectral sensitization.

The amount of the sulfur, selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is preferably 10 ^-8 to 10 ^-2 mol per mol of silver halide. And preferably about 10 ^-7 to 10 ^-3 mol. The conditions for the 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 thiosulfonate compound may be added to the silver halide emulsion used in the present invention by the method described in EP-A-293917. The photosensitive silver halide emulsion in the photosensitive material used in the present invention,
One type may be used alone, or two or more types may be used in combination (for example, those having different average grain sizes, different halogen compositions, different crystal habits, different chemical sensitization conditions, etc.). By using a plurality of photosensitive silver halides having different sensitivities, the gradation can be adjusted. Japanese Patent Application Laid-Open Nos. 57-119341 and 53-10
No. 6125, No. 47-3929, No. 48-55730
Nos. 46-5187, 50-73627, 57
-150841 and the like. As the sensitivity difference, it is preferable that each emulsion has a difference of 0.2 logE or more.

The amount of photosensitive silver halide added is 0.03 to 0.6 g / m ² , expressed as the amount of silver applied per m ² of the light-sensitive material.
is preferably m ^2, and more preferably from 0.07~0.4g / m ^2, and most preferably from 0.05 to 0.3 g / m ^2, relative to the organic silver salt to 1 mole The amount of the photosensitive silver halide is preferably from 0.01 mol to 0.5 mol, more preferably from 0.02 mol to 0.3 mol.

Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, and vibrator. Mills, a method of mixing with a homogenizer, etc., or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, etc. There is no particular limitation as long as the effect appears sufficiently. In addition, mixing two or more kinds of aqueous dispersions of organic silver salts and two or more kinds of aqueous dispersions of photosensitive silver salts is a preferable method for adjusting photographic characteristics.

The timing of adding the silver halide of the present invention to the coating solution for the image forming layer is preferably from 180 minutes to immediately before coating, and preferably from 60 minutes to 10 seconds before coating. Is not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, the average residence time calculated from the addition flow rate and the amount of liquid sent to the coater, a method of mixing in a tank so as to be a desired time and N. Harnby, MFEdwards, AWNienow,
"Liquid mixing technology" translated by Koji Takahashi (published by Nikkan Kogyo Shimbun, 19
(1989), a method using a static mixer or the like described in Chapter 8 and the like.

(Binder) The binder of the organic silver salt-containing layer of the present invention may be any polymer, and a suitable binder is transparent or translucent, generally colorless.
Natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other film-forming media such as gelatins, rubbers, poly (vinyl alcohol)
, Hydroxyethylcellulose, cellulose acetates, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (Methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (vinyl acetal) s (for example, poly (vinyl 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 (olefins) , Cellulose esters, poly (amide)
There is kind. The binder may be coated from water or an organic solvent or an emulsion.

In the present invention, the binder in the layer containing the organic silver salt preferably has a glass transition temperature of 10 ° C. or more and 80 ° C. or less (hereinafter sometimes referred to as a high Tg binder), and more preferably 20 ° C. to 70 ° C. More preferably, 23
More preferably, it is not less than 65 ° C. In this specification, Tg was calculated by the following equation. 1 / Tg = Σ (Xi / Tgi)

Here, it is assumed that the polymer is a copolymer of n monomer components from i = 1 to n. Xi is i
Weight fraction of the second monomer (ΣXi = 1), Tgi is i
The glass transition temperature (absolute temperature) of the homopolymer of the second monomer. Where Σ is the sum of i = 1 to n.
The homopolymer glass transition temperature of each monomer (Tg
i) is the Polymer Handbook (3rd Edition) (J. Brandrup, E.
The value of H. Immergut (Wiley-Interscience, 1989) was adopted.

The polymer serving as a binder may be used alone or in combination of two or more as necessary. Further, those having a glass transition temperature of 20 ° C. or more and those having a glass transition temperature of less than 20 ° C. may be used in combination. When two or more polymers having different Tg are blended and used, the weight average Tg is preferably in the above temperature range.

In the present invention, when the organic silver salt-containing layer is formed by coating using a coating solution in which 30% by mass or more of water is water and then drying, the binder of the organic silver salt-containing layer is further added. When soluble or dispersible in an aqueous solvent (aqueous solvent), the equilibrium water content at 25 ° C. and 60% RH is 2% by mass.
The performance is improved when a latex of the following polymer is used. The most preferred form has an ionic conductivity of 2.5 mS
/ Cm or less. Examples of such a preparation method include a method of purifying a polymer using a separation functional membrane after synthesis.

The aqueous solvent in which the polymer is soluble or dispersible is water or a mixture of 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; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; ethyl acetate; and dimethylformamide. Note that the term “aqueous solvent” is used herein even in a system in which the polymer is not thermodynamically dissolved but exists in a so-called dispersed state.

The “equilibrium moisture content at 25 ° C. and 60% RH” is defined as the weight W1 of the polymer in the moisture-conditioning equilibrium under the atmosphere of 25 ° C. and 60% RH and the weight W0 of the polymer in the absolute dry state at 25 ° C. It can be expressed as follows.
Equilibrium water content at 25 ° C. and 60% RH = [(W1-W0) / W
0] × 100 (% by mass) For the definition and measurement method of the water content, for example, reference can be made to Polymer Engineering Course 14, Polymer Material Testing Method (edited by The Society of Polymer Science, Jinjinshokan).

The binder polymer of the present invention has a temperature of 25.degree.
The equilibrium water content at% RH 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% by mass or more and 1% by mass or less.

In the present invention, a polymer dispersible in an aqueous solvent is particularly preferred. Examples of the dispersion state include a latex in which fine particles of a water-insoluble hydrophobic polymer are dispersed, and a dispersion in which polymer molecules are dispersed in a molecular state or in the form of micelles. The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably 5 to 50,000 nm.
A range of about 1,000 nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a broad particle size distribution or a monodispersed particle size distribution.

In the present invention, preferred examples of the polymer dispersible in an aqueous solvent include acrylic polymers, poly (esters), rubbers (for example, SBR resin), poly (urethane) s, poly (vinyl chloride) s, Hydrophobic polymers such as poly (vinyl acetate) s, poly (vinylidene chloride) s and poly (olefins) can be preferably used. These polymers may be a linear polymer, a branched polymer, a crosslinked polymer, a so-called homopolymer obtained by polymerizing a single monomer, or a copolymer 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 in number average molecular weight.
0, preferably 10,000 to 200,000.
If the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the preferred polymer latex include the following. In the following, the raw material monomers are used, and the numerical value in parentheses is% by mass, and the molecular weight is the number average molecular weight. When a polyfunctional monomer is used, the concept of molecular weight cannot be applied because a crosslinked structure is formed. Tg represents a glass transition temperature.

Latex of P-1; -MMA (70) -EA (27) -MAA (3)-(molecular weight 37,000) P-2; -MMA (70) -2EHA (20) -St (5) -AA (5) -Latex (molecular weight 40,000) P-3; -St (50) -Bu (47) -MAA (3) -Latex (crosslinkable) P-4; -St (68) -Bu (29) -AA (3)-latex (crosslinkable) P-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg 24 ° C) P-6; -St (70) -Bu (27) -IA (3)-latex (crosslinkable) P-7; -St (75) -Bu (24) -AA (1)-latex (crosslinkable) P-8; -St ( Latex of 60) -Bu (35) -DVB (3) -MAA (2)-(crosslinkable) P-9; -St (70) -Bu (25) -DVB (2) -AA (3)- Latex (crosslinkable) P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-latex (molecular weight 80,000) P-11; -VDC (85) -MMA (5) -EA (5) -MAA (5)-latex (molecular weight 67,000) P-12; -Et (90) -MAA (10)-latex (molecular weight 12,00
0) P-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130,000) P-14; -MMA (63) -EA (35) -AA (2) latex (molecular weight) 33,000) Latex of P-15; -St (70.5) -Bu (26.5) -AA (3)-
(Crosslinkability, Tg 23 ° C) P-16; -St (69.5) -Bu (27.5) -AA (3)-latex
(Crosslinkability, Tg 20.5 ° C)

The abbreviations of 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, A
N; acrylonitrile, VDC; vinylidene chloride, Et; ethylene, IA; itaconic acid.

The polymer latex described above is commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-463.
5, 4718, 4601 (Daicel Chemical Industries, Ltd.)
Nipol Lx811, 814, 821, 82
Examples of poly (esters) such as 0, 857 (all manufactured by Zeon Corporation) are FINETEX ES65.
Examples of poly (urethane) s such as 0, 611, 675, and 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, and WMS (all manufactured by Eastman Chemical) include HYDRAN AP10, 20, 30, Examples of rubbers such as 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR 7310K, 3307B, 470
0H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.),
Nipol Lx416, 410, 438C, 2507
(Nippon Zeon Co., Ltd.) and other poly (vinyl chloride)
Examples of poly (olefin) s include G351 and G576 (all manufactured by Zeon Corporation), and examples of poly (vinylidene chloride) s include L502 and L513 (all manufactured by Asahi Chemical Industry Co., Ltd.). For example, Chemipearl S
120, SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like.

These polymer latexes may be used alone or, if necessary, may be blended in two or more kinds. As the polymer latex used in the present invention,
Particularly, a latex of a styrene-butadiene copolymer is preferred. The mass ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably from 40:60 to 95: 5. Also,
The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by mass. The preferred molecular weight range is the same as described above.

Styrene which is preferably used in the present invention
As the latex of butadiene copolymer, the above-mentioned P-
3-P-8, 14, 15; LACSTAR, a commercial product
−3307B, 7132C, Nipol Lx416 and the like.

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

The organic silver salt-containing layer (that is, the image forming layer) of the present invention is preferably formed using a polymer latex. As for the amount of the binder in the organic silver salt-containing layer, the weight ratio of total binder / organic silver salt is preferably in the range of 1/10 to 10/1, more preferably 1/5 to 4/1.

The organic silver salt-containing layer is usually a photosensitive layer (emulsion layer) containing a photosensitive silver halide, which is a photosensitive silver salt. The weight ratio of silver / silver halide is preferably in the range of 400 to 5, more preferably 200 to 10.

The total amount of the binder in the image forming layer of the present invention is 0.2 to 30 g / m ² , more preferably 1 to 15 g / m ^2.
Is preferable. A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer of the invention.

In the present invention, the solvent of the coating solution for the organic silver salt-containing layer of the light-sensitive material (the solvent and the dispersion medium are collectively referred to as a solvent for simplicity) 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 in the coating liquid is preferably 50% by mass or more, more preferably 70% by mass or more. Examples of preferred solvent composition include, in addition to 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. (the numerical value is% by mass).

(Polyhalogen compound) Antifoggants, stabilizers and stabilizer precursors that can be used in the present invention are as follows:
Japanese Patent Application Laid-Open No. 10-62899, paragraph [0070], EP-A-0803764A1, from page 20, line 57 to page 21, line 7;
Compounds described in JP-A-9-281637 and JP-A-9-329864 are exemplified. The antifoggant preferably used in the present invention is an organic halide, which is described in paragraph [0111] of JP-A-11-65021.
To 0112]. In particular, an organic halogen compound represented by the formula (P) in Japanese Patent Application No. 11-87297, JP-A-10-33993
No. 4, an organic polyhalogen compound represented by the general formula (II),
Organic polyhalogen compounds described in Japanese Patent Application No. 11-205330 are preferred.

Hereinafter, the organic polyhalogen compound preferred in the present invention will be specifically described. In the present invention, a preferred polyhalogen compound is a compound represented by the following general formula (III).

Formula (III) Q- (Y) nC (Z ₁ ) (Z ₂ ) X

In the general formula (III), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, and Z ₁ and Z ₂ represent a halogen atom. And X represents a hydrogen atom or an electron-withdrawing group.

In the general formula (III), Q preferably represents a phenyl group substituted by an electron-withdrawing group having a positive Hammett's substituent constant (σp). Regarding Hammett's substituent constant, see Journal of Medicinal Chemistry,
1973, Vol. 16, No. 11, 1207-1216 and the like. Examples of such an electron-withdrawing group include, for example, a halogen atom (a fluorine atom (σp value: 0.
06), chlorine atom (σp value: 0.23), bromine atom (σ
p value: 0.23), iodine atom (σp value: 0.1)
8)), a trihalomethyl group (tribromomethyl (σp
Value: 0.29), trichloromethyl (σp value: 0.3)
3), trifluoromethyl (σp value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.
78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)),
Aliphatic / aryl or heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value:
0.43)), an alkynyl group (for example, C≡CH (σp
Value: 0.23)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp
Value: 0.45), phenoxycarbonyl (σp value: 0.
44)), a carbamoyl group (σp value: 0.36), a sulfamoyl group (σp value: 0.57), a sulfoxide group,
Examples include a heterocyclic group and a phosphoryl group. The σp value is preferably in the range of 0.2 to 2.0, and more preferably in the range of 0.4 to 1.0. Particularly preferred electron-withdrawing groups are a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylphosphoryl group, and among them, a carbamoyl group is most preferred.

X is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic / aromatic or heterocyclic acyl group, an aliphatic / aromatic or heterocyclic group. It is a ring oxycarbonyl group, carbamoyl group or sulfamoyl group, and particularly preferably a halogen atom. Among the halogen atoms,
Preferred are chlorine, bromine and iodine, more preferred are chlorine and bromine, and particularly preferred is bromine.

Y is preferably -C (= O)-, -SO-
Or —SO ₂ —, more preferably —C (ＯO)
—, —SO ₂ —, and particularly preferably —SO ₂ —. n represents 0 or 1, and is preferably 1.

Hereinafter, specific examples of the compound represented by formula (III) of the present invention will be shown.

Embedded image

[0132]

Embedded image The compound represented by formula (III) of the present invention is preferably used in an amount of 10 ^-4 to 1 mol, more preferably 10 ^-3 , per 1 mol of the non-photosensitive silver salt in the image forming layer.
In the range of from 0.8 to 0.8 mol, more preferably from 5 × 10 ^-3 to
It is preferable to use it in the range of 0.5 mol.

In the present invention, as a method for incorporating an antifoggant into a light-sensitive material, the method described in the above-mentioned method for containing a reducing agent can be mentioned, and an organic polyhalogen compound can also be added in the form of a solid fine particle dispersion. preferable.

Other antifoggants include those described in
No. 1-65021 paragraph number [0113] mercury (II) salt,
Benzoic acids of the same paragraph number [0114], JP-A-2000-2000
-206642, salicylic acid derivative, JP-A-2000-2
Formalin scavenger compound represented by formula (S) of JP 21634, JP-A-11-352624
A compound represented by the general formula (III) in JP-A-6-11791, 4-hydroxy-6-methyl
-1,3,3a, 7-tetrazaindene and the like.

The photothermographic material according to the invention may contain an azolium salt for the purpose of preventing fog. Examples of the azolium salt include compounds represented by the general formula (XI) described in JP-A-59-193449, JP-B-55-12581.
And compounds represented by the general formula (II) described in JP-A-60-153039. The azolium salt may be added to any part of the light-sensitive material, but it is preferable to add the azolium salt to the layer having the photosensitive layer, and it is more preferable to add it to the organic silver salt-containing layer.

The azolium salt may be added at any time during the preparation of the coating solution, and when the azolium salt is added to the organic silver salt-containing layer, it may be at any stage from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable after the preparation of the silver salt and immediately before the coating. The azolium salt may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent.

In the present invention, the azolium salt may be added in any amount.
^It is preferably from ^-6 mol to 2 mol, more preferably from 1 x 10 ^-3 mol to 0.5 mol.

In the present invention, a mercapto compound, a disulfide compound and a thione compound are used for controlling development by suppressing or accelerating development, improving spectral sensitization efficiency, and improving storage stability before and after development. And paragraph No. [00] of JP-A-10-62899.
67-0069], compounds represented by the general formula (I) of JP-A-10-186572, and paragraphs [0033 to 0052] as specific examples thereof and European Patent Publication No. 080376.
4A1, Page 20, lines 36-56, Japanese Patent Application No. 11-27
No. 3670 and the like. Among them, mercapto-substituted heteroaromatic compounds are preferred.

(Color Toning Agent) In the photothermographic material of the present invention,
It is preferable to add a color toning agent.
No. 0-62899, paragraph numbers [0054 to 0055],
European Patent Publication No. 0803764A1, page 21, page 23
To 48 lines, JP-A-2000-356317 and Japanese Patent Application No. 200
And phthalazinones (phthalazinones, phthalazinone derivatives or metal salts; for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,2). 3-dihydro-1,4-phthalazinediones); phthalazinones and phthalic acids (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, diammonium phthalate,
Combinations with sodium phthalate, potassium phthalate and tetrachlorophthalic anhydride; phthalazines (phthalazine, phthalazine derivatives or metal salts; for example, 4- (1-
Naphthyl) phthalazine, 6-isopropylphthalazine, 6
-t-butylfuratazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine);
A combination of phthalazines and phthalic acids is preferred, and a combination of phthalazines and phthalic acids is particularly preferred.

The plasticizers and lubricants that can be used in the photosensitive layer of the present invention are described in JP-A No. 11-65021, paragraph [0117], a super-high contrast agent for forming a super-high contrast image, a method of adding the super-high contrast agent, and the like. For the amount, refer to the same paragraph number [0
118], JP-A-11-223898, paragraph [01
36-0193], the formula (H) of Japanese Patent Application No. 11-87297,
Compounds of formulas (1) to (3), formulas (A) and (B),
Compounds of the general formulas (I) to (III) described in JP-A-91652 (concrete compounds: Chemical formulas 21 to 24) and a contrast enhancement accelerator are described in JP-A-11-65021, paragraph [010].
2], paragraph number [0194] of JP-A-11-223898.
To 0195].

In order to use formic acid or formate as a strong fogging substance, 5 mmol or less, more preferably 1 mmol or less, per mole of silver is provided on the side having the image forming layer containing photosensitive silver halide.
It is preferable to contain it in an amount of not more than mmol.

When a super-high contrast agent is used in the photothermographic material of the present invention, it is preferable to use an acid or a salt thereof formed by hydration of diphosphorus pentoxide 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), hexametaline Acid (salt)
And the like. Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and the like.

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

(Surface Protective Layer) The photothermographic material of the present invention may have a non-photosensitive protective layer (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. Regarding the surface protective layer, JP-A-11-65021, paragraph [01]
19-0120] and Japanese Patent Application No. 2000-171936.

As the binder for the surface protective layer of the present invention, a hydrophilic binder is preferably used. The hydrophilic binder is not particularly limited. For example, gelatin is preferable, but polyvinyl alcohol (P
It is also preferable to use or use VA). As gelatin, inert gelatin (for example, Nitta Gelatin 750), phthalated gelatin (for example, Nitta Gelatin 801) and the like can be used. As PVA,
JP-A-2000-171936, paragraph number [0009-
0020], and a completely saponified PV
A-105, partially saponified PVA-205, PVA-3
35, and modified polyvinyl alcohol MP-203 (these are trade names manufactured by Kuraray Co., Ltd.). Polyvinyl alcohol coating amount of the protective layer (per one layer) as (Support 1 m ² per) 0.3 to 4.0 g / m ²
Is preferable, and 0.3 to 2.0 g / m < ² > is more preferable.

In particular, 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 and the back layer. For such polymer latex, see "Synthetic Resin Emulsion (edited by Hira Okuda and Hiroshi Inagaki, published by Kobunshi Kanko (1978))" and "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Keiji Kasahara) Molecular publishing society (1993)), "Synthesis of synthetic latex (Souichi Muroi, published by Kobunshi Kankokai (1970))", and specifically, methyl methacrylate (33.5% by mass). / Ethyl acrylate (50% by mass) / methacrylic acid
(16.5% by mass) copolymer latex, methyl methacrylate (47.5% by mass) / butadiene (47.5% by mass) / itaconic acid (5% by mass) copolymer latex,
Latex of ethyl acrylate / methacrylic acid copolymer, methyl methacrylate (58.9% by mass) / 2-
Latex of ethylhexyl acrylate (25.4% by weight) / styrene (8.6% by weight) / 2-hydroxyethyl methacrylate (5.1% by weight) / acrylic acid (2.0% by weight) copolymer, methyl methacrylate (64.5% by weight) 0% by mass)
/ Styrene (9.0% by mass) / butyl acrylate (20.
0% by mass) / 2-hydroxyethyl methacrylate (5.
0% by mass) / latex of acrylic acid (2.0% by mass) copolymer. Further, as a binder for the surface protective layer, a combination of a polymer latex described in Japanese Patent Application No. 11-6872, a technique described in paragraph Nos. [0021 to 0025] of Japanese Patent Application No. 11-143058, and a technology described in Japanese Patent Application No. No. 11-6872, paragraph [002]
7-0028], Japanese Patent Application No. 10-19962.
The technique described in paragraph No. [0023 to 0041] of the specification of No. 6 may be applied. The ratio of the polymer latex in the surface protective layer is preferably from 10% by mass to 90% by mass of all the binders, and particularly preferably from 20% by mass to 80% by mass.

The coating amount of the binder (including the water-soluble polymer and the latex polymer) of the surface protective layer (per layer) (per 1 m ^{2 of the} support) was 0.3 to 5.0 g / m 2.
² is preferable, and 0.3 to 2.0 g / m ² is more preferable.

(Crosslinking Agent) In the present invention, a crosslinking agent can be preferably used. The crosslinking agent is not particularly limited, and examples of the crosslinking agent include “THE THEORY OF T” by TH James.
HE PHOTOGRAPHICPROCESS FOURTH EDITION ”(Macmillan
Publishing Co., Inc., 1977) 77 pages to 8
There are various methods described on page 7, chromium alum, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N, N-propylenebis (vinylsulfone) Acetamide),
Polyvalent metal ions described in page 78 of the same book, U.S. Pat.
Polyisocyanates such as No. 1060 and JP-A-6-208193, epoxy compounds such as U.S. Pat. No. 4,791,042, and vinylsulfone compounds such as JP-A-62-89048 are preferably used.

The cross-linking agent is added as a solution. The timing of adding this solution to the coating solution for the protective layer is from 180 minutes to immediately before coating, preferably from 60 minutes to 10 seconds before coating. The conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, a method of mixing the average residence time calculated from the addition flow rate and the amount of liquid sent to the coater in a tank so as to have a desired time, N. Harnby, MFEdwards, AWN
ienow, translated by Koji Takahashi, "Liquid Mixing Technology" (Nikkan Kogyo Shimbun, 1989), a method using a static mixer described in Chapter 8 and the like.

The preparation temperature of the coating solution for the image forming layer of the present invention is as follows.
The temperature is preferably 30 ° C. or more and 65 ° C. or less, more preferably 3 ° C.
5 ° C or more and less than 60 ° C, more preferably 35 ° C or more and 5 ° C or less.
5 ° C. or less. Further, the temperature of the image forming layer coating solution immediately after the addition of the polymer latex is preferably maintained at 30 ° C. or higher and 65 ° C. or lower.

The image forming layer of the present invention comprises one or more layers on a support. When it is composed of a single layer, it is composed of an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, and if necessary, further contains additional materials such as a toning agent, a coating auxiliary and other auxiliary agents. When it is composed of two or more layers, the first image-forming layer (usually a layer adjacent to the support) contains an organic silver salt and a photosensitive silver halide, and the second image-forming layer or some of them are contained in both layers. Other components must be included. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, or may include all components in a single layer as described in U.S. Pat. No. 4,708,928. May be. In the case of a multi-dye, multi-color photothermographic material, each emulsion layer generally comprises a functional or non-functional barrier layer between the light-sensitive layers, as described in U.S. Pat. No. 4,460,681. By use, they are kept distinct from each other.

In the photosensitive layer of the present invention, various dyes and pigments (for example, CI Pig / Ment Blue) are used from the viewpoint of color tone improvement, prevention of interference fringe generation during laser exposure, and prevention of irradiation.
60, CIPig / ment Blue 64, CIPig / ment B
lue 15: 6) can be used. These are described in WO 98/36322, JP-A-10-268465.
And No. 11-338098.

In the photothermographic material of the present invention, an antihalation layer can be provided on the side farther from the light source than the photosensitive layer. A photothermographic material generally has a non-photosensitive layer in addition to a photosensitive layer. The non-photosensitive layer may be arranged as follows: (1) a protective layer provided on the photosensitive layer (on the side farther than the support); (2) between a plurality of photosensitive layers or between the photosensitive layer and the protective layer (3) an undercoat layer provided between the photosensitive layer and the support, and (4) a back layer provided on the opposite side of the photosensitive layer. The filter layer is provided on the photosensitive material as the layer (1) or (2). The antihalation layer is provided on the photosensitive material as the layer (3) or (4).

With respect to the antihalation layer, JP-A-11-65021, paragraph numbers [0123 to 0124],
JP-A Nos. 11-223898, 9-230531, 10-36695, 10-104779, and 11-JP
No. 231457, No. 11-352625, No. 11-35
No. 2626 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.

In the case where halation is prevented by using a dye having absorption in the visible region, it is preferable that substantially no color of the dye remains after the image is formed. It is particularly preferable to add a thermal decoloring dye and a base precursor to the non-photosensitive layer to function as an antihalation layer. These techniques are described in Japanese Patent Application Laid-Open No. 11-231457.
No. etc.

The amount of the decolorizable dye is determined depending on the use of the dye. Generally, the optical density (absorbance) measured at the desired wavelength is used in an amount exceeding 0.1. The optical density is preferably from 0.2 to 2. The amount of the dye used to obtain such an optical density is generally 0.00.
It is about 1 to 1 g / m ² .

When the dye is decolored in this manner, the optical density after thermal development can be reduced to 0.1 or less. Two or more decolorizable dyes may be used in combination in a heat-decolorable recording material or a photothermographic material. Similarly, two or more base precursors may be used in combination.

In such thermal decoloring using a decolorizing dye and a base precursor, as described in JP-A-11-352626, when mixed with a base precursor, the melting point becomes 3%.
A substance that lowers by more than ° C (deg) (eg, diphenylsulfone, 4-chlorophenyl (phenyl) sulfone)
It is preferable to use in combination from the viewpoint of thermal decoloring property and the like.

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 tone and the aging of the image. Such colorants are described in JP-A-62-1210458 and JP-A-63-104046.
No., No. 63-103235, No. 63-208846,
Nos. 63-306436 and 63-314535, JP-A-01-61745, and Japanese Patent Application No. 11-276551. Such colorants are usually 0.1
It is added in the range of mg / m ^{2 to 1} g / m ² , and the layer to be added is preferably a back layer provided on the opposite side of the photosensitive layer.

The photothermographic material of the present invention is a so-called single-sided light-sensitive material having at least one photosensitive layer containing a silver halide emulsion on one side of a support and a back layer on the other side. Preferably, there is.

In the present invention, it is preferable to add a matting agent for improving transportability.
JP-A-11-65021, paragraph numbers [0126 to 012]
7]. The matting agent is preferably used in an amount of 1 to 400 mg when represented by the coating amount per 1 m ² of the photosensitive material.
/ M ² , more preferably 5 to 300 mg / m ² .

The degree of matting of the emulsion surface may be any value as long as no star dust failure occurs, but the Beck smoothness is preferably 30 seconds or more and 2,000 seconds or less, particularly 40 seconds or more and 1,50 seconds or less.
0 second or less is preferable. The Beck smoothness can be easily determined by Japanese Industrial Standards (JIS) page 8119 “Smoothness test method of paper and paperboard with Beck tester” and TAPPI standard method T479.

In the present invention, the matting degree of the back layer is such that the Bekk smoothness is preferably 1,200 seconds to 10 seconds, more preferably 800 seconds to 20 seconds, and further preferably 500 seconds to 40 seconds.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferable to be contained.

The back layer applicable to the present invention is described in JP-A No. 11-65021, paragraph [012].
8 to 0130].

The surfactant applicable to the present invention is described in JP-A-11-65021, paragraph [0132],
The same paragraph number [0133] for the solvent, the same paragraph number [0134] for the support, the same paragraph number [0135] for the antistatic or conductive layer, and the same paragraph number [ [0136] As for the slipping agent, JP-A-11-84573, paragraph [006]
1-0064] and Japanese Patent Application No. 11-106881, paragraph numbers [0049-0062].

The photothermographic material of the present invention preferably has a film surface pH before thermal development treatment of 7.0 or less, more preferably 6.6 or less. The lower limit is not particularly limited, but is about 3. The most preferred pH range is between 4 and
6.2. The adjustment of the film surface pH is preferably performed using an organic acid such as a phthalic acid derivative, a nonvolatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is preferable in achieving a low film surface pH since ammonia is easily volatilized and can be removed before the application step and the heat development.

It is also preferable to use a non-volatile base such as sodium hydroxide, potassium hydroxide and lithium hydroxide in combination with ammonia. The method for measuring the film surface pH is described in paragraph [0123] of Japanese Patent Application No. 11-87297.

The transparent support is a polyester which has been subjected to a heat treatment at a temperature in the range of 130 to 185 ° C. in order to alleviate the internal strain remaining in the film at the time of biaxial stretching and to eliminate the heat shrinkage strain generated during the heat development processing. Particularly, polyethylene terephthalate is preferably used. In the case of a photothermographic material for medical use, the transparent support is made of a blue dye (for example,
It may be colored with the dye-1) described in Examples of -240877 or uncolored. The support is disclosed in
No. 84574, water-soluble polyester, 10-1865
No. 65 styrene butadiene copolymer,
It is preferable to apply an undercoating technique such as a vinylidene chloride copolymer described in Japanese Patent Application No. 39684 or Japanese Patent Application No. 11-106881, paragraphs [0063 to 0080]. Japanese Patent Application Laid-Open No. 56-143430 discloses an antistatic layer or an undercoat.
No. 56-143431, No. 58-62646, No. 56-120519, Paragraph No. [0040-0051] of JP-A-11-84573, U.S. Pat. No. 5,575,9
No. 57, paragraph number [00] of JP-A-11-223898.
78 to 0084] can be applied.

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

The photothermographic material further comprises an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers or coating aids may be added. Various additives are added to either the photosensitive layer or the non-photosensitive layer. WO98 about them
/ 36322, EP803376A1, JP-A-10-
186567 and 10-18568 can be referred to.

The photothermographic material of the present invention may be applied by any method. Specifically, extrusion coating, slide coating, curtain coating, dip coating, knife coating,
Various coating operations are used, including flow coating, or extrusion coating using a hopper of the type described in U.S. Patent No. 2,681,294, to which Stephen F. Kis
"LIQUID FILM COATING" by tler, Petert M. Schweizer
(CHAPMAN & HALL, 1997) p.399-536
Extrusion coating or slide coating described on the page is preferably used, and slide coating is particularly preferably used. An example of the shape of a slide coater used for slide coating is described in Ibid.
Figure 11b.1 on the page. Ibid 39
The method described on pages 9 to 536, U.S. Pat.
No. 1 and British Patent No. 837095 can simultaneously coat two or more layers.

The coating solution for the organic silver salt-containing layer in the present invention comprises:
Preferably, it is a so-called thixotropic fluid. For this technique, reference can be made to JP-A-11-52509. The viscosity of the coating solution for the organic silver salt-containing layer in the present invention at a shear rate of 0.1 S ^-1 is preferably from 400 mPa · s to 100,000 mPa · s, more preferably from 500 mPa · s to 20,000 mPa · s.
It is as follows. Further, at a shear rate of 1000 S ^-1 , 1
It is preferably from mPa · s to 200 mPa · s, more preferably from 5 mPa · s to 80 mPa · s.

Techniques that can be used in the photothermographic material of the present invention include EP803376A1 and EP88.
3022A1, WO98 / 36322, JP-A-56-
Nos. 62648 and 58-62644, JP-A-9-437
Nos. 66, 9-281637, 9-29767, 9
-304869, 9-31405, 9-329
No. 865, No. 10-10669, No. 10-62899
No. 10-69023, No. 10-186568, No. 10-90823, No. 10-171063, No. 10-
No. 186565, No. 10-186567, No. 10-18
No. 6569-No. 10-186572, No. 10-1979
No. 74, No. 10-197982, No. 10-197983
No. 10-197985 to 10-197987,
No. 10-207001, No. 10-207004, No. 1
No. 0-221807, No. 10-282601, No. 10-
288823, 10-288824, 10-30
No. 7365, No. 10-312038, No. 10-3399
No. 34, No. 11-7100, No. 11-15105, No. 11-24200, No. 11-24201, No. 11-3
0832, 11-84574, 11-65021
No. 11-109947, No. 11-125880,
11-129629 and 11-133536 to 1
No. 1-133539, No. 11-133542, No. 11-
No. 133543, No. 11-223898, No. 11-35
No. 2627, No. 11-305377, No. 11-3053
No. 78, No. 11-305384, No. 11-305380
No., 11-316435, 11-327076,
No. 11-338096, No. 11-338098, No. 1
No. 1-338099, No. 11-343420, Japanese Patent Application No. 20
00-187298, 2000-10229, 2
Nos. 000-47345, 2000-206642, 2000-98530, 2000-98531, 2000-112059, 2000-112060
No. 2000-112104, 2000-1120
No. 64 and 2000-171936.

The photothermographic material of the present invention may be developed by any method, but is usually developed by elevating the temperature of the photothermographic material exposed imagewise. The preferred development temperature is 80 to 250 ° C, more preferably 1 to 250 ° C.
00-140 ° C. The development time is preferably 1 to 60 seconds, more preferably 5 to 30 seconds, and particularly preferably 10 to 20 seconds.

As a method of thermal development, a plate heater method is preferable. The heat development method using a plate heater method is preferably a method described in JP-A-11-133572, in which a heat-developable photosensitive material on which a latent image is formed is brought into contact with a heating means in a heat development section to obtain a visible image. A developing device, wherein the heating means comprises a plate heater, and a plurality of pressing rollers are provided to face each other along one surface of the plate heater, and the heating means is provided between the pressing roller and the plate heater. A thermal developing apparatus for performing thermal development by passing a developing photosensitive material. It is preferable to divide the plate heater into two to six stages and lower the temperature at the tip part by about 1 to 10 ° C. Such a method is also described in JP-A-54-30032, in which water and organic solvents contained in the photothermographic material can be excluded from the system. The change in the shape of the support of the photothermographic material due to the heating of the photothermographic material can also be suppressed.

The light-sensitive material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source.
As the laser beam according to the present invention, a gas laser (Ar ⁺ ,
He-Ne), a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a semiconductor laser and a second harmonic generation element can be used. Preferably, a gas or semiconductor laser emitting red to infrared light is used.

As a medical laser imager having an exposure section and a heat development section, Fuji Medical Dry Laser Imager FM-DPL can be mentioned.
Regarding FM-DPL, Fuji Medical Review No.
8, pages 39 to 55, and it goes without saying that those techniques are applied to the laser imager of the photothermographic material of the present invention. It can also be used as a photothermographic material for laser imagers in the "AD network" proposed by Fuji Medical System as a network system conforming to the DICOM standard.

The photothermographic material of the present invention forms a black-and-white image using a silver image, and is used for medical diagnosis, photothermographic material for industrial photography, photothermographic material for printing, and COM.
Is preferably used as a photothermographic material.

[0181]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

(Preparation of PET support) Using terephthalic acid and ethylene glycol, the intrinsic viscosity IV =
This gave polyethylene terephthalate (PET) of 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.). After pelletizing this, 130
After drying at 400C for 4 hours and melting at 300C, it was extruded from a T-die and quenched to prepare an unstretched PET film having a thickness of 175 µm after heat setting.

This is achieved by using rolls having different peripheral speeds.
The film was longitudinally stretched by a factor of 2. Then, the film was horizontally stretched by a factor of 4.5 with a tenter. The temperatures at this time are 110 ° C and 130 ° C, respectively.
Met. After that, it was heat-set at 240 ° C. for 20 seconds, and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling is performed on both ends, and wound at 4 kg / cm ² , and PE having a thickness of 175 μm is formed.
A roll of T film was obtained.

(Surface Corona Treatment) Using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, 0.375 kV was applied to the support.
-It turned out that the processing of A * min / m < ² > was performed. At this time, the corona treatment frequency was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

(Preparation of Undercoating Support) (1) Preparation of Coating Solution for Undercoating Layer Formulation <for undercoating layer on photosensitive layer side> 234 g (30% by mass solution) of Pesresin A-515GB manufactured by Takamatsu Yushi Co., Ltd. Monononyl phenyl ether 21.5 g (average ethylene oxide number = 8.5) 10 mass% solution ・ 0.91 g of MP-1000 manufactured by Soken Chemical Co., Ltd. (polymer fine particles, average particle diameter 0.4 μm) ・ Distilled water 744 ml

Formulation <for Back Layer First Layer> Styrene-butadiene copolymer latex 158 g (solid content 40% by mass, styrene / butadiene mass ratio = 68/32) 2,4-dichloro-6-hydroxy- S-triazine sodium salt (8% by mass aqueous solution) 20 g 1% by mass aqueous solution of sodium laurylbenzenesulfonate 10 ml Distilled water 854 ml

Formulation <for back surface side second layer> SnO ₂ / SbO (9/1 mass ratio, average particle size 0.038 μm, 17% by mass dispersion) 84 g Gelatin (10% by mass aqueous solution) 89.2 g 8.6 g of Metroze TC-5 (2 mass% aqueous solution) manufactured by Shin-Etsu Chemical Co., Ltd. 0.01 g of MP-1000 manufactured by Soken Chemical Co., Ltd. 10 ml of 1 mass% aqueous solution of sodium dodecylbenzenesulfonate ・ NaOH (1 mass%) 6 ml ・ Proxel (ICI) 1 ml ・ Distilled water 805 ml

(Preparation of Undercoat Support) The above thickness of 175 μm
After performing the above-described corona discharge treatment on both sides of the biaxially stretched polyethylene terephthalate support, the undercoating coating solution formulation was applied on one side (photosensitive layer side) with a wire bar at a wet application amount of 6.6 ml / m ² (one side). ) And dried at 180 ° C. for 5 minutes. Then, the undercoat coating solution was coated on the back surface (back surface) with a wire bar so that the wet coating amount was 5.7 ml / m ^2. And dried at 180 ° C for 5 minutes.
The above-mentioned undercoating coating liquid formulation was applied with a wire bar so that the wet coating amount was 7.7 ml / m ² , and the temperature was 180 ° C.
For 6 minutes to prepare an undercoat support.

(Preparation of Back Surface Coating Solution) (Preparation of Solid Precursor Dispersion (a) of Base Precursor) 64 g of base precursor compound 11, 28 g of diphenylsulfone and Demol N, a surfactant manufactured by Kao Corporation
Was mixed with 220 ml of distilled water, and the mixture was dispersed in beads using a sand mill (1/4 Gallon sand grinder mill, manufactured by Imex Co., Ltd.) to disperse solid fine particles of a base precursor compound having an average particle diameter of 0.2 μm. Liquid (a) was obtained.

(Preparation of Dye Solid Fine Particle Dispersion) 9.6 g of cyanine dye compound 13 and 5.8 g of sodium p-dodecylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixture was subjected to a sand mill (1/4 Gallon sand grinder). The resulting mixture was dispersed in beads using a mill (manufactured by IMEX Co., Ltd.) to obtain a dye solid fine particle dispersion having an average particle size of 0.2 μm.

(Preparation of Coating Solution for Antihalation Layer) 17 g of gelatin, 9.6 g of polyacrylamide, 70 g of solid fine particle dispersion (a) of the above base precursor, 56 g of solid fine particle dispersion of dye, and monodispersed polymethyl methacrylate fine particles (average (Particle size 8 μm, particle size standard deviation 0.4)
1.5 g, benzoisothiazolinone 0.03 g, sodium polyethylene sulfonate 2.2 g, blue dye compound 14 0.2 g, yellow dye compound 15 3.9 g, water 8
44 ml were mixed to prepare an antihalation layer coating solution.

(Preparation of Coating Solution for Back Surface Protective Layer)
Incubate at 0 ° C., gelatin 50 g, polystyrene sodium 0.2 g, N, N-ethylenebis (vinylsulfoneacetamide) 2.4 g, t-octylphenoxyethoxyethaneethanesulfonate 1 g, benzoisothiazolinone 30 mg, fluorine Surfactant (F-
1: 37 mg of 1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt; fluorinated surfactant (F-2: polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl))
Ether [average degree of polymerization of ethylene oxide 15]) 0.1
5 g, fluorinated surfactant (F-3) 64 mg, fluorinated alert surfactant (F-4) 32 mg, acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) 8.
8g, Aerosol OT (American Cyanamid)
0.6 g, 1.8 g of the liquid paraffin emulsion as liquid paraffin, and 950 ml of water were mixed to prepare a coating liquid for the back surface protective layer.

<< Preparation of Silver Halide Emulsion 1 >> Distilled Water 14
While adding 3.1 ml of a 1% by weight potassium bromide solution to 21 ml, further adding 3.5 ml of 0.5 mol / L sulfuric acid, and 31.7 g of phthalated gelatin, stirring the solution in a stainless steel reaction bottle, Keep the solution temperature at 30 ° C and add silver nitrate 2
Solution A diluted to 95.4 ml by adding distilled water to 2.22 g
And a solution B obtained by diluting potassium bromide (15.3 g) and potassium iodide (0.8 g) with distilled water to a volume of 97.4 ml was added at a constant flow rate over 45 seconds. After that, 3.5 mass%
Was added, and 10.8 ml of a 10% by mass aqueous solution of benzimidazole was further added. Further, distilled water was added to 51.86 g of silver nitrate to obtain 31.
Solution C diluted to 7.5 ml, solution D prepared by diluting potassium bromide 44.2 g and potassium iodide 2.2 g to a volume of 400 ml with distilled water, and solution C were all added at a constant flow rate over 20 minutes. Solution D was added by the controlled double jet method while maintaining the pAg at 8.1. The total amount of potassium hexachloride iridate (III) was added 10 minutes after starting to add the solution C and the solution D so as to be 1 × 10 ⁻⁴ mol per mol of silver. In addition, 5 of completion of addition of solution C
After 2 seconds, an aqueous solution of potassium hexacyanoferrate (II) 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, the stirring was stopped, and the sedimentation / desalting / water washing steps were 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.

While stirring the silver halide dispersion, 3
While maintaining the temperature at 8 ° C., 5 ml of a methanol solution of 0.34% by mass of 1,2-benzoisothiazolin-3-one was added, and 40
After 1 minute, a methanol solution having a molar ratio of 1: 1 between the spectral sensitizing dye A and the sensitizing dye B was added at 1.2 × 10 ⁻³ mol per mol of silver, and 1 minute after the addition, 47% was added. The temperature was raised to ° C. Twenty minutes after the temperature rise, 7.6 × 1 sodium benzenethiosulfonate was added to 1 mol of silver with a methanol solution.
0 ^-5 mols, further 5 minutes after the tellurium sensitizer B added 2.9 × 10 ^-4 mol per 1 mol of silver in methanol solution 9
Aged for 1 minute. 1.3 ml of a 0.8% by weight methanol solution of N, N'-dihydroxy-N "-diethylmelamine was added, and 4 minutes later, 5-methyl-2-mercaptobenzimidazole was added with methanol solution at a concentration of 4 mol / mol silver. .8 × 10
^-3 mol and 1-phenyl-2-heptyl-5-mercapto-
Silver halide emulsion 1 was prepared by adding 5.4 × 10 ^-3 mol of 1,3,4-triazole to 1 mol of silver in a methanol solution.

The grains in the prepared silver halide emulsion were as follows:
Average sphere equivalent diameter 0.042 μm, coefficient of variation of sphere equivalent diameter 20
% Iodide was uniformly contained in 3.5 mol% of silver iodobromide grains. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The [100] plane 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 set at 34 ° C.
The temperature was changed to 7 ° C., solution B was changed to dilute 15.9 g of potassium bromide to a volume of 97.4 ml with distilled water, and solution D was prepared by diluting 45.8 g of potassium bromide with a volume of 400 m in distilled water.
The silver halide emulsion 2 was prepared in the same manner except that the dilution was changed to 1 and the addition time of the solution C was changed to 30 minutes to remove potassium hexacyanoferrate (II). Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1.
Further, the molar ratio of the spectral sensitizing dye A to the spectral sensitizing dye B is 1: 1.
Sensitizing dye A per mole of silver
And sensitizing dye B in a total amount of 7.5 × 10 ^-4 mol, and the amount of tellurium sensitizer B added was 1.1 × 10 ^-4 mol per mol of silver and 1-phenyl-2-heptyl-5-mercapto. -1,3,4
Spectral sensitization, chemical sensitization, and 5-methyl-2-mercaptobenzimidazole, and 1-phenyl were performed in the same manner as in Emulsion 1, except that the amount of ^3- triazole was changed to 3.3 × 10 ^-3 mol per mol of silver. -2-Heptyl-5-mercapto-1,3,4-triazole was added to obtain a silver halide emulsion 2. The emulsion grains of the silver halide emulsion 2 have an average sphere equivalent diameter of 0.080 μm.
m, pure silver bromide cubic grains having a sphere equivalent diameter variation coefficient of 20%.

<< Preparation of Silver Halide Emulsion 3 >> In the preparation of silver halide emulsion 1, the liquid temperature at the time of grain formation was set at 34 ° C. for 2 hours.
Except that the temperature was changed to 7.degree.
Was prepared. Further, precipitation / desalting / washing / dispersion / dispersion was carried out in the same manner as in silver halide emulsion 1. The molar ratio of the spectral sensitizing dye A to the spectral sensitizing dye B was 1: 1 as a solid dispersion (aqueous gelatin solution), and the addition amount was 6 × 10 ⁻ as the total amount of the sensitizing dye A and the sensitizing dye B per mole of silver. Silver halide emulsion 3 was obtained in the same manner as in emulsion 1, except that the amount of ³ mol of tellurium sensitizer B was changed to 5.2 × 10 ^-4 mol per mol of silver.
The emulsion grains of the silver halide emulsion 3 had an average equivalent sphere diameter of 0.0.
The particles were silver iodobromide particles containing 3.5 mol% of iodine having a uniform particle diameter of 34% and a variation coefficient of 20%.

<< Preparation of Mixed Emulsion A for Coating Solution >> A silver halide emulsion 1 was dissolved in 70% by mass, a silver halide emulsion 2 was dissolved in 15% by mass, and a silver halide emulsion 3 was dissolved in 15% by mass. 7 × 10 ⁻³ mol per mol of silver was added as a 1% by mass aqueous solution of the amide. Further, the content of silver halide per kg of the mixed emulsion for coating solution was 38.2 as silver.
g.

<< Preparation of Fatty Acid Silver Dispersion >> 87.6 Kg of behenic acid (product name: Edenor C22-85R) manufactured by Henkel, 423 L of distilled water, 49.2 L of 5 mol / L NaOH aqueous solution, tert.
-Butanol (120 L) was mixed and reacted at 75 ° C. with stirring for 1 hour to obtain a sodium behenate solution. Separately, 206.2 L (pH 4.0) of an aqueous solution containing 40.4 kg of silver nitrate was prepared and kept at 10 ° C. 635L of distilled water and 30L of te
The reaction vessel containing rt-butanol was kept at 30 ° C., and the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were added at a constant flow rate over 93 minutes, 15 seconds and 90 minutes, respectively, with sufficient stirring. At this time, only the aqueous silver nitrate solution was added for 11 minutes after the addition of the aqueous silver nitrate solution was started, and then the addition of the sodium behenate solution was started. After the addition of the aqueous silver nitrate solution was completed, only the sodium behenate solution was added for 14 minutes and 15 seconds. I was doing it. At this time, the temperature inside the reaction vessel was set at 30 ° C., and the external temperature was controlled so that the liquid temperature became constant. In addition, the piping of the addition system of the sodium behenate solution is kept warm by circulating hot water outside the double pipe, and the liquid temperature at the outlet of the addition nozzle tip is 75 ° C.
° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution.

After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and then stirred for 35 minutes.
C., and aging was performed for 210 minutes. Immediately after the completion of the ripening, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtered water became 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying.

The morphology of the obtained silver behenate particles was evaluated by electron microscopic photographing. The average value was a = 0.14 μm.
m, b = 0.4 μm, c = 0.6 μm, average aspect ratio 5.
2. Average sphere equivalent diameter 0.52 μm, variation coefficient of sphere equivalent diameter 1
5% scaly crystals. (A, b, c are the rules of the text)

A wet cake having a dry solid content of 260 kg was added to polyvinyl alcohol (trade name: PVA-21).
7) Add 19.3Kg and water to make the total amount 1000K
Then, the slurry was made into a slurry with a dissolver blade, and further pre-dispersed with a pipeline mixer (PM-10, manufactured by Mizuho Kogyo).

Next, the pre-dispersed undiluted solution was subjected to a pressure of 1 using a dispersing machine (trade name: Microfluidizer M-610, manufactured by Microfluidics International Corporation, using a Z-type interaction chamber).
The mixture was adjusted to 260 kg / cm ² and treated three times to obtain a silver behenate dispersion. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the dispersion temperature was set at 18 ° C. by adjusting the temperature of the refrigerant.

<< Preparation of Dispersion of Reducing Agent-1 >> Reducing Agent-1
(1,1-bis (2-hydroxy-3,5-dimethylphenyl)
10 kg of -3,5,5-trimethylhexane) and modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
16 kg of water was added to 10 kg of a 20% by mass aqueous solution of
The slurry was mixed well to form a slurry. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then sodium benzoisothiazolinone was added. 0.2 g and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a reducing agent-1 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.42 μm and a maximum particle diameter of 2.0 μm or less. The obtained reducing agent 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 Reducing Agent-2 Dispersion >> Reducing Agent-2
16 kg of water was added to 10 kg of (2,2′-isobutylidene-bis- (4,6-dimethylphenol)) and 10 kg of a 20% by mass aqueous solution of a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203). Mix to form a slurry. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then sodium benzoisothiazolinone was added. 0.2 g and water are added to reduce the concentration of the reducing agent to 25.
% By mass to obtain a reducing agent-2 dispersion.
The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.38 μm and a maximum particle diameter of 2.0 μm or less. The obtained reducing agent 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 Dispersion of Reducing Agent Complex-3 >> 10 kg of Reducing Agent Complex-3 (1: 1 complex of 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol) and triphenylphosphine oxide) , 0.12 kg of triphenylphosphine oxide and a 10% by mass aqueous solution of a modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
To 6 kg, 7.2 kg of water was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 4 hours and 30 minutes, and then benzoisothiazolinone sodium salt was added. 0.2 g and water are added to reduce the concentration of the reducing agent to 25.
It was adjusted so as to be mass%, and a reducing agent complex-3 dispersion was obtained. The reducing agent complex particles contained in the thus obtained reducing agent complex dispersion had a median diameter of 0.46 μm and a maximum particle diameter of 1.6 μm.
m or less. The obtained reducing agent complex dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Reducing Agent-4 Dispersion >> Reducing Agent-4
6 kg of water was added to 10 kg of (2,2′-methylenebis- (4-ethyl-6-tert-butylphenol)) and 20 kg of a 10% by mass aqueous solution of a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203). The slurry was mixed well to form a slurry. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then sodium benzoisothiazolinone was added. 0.2 g and water are added to reduce the concentration of the reducing agent to 25.
It was adjusted so as to be mass% to obtain a reducing agent-4 dispersion.
The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Dispersion of Reducing Agent-5 >> Reducing Agent-5
6 kg of water was added to 10 kg of (2,2′-methylenebis- (4-methyl-6-tert-butylphenol)) and 20 kg of a 10% by mass aqueous solution of a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203). The slurry was mixed well to form a slurry. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then sodium benzoisothiazolinone was added. 0.2 g and water are added to reduce the concentration of the reducing agent to 25.
% By mass to obtain a reducing agent-5 dispersion.
The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.38 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Hydrogen Bonding Compound-2 Dispersion >> Hydrogen bonding compound-2 (tri (4-t-butylphenyl))
10 kg of water was added to 10 kg of a 10 mass% aqueous solution of 10 kg of a phosphine oxide) and a 10% by mass aqueous solution of a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203) and mixed well to form a slurry. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then sodium benzoisothiazolinone was added. 0.2 g and water were added to adjust the concentration of the reducing agent to 22% by mass to obtain a hydrogen bonding compound-2 dispersion. The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.35 μm and a maximum particle diameter of 1.5 μm or less. The obtained hydrogen bonding compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Dispersion of Organic Polyhalogen Compound-1 >> 10 kg of organic polyhalogen compound-1 (2-tribromomethanesulfonylnaphthalene) and 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) And 0.4 kg of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate;
16 kg of water was added and mixed well to form a slurry.
The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then sodium benzoisothiazolinone sodium salt was added. 2
g and water, and the concentration of the organic polyhalogen compound is 23.
It was adjusted to 5% 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 0.36 μm and a maximum particle diameter of 2.0 μm or less.
The resulting organic polyhalogen compound dispersion had a pore size of 10.
Filtered with a 0 μm polypropylene filter,
Foreign matter such as dust was removed and stored.

<< Preparation of Dispersion of Organic Polyhalogen Compound-2 >> 10 kg of organic polyhalogen compound-2 (tribromethanesulfonylbenzene) and 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) 0.4 kg of a 20 mass% aqueous solution of sodium isopropylnaphthalenesulfonate and 14 k of water
g was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and has an average diameter of 0.5 m.
m horizontal zirconia beads filled horizontal sand mill (UV
M-2: manufactured by Imex Co., Ltd.) for 5 hours, and then 0.2 g of sodium benzoisothiazolinone and water were added to adjust the concentration of the organic polyhalogen compound to 26% by mass. A polyhalogen compound-2 dispersion was obtained. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained have a median diameter of 0.4.
1 μm and the maximum particle size was 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-3 Dispersion >> 10 kg of a chronological polyhalogen compound-3 (N-butyl-3-tribromomethanesulfonylbenzamide) and modified polyvinyl alcohol (Poval MP2 manufactured by Kuraray Co., Ltd.)
20 kg of a 10% by mass aqueous solution of No. 03), 0.4 kg of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate, and 8 kg of water were added and mixed well to form a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then sodium benzoisothiazolinone sodium salt was added. 2 g and water were added to adjust the concentration of the organic polyhalogen compound to 25% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-3 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.36 μm and a maximum particle diameter of 1.5 μm or less. The resulting organic polyhalogen compound dispersion has a pore size of 3.0 μm.
And filtered to remove foreign matter such as dust, and stored.

<< Preparation of Phthalazine Compound-1 Solution >> 8k
g modified Kuraray Co., Ltd. modified polyvinyl alcohol MP20
Was dissolved in 174.57 kg of water, and then 3.15 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28 kg of a 70% by weight aqueous solution of phthalazine compound-1 (6-isopropylphthalazine) were added. A 5% by mass solution of compound-1 was prepared.

<< Preparation of Mercapto Compound- 1 Aqueous Solution >> Mercapto compound-1 (1- (3-sulfophenyl) -5
7 g of mercaptotetrazole sodium salt) in water 99
3 g to give a 0.7% by mass aqueous solution.

<< Preparation of Pigment-1 Dispersion >> CI Pigment
250 g of water was added to 64 g of Blue 60 and 6.4 g of Demol N manufactured by Kao Corporation and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm is prepared, put into a vessel together with the slurry, and dispersed in a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.).
The mixture was dispersed for 5 hours to obtain a pigment-1 dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

<< Preparation of SBR Latex Liquid >> Tg = 23
C. SBR latex was prepared as follows. Using ammonium persulfate as a polymerization initiator and an anionic surfactant as an emulsifier, styrene (70.5 mass), butadiene (26.5 mass) and acrylic acid (3 mass) were emulsion-polymerized and then aged at 80 ° C. for 8 hours. Then 40 ° C
Then, the pH was adjusted to 7.0 with aqueous ammonia, and Sandet BL manufactured by Sanyo Kasei Co., Ltd. was added to 0.22%. Next, a 5% aqueous sodium hydroxide solution was added to adjust the pH to 8.3, and then the pH was adjusted to 8.3 with aqueous ammonia.
Adjusted to be 4. The molar ratio of Na ⁺ ion to NH ₄ ⁺ ion used at this time was 1: 2.3. further,
0.15 ml of a 7% aqueous solution of benzoisothiazolinone sodium salt was added to 1 kg of this solution to prepare an SBR latex solution. (SBR latex: -St (70.5) -Bu (26.5) -AA (3)
-Latex) Tg23 ℃

Average particle size: 0.1 μm, concentration: 43% by mass, 2
Equilibrium water content at 5 ° C and 60% RH: 0.6% by mass, ion conductivity: 4.2 ms / cm (Ion conductivity was measured using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd.).
3% by mass) at 25 ° C.), and the SBR latex having a different pH of 8.4 Tg was prepared in the same manner by appropriately changing the ratio of styrene and butadiene.

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1 >>
1,000 g of the fatty acid silver dispersion obtained above, 125 m of water
1, reducing agent-1 dispersion 113 g, reducing agent-2 dispersion 91
g, pigment-1 dispersion 27 g, organic polyhalogen compound-
82 g of 1 dispersion, organic polyhalogen compound-2 dispersion 4
0 g, phthalazine compound-1 solution 173 g, SBR latex (Tg: 20.5 ° C.) solution 1,082 g, and mercapto compound-1 aqueous solution 9 g were sequentially added. Immediately before coating, 158 g of silver halide mixed emulsion A for coating solution was added. The well-mixed emulsion layer coating solution-1 was directly fed to a coating die and coated.

The viscosity of the above emulsion layer coating solution was measured with a B-type viscometer (Tokyo Keiki) at 40 ° C. (No. 1 rotor, 60 rpm).
pm) was 85 [mPa · s]. The viscosity of the coating solution at 25 ° C. using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. was 1 at a shear rate of 0.1, 1, 10, 100, and 1,000 [1 / sec]. , 500, 220, 70, 40, 20
[mPa · s].

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-2 >>
1,000 g of the fatty acid silver dispersion obtained above, 104 m of water
1, 30 g of pigment- 1 dispersion, organic polyhalogen compound-
21 g of 2 dispersion, organic polyhalogen compound-3 dispersion 6
9 g, phthalazine compound-1 solution 173 g, SBR latex (Tg: 23 ° C.) solution 1,082 g, reducing agent complex-3
258 g of a dispersion and 9 g of a mercapto compound-1 solution were sequentially added, and immediately before coating, a silver halide mixed emulsion A11 for coating was added.
0 g was added, and the well-mixed emulsion layer coating solution-2 was directly sent to a coating die and coated.

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-3 >>
1,000 g of the fatty acid silver dispersion obtained above, 95 ml of water,
Reducing agent-4 dispersion 73, reducing agent-5 dispersion 68g, pigment-1 dispersion 30g, organic polyhalogen compound-2 dispersion 21g, organic polyhalogen compound-3 dispersion 69g, phthalazine compound-1 solution 173g, SBR core-shell type latex (core Tg: 20 ° C./shell Tg: 30 ° C. = 7)
0/30 mass ratio) 1,082 g of liquid , hydrogen bonding compound
124 g of a dispersion 2 and 9 g of a mercapto compound-1 solution were sequentially added, and immediately before coating, a silver halide mixed emulsion A1 for coating was added.
10 g was added, and the well-mixed emulsion layer coating solution-3 was directly sent to a coating die and coated.

<< Preparation of Emulsion Surface Intermediate Layer Coating Solution >> 10% by mass of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.)
772 g of an aqueous solution, 5.3 g of a 20% by mass dispersion of a pigment, methyl methacrylate / styrene / butyl acrylate /
Hydroxyethyl methacrylate / acrylic acid copolymer
(Copolymerization mass ratio 64/9/20/5/2) Latex 2
To 226 g of the 7.5% by mass liquid, 2 ml of a 5% by mass aqueous solution of aerosol OT (manufactured by American Cyanamid Co.) and 10.5 m of a 20% by mass aqueous solution of diammonium phthalate were used.
1, water was added to make the total amount 880 g, and the pH was 7.5.
It was adjusted with NaOH so that
The solution was fed to the coating die so as to be 10 ml / m ² . The viscosity of the coating solution was 21 mPa · s using a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).

<< Preparation of Coating Solution for First Layer of Emulsion Surface Protecting Layer >> 64 g of inert gelatin was dissolved in water, and a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer mass ratio: 6
4/9/20/5/2) 27.5% by mass latex liquid 8
0 g, 10% methanol solution of phthalic acid in 23m
1, 23 ml of a 10% by weight aqueous solution of 4-methylphthalic acid,
28 ml of sulfuric acid having a concentration of 0.5 mol / L, 5 ml of a 5% by mass aqueous solution of aerosol OT (manufactured by American Cyanamid), 0.5 g of phenoxyethanol, and 0.1 g of benzoisothiazolinone are added to make a total amount of 750 g. To a coating solution by adding water to the mixture, 26 ml of 4% by mass chromium alum
Is mixed with a static mixer immediately before application.
The solution was sent to the coating die so as to be 8.6 ml / m ² . The viscosity of the coating solution was 17 mPa · s using a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).

<< Preparation of Coating Solution for Emulsion Surface Protective Layer Second Layer >> Inert gelatin (80 g) was dissolved in water, and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio: 6)
4/9/20/5/2) 27.5% by mass latex liquid 1
3.2 g of a 5% by mass solution of a fluorine-based surfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt) in an amount of 3.2 g, and a fluorine-based surfactant (F-2: polyethylene glycol mono ( 32 ml of a 2% by weight aqueous solution of N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide = 15]) and a 5% by weight solution of aerosol OT (American Cyanamid) , 23 g of polymethyl methacrylate fine particles (average particle size 0.7 μm), 4 g of polymethyl methacrylate fine particles (average particle size 4.5 μm)
1 g, 4-methylphthalic acid 1.6 g, phthalic acid 4.8 g,
Water is added to 44 ml of 0.5 mol / L sulfuric acid and 10 mg of benzoisothiazolinone so that the total amount becomes 650 g, and 445 ml of an aqueous solution containing 4% by mass of chromium alum and 0.67% by mass of phthalic acid is applied. Immediately before, the mixture mixed with a static mixer was used as the coating solution for the surface protective layer.
The solution was sent to the coating die at 3 ml / m ² . The viscosity of the coating solution was 9 mPa · s using a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).

[Preparation of Photothermographic Material-101] An antihalation layer coating solution was applied on the back surface side of the undercoating support so that the coating amount of the solid fine particle dye was 0.04 g / m ^2. The coating solution for the back surface protective layer was simultaneously coated in a multilayer so that the amount of gelatin applied was 1.7 g / m ^2, and dried to form a back layer.

The emulsion layer (using emulsion layer coating solution-1), the intermediate layer, the first protective layer,
The protective layer was coated simultaneously with the second layer in the order of the second layer by a slide bead coating method to prepare Sample 101 of the photothermographic material.
At this time, the emulsion layer and the intermediate layer were kept at 31 ° C.
The temperature was adjusted to 6 ° C and the temperature of the second protective layer to 37 ° C.

Coating amount of each compound in emulsion layer (g / m ² )
Was as follows.・ Silver behenate 6.19 ・ Reducing agent-1 0.67 ・ Reducing agent-2 0.54 ・ Pigment (CIPigment Blue 60) 0.032 ・ Polyhalogen compound-1 0.46 ・ Polyhalogen compound-2 25-Phthalazine compound-1 0.21-SBR latex 11.1-Mercapto compound-1 0.002-Silver halide (as Ag) 0.145

The conditions for coating and drying were as follows. The coating was performed at a speed of 160 m / min, the gap between the tip of the coating die and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set 196 to 882 Pa lower than the atmospheric pressure. The support was neutralized with ion wind before coating.

In the subsequent chilling zone, the dry-bulb temperature was 1
After the coating solution is cooled by a wind of 0 to 20 ° C., the coating solution is conveyed in a non-contact type, and dried at a dry bulb temperature of 23 with a helix type non-contact drying device.
It dried with the dry air of -45 degreeC, and the wet bulb temperature of 15-21 degreeC. After drying, the film was conditioned at 25 ° C. and a 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 degree of matting of the produced photothermographic material was as follows:
The Beck smoothness was 550 seconds on the photosensitive layer side and 1 on the back side.
30 seconds. Further, the pH of the film surface on the side of the photosensitive layer was measured and found to be 6.0.

[Preparation of Photothermographic Materials-102 to 119] Table 1 was prepared for Sample 101 of the above photothermographic material.
Samples 102 to 119 of the photothermographic material were produced in the same manner as in Sample 101, except for the following changes.

<Evaluation of Photographic Performance> Fuji Medical Dry Laser Imager FM-DP L (Max.
IB) Exposure and thermal development of photographic material (112 ° C-119 ° C-121 ° C-
4 panel heaters set at 121 ° C for a total of 24
Seconds), the obtained image was evaluated using a densitometer.

<Evaluation of Image Preservation> Fuji Medical Dry Laser Imager FM-DP L (60 mW max.)
(IIIB) 660nm semiconductor laser output)
Exposure and thermal development (about 120 ° C) of the photographic material, then 30 ° C
In an environment of 70% RH, the illuminance is 10.0 under fluorescent light.
The image after being stored for 24 hours under the condition of 0 L was evaluated with a densitometer, and the difference from the result obtained by the above-described photographic performance evaluation method was calculated to evaluate the image storability.

<Evaluation of Blocking Property> The photothermographic material was heat-developed in the same manner as in the evaluation of photographic performance described above, and then humidified at 25 ° C. and 75% RH for 16 hours. Then, a load of 150 g was applied to an area of 35 mm × 35 mm, and the following criteria were used to evaluate the peeled area when peeled off at 50 ° C. for 48 hours. [Criterion] ：: There is no blocking at all. ：: There is a slight trace on the surface but no blocking. Δ: There is a slight blocking trace. ×: Blocking traces exist in nearly half the area. XX: Blocking marks are present in almost all areas. Table 1 shows the above evaluation results.

[0235]

[Table 1]

As is clear from Table 1, the photothermographic materials of the present invention containing the latex which reacts with gelatin (samples 102 to 119) are excellent in photographic performance, image storability and blocking ability. Was. On the other hand, it is presumed that the sample 101 having a configuration other than that of the present invention has poor blocking properties due to high binder fluidity under high temperature and high humidity.

[Preparation of Photothermographic Materials-201 to 219] In the preparation of photothermographic materials-101 to 119,
Except that the emulsion layer coating solution-1 was changed to the emulsion layer coating solution-2, and the yellow dye compound 15 was further removed from the antihalation layer, the photothermographic material- 201 to 219 were created.

At this time, the coating amount of each compound in the emulsion layer (g
/ M ² ) was as follows. -Silver behenate 6.19-Pigment (CIPigment Blue 60) 0.036-Polyhalogen compound-2 0.13-Polyhalogen compound-3 0.41-Phthalazine compound-1 0.21-SBR latex 11.1- Reducing agent complex-3 1.54 -mercapto compound-1 0.002 -silver halide (as Ag) 0.10

The obtained photothermographic materials 201 to 219
Was evaluated in the same manner as the photothermographic materials 101 to 119. Table 2 shows the evaluation results.

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[Table 2]

As is clear from Table 2, the photothermographic materials of the present invention (Samples 202 to 219) were found to be excellent in photographic performance, image storability and blocking ability.

[Preparation of Photothermographic Materials-301 to 311] In preparation of photothermographic materials-101 to 119,
Emulsion layer coating solution-1 was changed to emulsion layer coating solution-3, and yellow dye compound 15 was further removed from the antihalation layer.
Further, the fluorine-based surfactants F-1, F-2, F-3 and F-4 of the protective layer second layer and the back surface protective layer were combined with the same mass of F-5, F-6 and F-7, respectively. And F-8. Otherwise, the photothermographic materials 301 to 319 were prepared in the same manner as the photothermographic materials 101 to 119.

At this time, the coating amount (g) of each compound in the emulsion layer
/ M ² ) was as follows.・ Silver behenate 5.57 ・ Pigment (CIPigment Blue 60) 0.032 ・ Reducing agent-4 0.40 ・ Reducing agent-5 0.36 ・ Polyhalogen compound-2 0.12 ・ Polyhalogen compound-3 37 ・ Phthalazine compound-1 0.19 ・ SBR latex 10.0 ・ Hydrogen bonding compound-2 0.59 ・ Mercapto compound-1 0.002 ・ Silver halide (as Ag) 0.09

The photothermographic materials 301 to 319 were evaluated in the same manner as the photothermographic materials 101 to 119. As a result, the photothermographic materials of the present invention (samples 302 to 319) were obtained.
Showed good results with regard to photographic performance, image storability and blocking ability.

[Preparation of Photothermographic Materials-401 to 419]
Instead of Emulsion Layer Coating Solution-3, the following development accelerators
The composition was changed to Emulsion Layer Coating Solution-4 containing 7.8 g of 1 dispersion. Other than that, the photothermographic materials -401 to 419 were produced in the same manner as the photothermographic materials -301 to 319.

<< Preparation of Development Accelerator-1 Dispersion >> The preparation method of the development accelerator-1 used in the emulsion layer coating solution-4 was as follows.
It is shown below. 1 kg of development accelerator-1 and 1 part of modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
5 kg of water was added to 2 kg of a 0 mass% aqueous solution and mixed well to form a slurry. The slurry was sent by a diaphragm pump, dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 4 hours, and then sodium benzoisothiazolinone sodium salt was added. 02g and water were added to adjust the concentration of the development accelerator to 10% by mass.
One dispersion was obtained. The development accelerator particles contained in the thus obtained development accelerator-1 dispersion had a median diameter of 0.32 μm and a maximum particle diameter of 1.5 μm or less. The resulting development accelerator-1 dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored. At this time, the coating amount of each compound in the emulsion layer (g / m ² )
Is as follows.

・ Silver behenate 5.57 ・ Pigment (CIPigment Blue 60) 0.032 ・ Reducing agent-4 0.40 ・ Reducing agent-5 0.36 ・ Polyhalogen compound-2 0.12 ・ Polyhalogen compound -3 0.37 ・ phthalazine compound-1 0.19 ・ SBR latex 10.0 ・ hydrogen bonding compound-2 0.59 ・ development accelerator-1 0.028 ・ mercapto compound-1 0.002 ・ silver halide 0.09 (as Ag)

With respect to the photothermographic materials 401 to 419, except that the heat development time was changed from 24 seconds to 14 seconds,
The evaluation was performed in the same manner as the photothermographic materials 301 to 319. As a result, the photothermographic material of the present invention (samples 401 to 41)
In 9), good results were obtained with respect to photographic performance, image storability and blocking property.

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

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[0251]

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[0252]

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[0253]

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[0254]

According to the present invention, it is possible to provide a photothermographic material excellent in photographic performance, image storability and blocking property, and a method for producing the same.

Claims (4)

[Claims] 1. A support comprising, on one side of a support, at least one photosensitive layer containing photosensitive silver halide and a non-photosensitive protective layer, wherein the photosensitive layer comprises at least one photosensitive halide. In a photothermographic material containing silver, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, a latex that reacts with gelatin is contained on the side having the photosensitive layer. Photothermographic material. 2. A support comprising, on one side of a support, at least one photosensitive layer containing a photosensitive silver halide and a layer containing a non-photosensitive gelatin, wherein the photosensitive layer comprises at least one photosensitive halogen. In a photothermographic material containing silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, the non-photosensitive gelatin-containing layer on the side having the photosensitive layer reacts with gelatin. A photothermographic material comprising latex. 3. A support comprising, on one side of a support, at least one photosensitive layer containing a photosensitive silver halide and a non-photosensitive protective layer, wherein the photosensitive layer comprises at least one photosensitive halide. In a photothermographic material containing silver, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, a latex that reacts with gelatin is contained on the side having the photosensitive layer, and the latex is used. A method for producing a photothermographic material, which is added in a closed mixing vessel (inline). 4. A support comprising, on one side of a support, at least one photosensitive layer containing photosensitive silver halide and a layer containing non-photosensitive gelatin, wherein the photosensitive layer comprises at least one photosensitive halogen. In a photothermographic material containing silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, a color tone agent and a binder, the non-photosensitive gelatin-containing layer on the side having the photosensitive layer reacts with gelatin. A method for producing a photothermographic material, comprising a latex, wherein the latex is added in a closed mixing vessel (in-line).