JP2001083659A - Heat developable photographic sensitive material and image recording method, image forming method and processing method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photographic sensitive material having high sensitivity, excellent in sharpness and image preservability and excellent also in the uniformity of film density even when the sensitive material of different sizes is continuously developed and to provide an image recording method, an image forming method and a processing method for the sensitive material. SOLUTION: The heat developable photographic sensitive material contains a fluorine-containing surfactant of the formula Rf-A-X (where Rf is fluorinated alkyl, alkenyl or the like containing >=3 fluorine atoms, A is a divalent combining group and X is a water-soluble group), and when the elementary composition of the surface is inspected by X-ray photoelectron spectroscopy, the ratio of FIS peak intensity to CIS peak intensity is 0.01-1.0. In the continuous development of two or more heat developable photographic sensitive materials different from each other in size with a heat processing machine, the surface matting degree of at least one side of each of the sensitive materials is 20-300 mmHg and the coefficient of dynamic friction of each of the sensitive materials is <=0.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable photographic light-sensitive material, and more particularly to a heat-developable photographic light-sensitive material having good sensitivity, excellent sharpness, and excellent image storability. The present invention relates to a method for processing a heat-developable photographic light-sensitive material having excellent film density uniformity even when subjected to development processing.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical care,
The waste liquid caused by the wet processing of the image forming material has become a problem in terms of workability, and in recent years, it has been strongly desired to reduce the amount of the treated waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there has been a need for a technique relating to a photothermographic material capable of performing efficient exposure by a laser image setter or a laser imager and forming a high-resolution and clear black image.

As a technique for this purpose, heat-developable photographic light-sensitive materials which form a photographic image by heat treatment are known. For example, these materials are disclosed in US Pat. No. 3,152,904 and US Pat.
457,075 and D.C. Morgan and B.A. "Thermally Processed Silver System" by Shelly
ed Silver Systems), Imaging Processes and Materials (Imag
ing Processes and Materialia
ls) Neblette Eighth Edition, Sturge
ge), V.I. Walworth,
A. Shepp, 2nd page, 1969, etc.

In such a photothermographic material, a reducible silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, a silver halide), and a reducing agent are usually dispersed in an organic binder matrix. It is contained in a state. The photothermographic material is stable at room temperature, but generates silver by an oxidation-reduction reaction between a reducible silver source (acting as an oxidizing agent) and a reducing agent when heated to a high temperature after exposure.

[0005] This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and results in the formation of an image. An anti-fogging agent for controlling the fogging of the image is used, and the most effective method as a conventional anti-fogging technique has been a method using a mercury compound as the anti-fogging agent.

The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 89,903. However, the use of mercury compounds is not preferred, and the development of a non-mercury antifoggant has been desired. Non-mercury antifoggants include various polyhalides, for example, US Pat. Nos. 3,874,946 and 4,756,9.
No. 99, 5,340, 712 and European Patent No. 60
No. 5,981A1, No. 622,666A1, No. 6
No. 31,176A1, Japanese Patent Publication No. 54-165,
-2781 and the like. However, these compounds have problems such as a low fogging prevention effect and a deterioration in silver color tone, and thus need to be improved. Furthermore, if the photosensitive material is stored in a laminated form under humidifying and heating conditions, and then exposed and developed, there is a problem that the fogging in unexposed areas is increased. The development of was desired.

As a method for solving these problems, Japanese Patent Application Laid-Open No. 9-1
No. 60164, No. 9-244178, No. 9-2583
No. 67, No. 9-265150, No. 9-281640
And JP-A-9-319022 disclose polyhalides having the above-mentioned disadvantages improved. However,
In particular, these compounds are used for heat-developable photographic light-sensitive materials for medical laser imagers, or heat-developable photographic light-sensitive materials for output of laser image setters for printing, which contain a high contrast agent and have an oscillation wavelength of 600 to 800 nm. When applied, the above-mentioned drawbacks are considerably improved, but they have the drawback that the developed samples are fogged up with time and the storage stability of images over time is poor.

Further, JP-A-6-208193 discloses a heat-developable photographic material in which fog stability during storage is improved by including a halogenated antifogging compound and a compound having an isocyanate group. However, the storage stability of images over time is not at a sufficient level, and the reaction of these antifogging compounds progresses with time at the stage of the coating solution during the manufacturing process, and the sensitivity of the photosensitive material fluctuates accordingly. There was a major drawback of doing so.

When the above-mentioned photothermographic material is automatically processed by a photothermographic machine, if the photothermographic materials having different sizes are continuously processed, the heat developability at portions having different sizes is large. There is a problem that a difference appears and the uniformity of the film density is impaired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable photographic light-sensitive material having high sensitivity, excellent sharpness, excellent image storability, and a film which can be subjected to heat-development of photographic materials of different sizes continuously. An object of the present invention is to provide a photothermographic material having excellent density uniformity and to provide an image recording method, an image forming method and a processing method thereof.

[0011]

The above object has been attained by the following constitution of the present invention.

(1) When two or more heat-developable photosensitive materials having different sizes are continuously processed automatically by a heat developing machine,
A method for processing a photothermographic material, wherein the surface matte degree of at least one side of the photothermographic material is 20 mmHg or more and 300 mmHg or less.

(2) When two or more heat-developable photographic materials having different sizes are continuously processed automatically by a heat developing machine,
A method for processing a photothermographic material, wherein the coefficient of dynamic friction of the photothermographic material is 0.5 or less.

(3) The method for processing a photothermographic material according to (1) or (2), wherein the photothermographic material is exposed to an infrared laser.

(4) The image is recorded on a heat-developable photographic light-sensitive material by performing exposure using a laser scanning exposure device in which a scanning laser beam is a vertical multi-scan.
Or the method for processing a photothermographic material according to (3).

(5) Exposure is performed by a laser scanning exposure device in which the angle formed by a scanning laser beam when an image is recorded on a heat-developable photographic photosensitive material does not become substantially vertical. , (2), (3) or (4).

(6) The heat-developable photographic light-sensitive material is at least 80 ° C.
The method for processing a photothermographic material according to any one of (1) to (5), wherein the development is performed by heating at 50 ° C. or lower.

(7) The heat-developable photographic light-sensitive material contains 40 to 40
The method for processing a photothermographic material according to any one of (1) to (6), wherein the development is performed by heating in a state of containing 4500 ppm.

(8) A heat-developable photographic material containing an organic silver salt, photosensitive silver halide grains and a reducing agent on a support, containing a fluorine-containing surfactant represented by the general formula (F): When the elemental composition of the surface was examined by X-ray photoelectron spectroscopy, the ratio of F1S peak intensity / C1S peak intensity was 0.01.
A heat-developable photographic light-sensitive material, which falls within the range of from 1.0 to 1.0.

Formula (F) Rf-AX In the formula, Rf represents an alkyl group, alkenyl group, or aryl group containing at least three fluorine atoms. A represents a divalent linking group, and X represents a water-soluble group.

(9) In a photothermographic material containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a support, a binder having a Tg of 50 ° C. or more and 150 ° C. or less is contained. When the composition was examined by X-ray photoelectron spectroscopy, the ratio of F1S peak intensity / C1S peak intensity was 0.01%.
A heat-developable photographic light-sensitive material, which falls within the range of from 1.0 to 1.0.

(10) An image recording method, wherein the photothermographic material according to (8) or (9) is exposed with an infrared laser.

(11) The image recording method according to (10), wherein a scanning laser beam for recording an image on the heat-developable photographic photosensitive material is exposed by a laser scanning exposing machine which is a vertical multi-scan.

(12) Exposure is performed by a laser scanning exposing machine in which an angle formed by a scanning laser beam when recording an image on a photothermographic material is not substantially vertical. The image recording method according to (11).

(13) An image forming method, wherein the photothermographic material according to (8) or (9) is developed by heating at 80 ° C. or more and 250 ° C. or less.

(14) An image forming method, wherein the photothermographic material according to the above (8) or (9) is developed by heating while containing a solvent in an amount of 40 to 4500 ppm.

Hereinafter, the present invention will be described in detail.

In the method for processing a heat-developable photographic light-sensitive material of the present invention (hereinafter also simply referred to as a light-sensitive material), the surface matte degree of at least one side of the heat-developable photographic light-sensitive material is set to 20 mmHg.
It was found that by setting the pressure to 300 mmHg or less, even if the heat-developable photographic materials having different sizes were continuously processed, an image having a uniform film density and uniform images could be obtained. The coefficient of dynamic friction of the surface of the photosensitive material is 0.5
It has been found that, by performing the following, even if the heat-developable photographic materials having different sizes are continuously processed, an image having a uniform film density and uniformity can be obtained.

In the present invention, it is sufficient that at least one surface has a matte degree of 20 mmHg or more and 300 mmHg or less, and it may be on the photosensitive layer side or on the backing layer side on the back side. Surface mat degree is more than 20mmHg and 300m
There is no particular limitation on the method for adjusting the pressure to mHg or less, and the method can be adjusted by drying conditions and additives. The easiest method is to use a matting agent in the coating solution of the outermost layer.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a matting agent is preferably provided on the surface of the photosensitive material in order to prevent the image after thermal development from being damaged. It is preferred that the agent be contained in an amount of 0.5 to 30% by weight based on all binders on the photosensitive layer side.

When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent, and thus the slip property and the adhesion of fingerprints of the photosensitive material are improved. For prevention, it is preferable to provide a matting agent on the surface of the photosensitive material, and the matting agent is used in a weight ratio of 0.5 to 4 with respect to all binders in the layer on the side opposite to the photosensitive layer side.
It is preferable to contain 0%.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,198.
Derivatives, polyvinyl alcohol described in JP-B-44-3643 and the like, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent preferably has a variation coefficient of the particle size distribution of 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the coefficient of variation of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 These matting agents can be contained in any constituent layer, but are preferably photosensitive in order to achieve the object of the present invention. It is a constituent layer other than the layer, more preferably the outermost layer as viewed from the support.

The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed in a coating solution in advance and applied.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

In the method for processing a heat-developable photographic light-sensitive material of the present invention, the heat-developable photographic light-sensitive material has a dynamic friction coefficient of 0.5 when measured with stainless steel or neoprene rubber.
In the following, it is preferably from 0.5 to 0.05, more preferably from 0.4 to 0.05. In the automatic processing by a machine, a method for processing a photothermographic material having excellent uniformity of film density can be obtained. Here, stainless steel or neoprene rubber is used as a material of a nip roll attached to various devices in order to transport a photosensitive material. As a specific method of measuring the dynamic friction coefficient, the obtained photosensitive material was heated at a temperature of 30 ° C. 20
The measurement is carried out after standing for 84 hours or more under the condition of% RH. When the measurement is performed under conditions other than the same conditions, the measurement is performed according to the method specified in JIS (K7125).

In order to adjust the friction coefficient of the photothermographic material used in the present invention, various surfactants, sliding agents and the like can be used.

Examples of the slipping agent used in the present invention include polyorganosiloxanes disclosed in JP-B-53-292 and US Pat. No. 4,275,14.
6, higher fatty acid amides disclosed in JP-B-58-33541, British Patent No. 927,446 or JP-A-55-126238 and JP-A-58-906.
No. 33, higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms), and US Pat. No. 3,933,933.
No. 516, and higher fatty acid metal salts, and esters of straight-chain higher fatty acids and straight-chain higher alcohols as disclosed in JP-A-58-50534.
Higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in WO 90108115.8 can be used. They can also use natural oils and fats such as waxes and oils, such as montanic acid esters, kauna wax and beeswax.

Among these polyorganosiloxanes, generally known polyorganosiloxanes such as polydimethylsiloxane and polydiethylsiloxane, and polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane are known. 53-
No. 292, JP-B-55-49294, JP-A-60-1
No. 40341, etc., an organopolysiloxane having an alkyl group having 5 or more carbon atoms, an alkylpolysiloxane having a polyoxyalkylene group in a side chain, an alkoxy, hydroxy, hydrogen, carboxyl, amino, mercapto group in a side chain It is also possible to use a modified polysiloxane such as an organopolysiloxane having a siloxane unit, a block copolymer having a siloxane unit, or a graft copolymer having a siloxane unit in a side chain as shown in JP-A-60-191240. You can also. One of the preferred slip agents in the present invention is polyorganosiloxane, more preferably polyalkylsiloxane such as polydimethylsiloxane and polydiethylsiloxane, and polyarylsiloxane such as polydiphenylsiloxane and polymethylphenylsiloxane. Higher fatty acids and their derivatives, higher alcohols and their derivatives are also preferred slip agents. By using such a slipping agent, a photosensitive material having excellent scratch strength can be obtained.

The preferred higher fatty acids and derivatives thereof, higher alcohols and derivatives thereof include higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters and the like.
Also, higher aliphatic alcohols, monoalkyl phosphites of higher aliphatic alcohols, dialkyl phosphites, trialkyl phosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, higher aliphatic alkyl sulfonic acids, and amides thereof A compound or a salt thereof can be used.

Next, the fluorine-based surfactant represented by the following formula (F) used in the photothermographic material of the present invention will be described.

Formula (F) Rf-AX In the formula, Rf represents a fluorinated alkyl group, alkenyl group or aryl group containing at least three fluorine atoms. It may have another substituent. A represents a divalent linking group, and X represents a water-soluble group.

It is preferable to use a polyalkylene oxide-based surfactant represented by the following general formula (I) together with the fluorine-based surfactant represented by the general formula (F) used in the present invention.

[0046]

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In the general formula (I), R ₁ represents a substituted or unsubstituted alkyl or alkenyl group having 1 to 30 carbon atoms. m1 and n1 may be the same or different, and m1 and n1 are each 1 to 50, and preferably, m1 + n1 is 5 to 40. Further, the number of carbon atoms of R ₁ is preferably 8 to 18. Also, m2 and n2 are each 0 to
It is 50, and preferably both m2 + n2 are 0-40. More preferably, both m2 and n2 are preferably 0.

Specific examples of the compound of the general formula (I) include the following.

[0049]

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[0050]

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The layer to be added is not particularly limited, but is preferably a layer far from the support, and most preferably the top layer. Further, the amount to be added but it is 1 to 1000 mg / m ^2, further preferably from 10-100 mg / m ^2.

Among the fluorine-containing surfactant compounds represented by formula (F), preferred fluorine-containing surfactant compounds include those having the following structural formulas.

Rf ′-(CH ₂ ) _n3 — (OCH ₂ —CH ₂ ) _n4 —OH In the formula, Rf ′ is a partially fluorinated or fully fluorinated carbon atom containing at least 3 fluorine atoms and having 1 to 3 carbon atoms. Represents 30 substituted or unsubstituted alkyl, alkenyl, or aryl groups. n3 is 0 to 5, n4 is 2 to 50, and more preferably 5 to 20.

Specific structures of preferred fluorine-containing surfactant compounds are shown below, but the present invention is not limited thereto.

[0055]

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[0056]

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The element composition of the surface of the photothermographic material was measured by X-ray photoelectron spectroscopy. M as excitation X-ray source
The g-Kα ray is used, the degree of vacuum is 5 × 10 ⁻⁵ Pa or less, and photoelectrons are detected in a direction perpendicular to the sample surface. C1S
For the detection of electrons, the binding energy is from 300 eV to 270
The eV range is measured at a scan speed of 0.2 eV / sec or less, and the binding energy is 700 e for F1S electron detection.
Scan speed 0.2 eV in the range from V to 680 eV
/ Second or less. At this time, the signal of the F1S electron rapidly attenuates from the irradiation of the excitation X-ray,
It is necessary to adjust according to the range of the scan so that the time required to complete the measurement of the 1S peak does not exceed 50 seconds.
Peak intensity is determined by measuring the interval from the baseline to the peak maximum. The F1S peak intensity / C1S peak intensity ratio determined by this method represents the composition ratio of fluorine and carbon near the sample surface.

In the present invention, it is preferable to adjust the amount of the fluorine-based compound to be added to each layer as a ratio of F1S peak intensity / C1S peak intensity in the range of 0.01 to 1.0.
In particular, it is preferable to adjust the range to 0.05 to 0.7.

When a binder having a Tg of 50 ° C. or more and 150 ° C. or less is contained and the elemental composition of the surface is examined by X-ray photoelectron spectroscopy, the ratio of F1S peak intensity / C1S peak intensity is 0.1%.
It has been found that a photothermographic material having a high sensitivity, excellent sharpness and excellent image storability can be obtained by being within the range of 01 to 1.0.

The photothermographic material of the present invention contains a photosensitive silver halide, an organic silver salt and a reducing agent.

The photosensitive silver halide used in the photothermographic material of the present invention will be described.

Photographic emulsions containing photosensitive silver halide are described in Chimie et P by Glafkids
hysique Photographique (Pa
ulMontel, 1967); F. Duf
fin Photographic Emulsio
n Chemistry (The Focal Pre
ss, 1966); L. Zelikman e
Making and Coating by tal
Photographic Emulsion (The
Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof, and the like may be used, but a so-called controlled double jet method of preparing silver halide grains while controlling the formation conditions is preferable among the above methods. The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

Grain formation is usually divided into two stages of silver halide seed grain (nucleus) generation and grain growth, and these may be performed continuously at a time. Alternatively, nucleus (seed grain) formation and grain growth may be performed. A method in which separation is performed may be used. The controlled double jet method of forming particles by controlling pAg, pH, and the like, which are the conditions for forming particles, is preferred because the shape and size of the particles can be controlled. For example, when performing a method in which nucleation and grain growth are performed separately, first, a soluble silver salt and a soluble halide are uniformly and rapidly mixed in an aqueous gelatin solution to form nuclei (seed particles) (nucleation step). rear,
Silver halide grains are prepared by a grain growing step of growing grains while supplying a soluble silver salt and a soluble halogen salt under controlled pAg, pH and the like. After grain formation, a desired silver halide emulsion can be obtained by removing unnecessary salts and the like by a desalting step by a known desalting method such as a noodle method, a flocculation method, an ultrafiltration method, and an electrodialysis method. I can do it.

The silver halide of the present invention preferably has a small average grain size in order to suppress white turbidity after image formation and obtain good image quality, and the average grain size is preferably 0.2 μm or less, more preferably 0.01 μm to 0.1
7 μm, particularly preferably 0.02 μm to 0.14 μm.
The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface.

In the present invention, the silver halide grains are preferably monodispersed. The term “monodisperse” as used herein means that the coefficient of variation of the particle size determined by the following equation is 7
% Or less. The particles are preferably at most 5%, more preferably at most 3%, particularly preferably at most 1%.

Coefficient of variation of grain size% = standard deviation of grain size / average grain size × 100 The shape of silver halide grains is cubic, octahedral, 14
Examples thereof include facet particles, tabular particles, spherical particles, rod-like particles, potato-like particles, and the like, and in the present invention, cubic particles, octahedral particles, tetrahedral particles, and tabular particles are particularly preferable.

When tabular silver halide grains are used, the average aspect ratio is preferably from 2 to 100, more preferably from 3 to 50. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958, and can easily obtain target tabular grains. Further, grains having rounded corners of silver halide grains can also be preferably used.

The outer surface of the silver halide grains is not particularly limited, but it is preferable that the ratio occupied by the Miller index [100] plane is high, and this ratio is 50% or more, and more preferably 70%.
It is preferably at least 80%. The ratio of the Miller index [100] plane is [11] in the adsorption of the sensitizing dye.
T] utilizing the adsorption dependency between the [1] plane and the [100] plane. T
ani, J .; Imaging Sci. , 29,165
(1985).

The silver halide grains used in the present invention are:
It is preferable to use a low molecular weight gelatin having an average molecular weight of 50,000 or less when forming the grains, but it is particularly preferable to use the same when forming nuclei of silver halide grains.

In the present invention, the low molecular weight gelatin has an average molecular weight of 50,000 or less, and preferably has a molecular weight of 2,000 to 4,000.
0000, more preferably 5,000 to 25,000. The average molecular weight of gelatin can be measured by gel filtration chromatography.

The low-molecular-weight gelatin may be enzymatically decomposed by adding a gelatin-degrading enzyme to a commonly used aqueous gelatin solution having an average molecular weight of about 100,000, or may be hydrolyzed by adding an acid or an alkali and heating, or under atmospheric pressure or pressure. , Or by irradiation with ultrasonic waves, or by using these methods in combination.

The concentration of the dispersion medium at the time of nucleation is preferably 5% by weight or less, and it is effective to carry out at a low concentration of 0.05 to 3.0% by weight.

The silver halide grains used in the present invention are:
It is preferable to use a compound represented by the general formula [5] at the time of forming the particles.

The general formula [5] YO (CH ₂ CH ₂ O) _m (C (CH ₃ ) HCH ₂ O) _p (C
H ₂ CH ₂ O) _n Y wherein Y is a hydrogen atom, —SO ₃ M, or —CO—B—C
OOM, M represents a hydrogen atom, an alkali metal atom, an ammonium group or an ammonium group substituted with an alkyl group having 5 or less carbon atoms, and B represents a linear or cyclic group forming an organic dibasic acid. Represents m and n are each 0 to 5
0 and p represent 1 to 100.

The compound represented by the general formula [5] is used for producing a silver halide photographic light-sensitive material, a step of producing an aqueous gelatin solution, a step of adding a water-soluble halide and a water-soluble silver salt to the gelatin solution, It has been preferably used as an antifoaming agent against remarkable foaming when the emulsion raw material is stirred or moved, such as a step of coating the emulsion on a support. No. 44-9497. The compound represented by the general formula [5] also functions as an antifoaming agent at the time of nucleation.

The compound represented by the general formula [5] is preferably used in an amount of 1% by weight or less, more preferably 0.01 to 0.1% by weight, based on silver.

The compound represented by the general formula [5] may be present at the time of nucleation, and is preferably added in advance to the dispersion medium before nucleation, but may be added during nucleation. And
It may be used by being added to an aqueous silver salt solution or an aqueous halide solution used for nucleation. Preferably, it is used by adding to the aqueous halide solution or both aqueous solutions at 0.01 to 2.0% by weight. Also, the compounds of the present invention are preferably present for at least 50% of the time of the nucleation step,
More preferably, it is present for a time spanning at least 70%.
Even when the compound represented by the general formula [5] is added as a powder, it is dissolved in a solvent such as methanol, and typical specific examples of the compound represented by the general formula [5] are shown below, but are not limited thereto. Not something.

E-1 HO (CH ₂ CH ₂ O) _m (C (CH ₃ ) HCH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) E-2 NaO ₂ C (CH ₂ ) OCO (CH ₂ CH ₂ O) _m (C (CH ₃ ) HCH ₂ O) ₁₇ (CH ₂ CH ₂ O) _n CO (CH ₂ ) ₂ CO ₂ Na (m + n = 5.7) E-3 KO ₂ CCH = CHCOO (CH ₂ CH ₂ O) _m (C (CH ₃ ) HCH ₂ O) _34.2 (CH ₂ CH ₂ O) _n COCH = CHCO ₂ K (m + n = 8.5) E-4 NaO ₃ SO ( C (CH ₃ ) HCH ₂ O) ₁₇ SO ₃ Na

[0079]

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The temperature at the time of nucleation is about 5 to 60 ° C., preferably 15 to 50 ° C. Even if the temperature is constant, the temperature rise pattern (for example, the temperature at the start of nucleation is 25 ° C., The temperature is gradually raised during formation, and the temperature at the end of nucleation is 40 ° C.
It is preferable to control the temperature within the above-mentioned temperature range even if the pattern is the same as above) or vice versa.

The concentration of the silver salt aqueous solution and the halide aqueous solution used for nucleation is preferably 3.5 N or less, more preferably 0.03 N or less.
It is preferably used in a low concentration range of 1 to 2.5 normal.
The rate of addition of silver ion during nucleation is preferably reaction 1l per 1.5 × 10 ^-3 mol / min to 3.0 × 10 ^-1 mol / min, more preferably 3.0 × 10 ^-3 mol / Min ~ 8.
It is 0 × 10 ^-2 mol / min.

The pH at the time of nucleation can be set in the range of 1.7 to 10, but the pH at the alkali side is preferably pH 2 to 6 in order to broaden the particle size distribution of nuclei to be formed. Also, pBr at the time of nucleation is about 0.05 to 3.0, preferably 1.
0 to 2.5, further 1.5 to 2.0.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source. Generally, silver halide is prepared in advance and added to a solution for preparing an organic silver salt. Since the silver halide preparation step and the organic silver salt preparation step can be handled separately, it is difficult to control the production. As described in British Patent No. 1,447,454, a halogen component such as a halide ion coexists with an organic silver salt-forming component when preparing an organic silver salt, and silver ions are injected into the organic silver salt. By doing so, it can be produced almost simultaneously with the production of the organic silver salt.

It is also possible to prepare a silver halide by subjecting an organic silver salt to a halogen-containing compound and converting the organic silver salt. That is, a silver halide-forming component is applied to a solution or dispersion of an organic silver salt prepared in advance or a sheet material containing the organic silver salt to convert a part of the organic silver salt into photosensitive silver halide. Can also. The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, the organic silver salt and the compound to be tested are mixed and, if necessary, heated, and thereafter, the presence of a peak specific to silver halide is examined by X-ray diffraction. Silver halide-forming components confirmed to be effective by such tests include inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Are U.S. Pat. Nos. 4,009,039 and 3,45
7,075, 4,003,749, British Patent 1,498,956 and JP-A-53-27027;
The details are described in JP-B Nos. 53-25420, and an example is shown below.

[0085] (1) inorganic halide: halide (wherein M represented by e.g. MX _n, H, NH _4, and represents a metal atom, n represents 1 when the M is H and NH _4, M
When is a metal atom, it represents the same value as its valence. Examples of the metal atom include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, manganese, iron, cobalt, nickel, rhodium, and cerium. ). Further, halogen molecules such as bromine water are also effective.

(2) Onium halides: quaternary ammonium halides such as, for example, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, and quaternary phosphonium halides such as tetraethylphosphonium bromide And tertiary sulfonium halides such as trimethylsulfonium iodide.

(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like.

(4) N-halogen compounds: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-bromooxazolinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide,
1,3-dibromo-4,4-dimethylhydantoin, N
-Bromourazole and the like.

(5) Other halogen-containing compounds: for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like. Two or more of these silver halide forming components may be used in combination. As described above, the silver halide can be prepared by converting part or all of silver in the organic acid silver salt to silver halide by reacting the organic acid silver with the halide ion, but the silver halide separately prepared can be used. It is preferable to use silver because the size and shape of silver halide can be controlled. However, a silver halide produced by converting a part of the organic silver salt to these separately prepared silver halides may be used in combination.

These silver halides may be used in an amount of 0.001 mol to 0.7 mol, preferably 0.03 mol, per 1 mol of the organic silver salt, together with silver halide prepared separately and silver halide obtained by conversion of an organic silver salt. It is preferable to use from 1 mol to 0.5 mol.

The silver halide used in the present invention preferably contains ions of transition metals belonging to Groups 6 to 10 of the periodic table. As the above metal, W,
Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, O
s, Ir, Pt, and Au are preferred. These may be used alone or in combination of two or more of the same or different metal complexes.
These metal ions may be directly introduced into silver halide as a metal salt, but can be introduced into silver halide in the form of a metal complex or complex ion. The preferred content is in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver, and more preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ . In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a ligand, and m is 0,-, 2-, 3-.
Or 4-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

The following are specific examples of the transition metal coordination complex ion.

[0094] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [IrCl _6] ^4- 8: [IrCl _6] ^3- 9: [Ru (NO) Cl _5] ^2- 10: [RuBr ₄ (H ₂ O)] ^2- 11: [Ru (NO) ( H ₂ O) Cl _4] ^- 12: [RhCl ₅ (H ₂ O)] ^2- 13: [Re (NO) Cl _5] ^2- 14: [Re (NO) (CN) _5] ^2- 15: [ Re (NO) Cl (CN) 4 ] ^2- 16: [Rh (NO) ₂ Cl _4] ^- 17: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 18: [Ru (NO) (CN) _5] ^2- 19: [Fe (CN) _6] ^3- 20: [Rh (NS) Cl _5] ^2- 21: [Os (NO) Cl _5] ^2- 22: [Cr (NO) Cl _5] ^{2 -} 23: [Re (NO) Cl ₅ ] ^- 24: _{[Os (NS) Cl 4 (TeCN} ) ] ^2- 25: [Ru (NS) Cl _5] ^2- 26: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 27: [Os (NS ) Cl (SCN) ₄ ] ^2-28 : [Ir (NO) Cl ₅ ] ^2- Cobalt and iron compounds are preferably 6-cyano metal complexes, representative examples of which are shown below.

29: [Fe (CN) ₆ ] ^4-30 : [Fe (CN) ₆ ] ³ -31: [Co (CN) ₆ ] ^3- Compounds which provide ions or complex ions of these metals include: It is preferably added during silver halide grain formation and incorporated into silver halide grains.Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and any addition before or after chemical sensitization Good, but especially nucleation, growth,
It is preferably added at the stage of physical ripening, more preferably at the stage of nucleation and growth, and most preferably at the stage of nucleation. In the addition, it may be added in several divided portions, and may be uniformly contained in the silver halide grains.
3, JP-A-2-306236, JP-A-3-167545
Nos. 4-76534, 6-110146, 5
As described in, for example, JP-A-273683, it can be contained in the particles with a distribution.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method of adding an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a method in which a silver salt solution and a halide solution are used. When they are mixed simultaneously, they are added as a third aqueous solution to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method in which halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains separately prepared can be desalted by a known desalting method such as a noodle method, flocculation method, ultrafiltration method, and electrodialysis method.
The heat-developable photographic material can be used without desalting.

The photosensitive silver halide grains in the present invention can be subjected to chemical sensitization. As the chemical sensitization method, known sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization, and reduction sensitization can be used. These sensitization methods can be used in combination of two or more. For sulfur sensitization, thiosulfates, thiourea derivatives, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization are described in JP-A-9-2.
The compounds described in No. 30527 can be mentioned. Compounds preferably used for the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent 618,061
And the like. Ascorbic acid, 2
Thiourea oxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like can be used. When the pH of the emulsion is 7 or more or pAg
Can be reduced and sensitized by keeping at 8.3 or less.

The photosensitive silver halide in the present invention is preferably subjected to spectral sensitization by absorbing a spectral sensitizing dye.
Cyanine dyes, merocyanine dyes as spectral sensitizing dyes,
Complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye,
Hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. For example, JP-A-63-1
No. 59841, No. 60-140335, No. 63-23
Nos. 1437, 63-259,651 and 63-304
No. 242, No. 63-15245, U.S. Pat.
9,414, 4,740,455, 4,7
No. 41,966, No. 4,751,175, No. 4,
Sensitizing dyes described in 835,096 can be used.
Useful sensitizing dyes for use in the present invention are, for example, RD176
43 IV-A (p.23, December 1978), 18
431X (August 1978, p. 437). In particular, it is preferable to use a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers and scanners. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-54409
The compounds described in No. 80679 are preferably used.

Useful cyanine dyes are, for example, cyanine dyes having a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including.

In the present invention, it is particularly preferable to use a sensitizing dye having a spectral sensitivity in the infrared. In the present invention, examples of the infrared spectral sensitizing dye preferably used include, for example, US Pat. Nos. 4,536,473 and 4,51.
And infrared spectral sensitizing dyes disclosed in US Pat. Nos. 5,888 and 4,959,294.

Further, particularly preferred spectral sensitizing dyes include dyes represented by the following formulas (1) to (4).

[0103]

Embedded image

In the general formulas (1) to (4), Y ₁ , Y ₂ ,
Y ₁₁ , Y ₂₁ , Y ₂₂ and Y ₃₁ each represent an oxygen atom, a sulfur atom, a selenium atom, a —C (R _a ) (R _b ) — group, or —CH
= CH- represents a group, Z ₁ represents a nonmetallic atomic group necessary for forming a condensed ring of 5- or 6-membered. R is a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aralkyl group, lower alkoxyl group, an aryl group, a hydroxyl group, a halogen atom, R _a and R _b are each a hydrogen atom, a lower alkyl group or R _a and R _b is joined by 5 members,
Represents a group of non-metallic atoms necessary to form a 6-membered aliphatic spiro ring. R ₁ , R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ are each an aliphatic group, or R ₁ is required to form a fused ring with W ₃ and R ₁₁ with W ₁₄ Represents a group of non-metallic atoms. R _c
And R _d are each a lower alkyl group, a cycloalkyl group,
Represents an aralkyl group, an aryl group, or a heterocyclic group. W ₁ ,
W ₂ , W ₃ , W ₄ , W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₂₁ ,
_{W 22, W 23, W 24} , W 31, W 32, W 33 and W ₃₄ each,
A hydrogen atom, a substituent or W ₁ is W ₂ , W ₁₁ is W ₁₂ ,
W ₂₁ and W _22, W ₂₃ and W _24, W ₃₁ and W _32, W ₃₃ is W
Represents a group of non-metallic atoms necessary for forming a condensed ring by bonding with ₃₄ . _{V 1 ~V 9, V 11 ~V} 13, V 21 ~V 29, V 31
To V ₃₃ each represent a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxyl group, an aryl group, or a heterocyclic group, or V ₁ is V ₃ and V ₂ is V and _4, V ₃ and V _5, V ₄ and V _6, V
₅ and V _7, V ₆ and V _8, V ₇ and V _9, V ₁₁ and V _13, V
₂₁ and V _23, V ₂₂ and V _24, V ₂₃ and V _25, V ₂₄ is V ₂₆
When, and V ₂₅ is V _27, and V ₂₆ are V _28, V ₂₇ and V _29, V ₃₁
Represents a non-metallic atomic group necessary for forming a 5- to 7-membered coupled between V _33, any one and V of V ₁ ~V _9
11 any one of ~V ₁₃ is a group other than a hydrogen atom.
X ₁ , X ₁₁ , X ₂₁ and X ₃₁ each represent an ion necessary for canceling the intramolecular charge, and 11, 11, 111 and 121 each represent an ion required for canceling the intramolecular charge. Represents a number. k1, k2, k21 and k22 are each 0
Or represents 1. n21, n22, n31 and n32 each represent an integer of 0 to 2, and n21, n22 and n31
And n32 do not become 0 at the same time. p1 and p11
Is each 0 or 1, q1 and q11 are each an integer of 1 and 2, and the sum of p1 and q1 and the sum of p11 and q11 does not exceed 2.

More preferred structures of the general formulas (1) and (2) are represented by the general formulas (1-1) and (2-1).

[0106]

Embedded image

In the general formulas (1-1) and (2-1),
Y ₁ , Y ₂ and Y ₁₁ each represent an oxygen atom, a sulfur atom, a selenium atom, a —C (R _a ) (R _b ) — group or —CH ＝ CH—
Z ₁ represents a group of non-metallic atoms required to complete a 5- or 6-membered fused ring. R is a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aralkyl group, lower alkoxyl group, an aryl group, a hydroxyl group, a halogen atom, each R _a and R _b, hydrogen atom, a lower alkyl group, or a R _a Represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered aliphatic spiro ring by bonding between _Rb . R ₁
And R ₁₁ each represent an aliphatic group or a non-metallic atomic group necessary for forming a fused ring between W _{1 and} W ₃ and R _{11 and} W ₁₄ . W ₁ , W ₂ , W ₃ , W ₄ , W ₁₁ , W ₁₂ , W ₁₃ and W ₁₄
Represents a hydrogen atom, a substituent, or a group of nonmetallic atoms necessary for forming a condensed ring by bonding between W _{1 and} W ₂ , W _{11 and} W ₁₂ , and W _{13 and} W _14. Represent. L _{1 to} L ₉ , L _{11 to} L ₁₅
Each represents a methine group. X ₁ and X ₁₁ each represent an ion required to cancel the charge in the molecule, and 11 and 11
Each 1 represents the number of ions required to offset the charge in the molecule. m1 to m3 each represent 0 or 1. p1 and p11 are each 0 or 1, q1 and q11 are each an integer of 1 or 2, and p1 and q1 and p11 and q
The sum of 11 does not exceed 2.

Each substituent will be described in more detail.

The general formulas (1), (2), (1-
The substituents of the compounds represented by 1), (2-1), (3) and (4) will be described below.

In the general formulas (1) and (1-1), the condensed ring completed by the group of nonmetallic atoms necessary to complete the 5- or 6-membered condensed ring represented by Z ₁ For example, a condensed cyclohexene ring, a condensed benzene ring, a condensed thiophene ring, a condensed pyridine ring, a condensed naphthalene ring, and the like are specifically mentioned. Thiazole ring, tetrahydrobenzothiazole ring, naphthothiazole ring, benzonaphthothiazole ring, etc. Selenazole ring, quinoline ring, , 3-dialkyl indolenine ring, 3,3-dialkyl pyrido pyrroline ring, and the like. Any of the groups described as substitutable groups represented by W _{1 to} W ₄ described below can be substituted on these rings.

The aliphatic groups represented by R ₁ , R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ include, for example, those having 1 to 10 carbon atoms.
Branched or linear alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, iso-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), and the number of carbon atoms 3 to 10 alkenyl groups (for example, 2-propenyl group, 3-butenyl group, 1-methyl-
3-propenyl group, 3-pentenyl group, 1-methyl-3
-Butenyl group, 4-hexenyl group, etc.), having 7 to 7 carbon atoms
And 10 aralkyl groups (eg, benzyl group, phenethyl group, etc.).

The above-mentioned groups further include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Vinyl group, aryl group (eg, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoromethyl group, alkoxyl group (eg, methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group ( For example, phenoxy group, p-tolyloxy group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group) Etc.), an amino group (for example, an amino group, a biscarboxymethylamino group, etc.),
Aryl group (eg, phenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, tetrahydrofurfuryl group, 2-pyrrolidinone-1-yl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido Groups (eg, ureido group, 3-methylureido group, 3-phenylureido group, etc.), thioureido groups (eg, thioureido group, 3-methylthioureido group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.), An arylthio group (for example, a phenylthio group or the like), a heterocyclic thio group (for example, a 2-thienylthio group, a 3-thienylthio group,
2-imidazolylthio group, etc.), carbonyloxy group (for example, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, etc.), thioamide group (for example, thioamide group) Acetamide group, thiobenzoylamino group, etc.) or, for example, a sulfo group, a carboxyl group, a phosphono group, a sulfate group, a hydroxyl group, a mercapto group, a sulfino group, a carbamoyl group (for example, a carbamoyl group, N-methylcarbamoyl) Group,
N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.) ), A sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), an acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), an acylaminocarbonyl group (eg, acetamidocarbonyl Group, methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.)
May be substituted with a hydrophilic group such as

Specific examples of the aliphatic groups substituted with these hydrophilic groups include carboxymethyl, carboxyethyl, carboxybutyl, carboxypentyl, and carboxypentyl groups.
-Sulfate butyl group, 3-sulfopropyl group, 2-
Hydroxy-3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3
-Sulfinobutyl group, 3-phosphonopropyl group, hydroxyethyl group, N-methanesulfonylcarbamoylmethyl group, 2-carboxy-2-propenyl group, o-sulfobenzyl group, p-sulfophenethyl group, p-carboxybenzyl And each group such as a group.

The lower alkyl group represented by R is a straight-chain or branched group having 5 or less carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Isopropyl group and the like. Examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a p-methoxyphenylmethyl group, an o-acetylaminophenylethyl group, and the like, and the lower alkoxyl group is a group having 4 or less carbon atoms. Is a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, and the like.Examples of the aryl group include substituted and unsubstituted aryl groups, for example, phenyl, 2-naphthyl, 1-naphthyl, o -Tolyl group, o-methoxyphenyl group, m-chlorophenyl group, m-bromophenyl group, p-tolyl group, p-ethoxyphenyl group and the like. These groups include phenyl group, halogen atom, alkoxyl group and the like. Groups such as groups and hydroxyl groups can be substituted. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom,
And iodine atoms.

The lower alkyl group represented by R _a and R _b is the same as the lower alkyl group for R.

The lower alkyl group represented by R _c and R _d is a linear or branched group having 5 or less carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group And an isopropyl group. Examples of the cycloalkyl group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.Examples of the aralkyl group include a benzyl group, a phenethyl group, a p-methoxyphenylmethyl group, and o-acetylamino. Examples include a phenylethyl group and the like, and the aryl group includes substituted and unsubstituted ones, for example, a phenyl group, a 2-naphthyl group, a 1-naphthyl group, an o-tolyl group,
o-methoxyphenyl group, m-chlorophenyl group, m-
Examples of the group include a bromophenyl group, a p-tolyl group, and a p-ethoxyphenyl group. Examples of the heterocyclic group include substituted and unsubstituted heterocyclic groups. For example, a 2-furyl group, 5-methyl-2
-Furyl, 2-thienyl, 2-imidazolyl, 2
-Methyl-1-imidazolyl group, 4-phenyl-2-thiazolyl group, 5-hydroxy-2-benzothiazolyl group, 2-pyridyl group, 1-pyrrolyl group and the like.

These groups can be further substituted with groups such as the phenyl group, halogen atom, alkoxyl group and hydroxyl group described above.

W _{1 to} W ₄ , W _{11 to} W ₁₄ , W _{21 to} W ₂₄ , W ₃₁
Substituents specifically represented by to _W-34, an alkyl group (e.g., methyl group, ethyl group, butyl group, etc. iso- butyl group) include, those aryl groups (monocyclic as well as polycyclic, e.g. Phenyl group, carboxyphenyl group, p-tolyl group, p-butylphenyl group, naphthyl group, etc.), heterocyclic group (for example, tetrahydrofuryl group, 2-pyrrolidinone-
1-yl group, thienyl group, furyl group, pyridyl group, carbazolyl group, pyrrolyl group, indolyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), vinyl group, trifluoromethyl Group, alkoxyl group (for example, methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (for example, phenoxy group,
p-tolyloxy group, etc.), sulfonyl group (for example, methanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (for example, ethoxycarbonyl group,
Butoxycarbonyl group), amino group (eg, amino group, biscarboxymethylamino group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido group (eg, ureido group, 3-methylureido group, 3 -Phenylureido group, etc.), thioureido group (eg, thioureido group, 3-methylthioureide group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), hydroxyl group, styryl And the like.

These groups can be substituted with the groups described in the description of the aliphatic group represented by R _{1 and the} like. Specific examples of the substituted alkyl group include, for example, 2-methoxyethyl group and 2-methoxyethyl group.
Hydroxyethyl group, 3-ethoxycarbonylpropyl group, 2-carbamoylethyl group, 2-methanesulfonylethyl group, 3-methanesulfonylaminopropyl group, benzyl group, phenethyl group, carboxymethyl group, carboxyethyl group, allyl group, And specific examples of the substituted aryl group include, for example, a p-carboxyphenyl group, a p-N, N-dimethylaminophenyl group, a p-morpholinophenyl group,
-Methoxyphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 3-chlorophenyl group, p-nitrophenyl group, etc., and specific examples of the substituted heterocyclic group For example, 5
-Chloro-2-pyridyl group, 5-ethoxycarbonyl-
Each group such as a 2-pyridyl group and 5-carbamoyl-2-pyridyl is exemplified.

W ₁ and W ₂ , W ₃ and W ₄ , W ₁₁ and W ₁₂ , W ₁₃ and W ₁₄ , W ₂₁ and W ₂₂ , W ₂₃ and W ₂₄ , W ₃₁ and W ₃₂ , R ₃₁ and W ₃₂ , R ₃₃ and R
₃₄ each as a fused ring which can be formed by connecting together, for example, 5-membered, and a fused carbocyclic 6-membered saturated or unsaturated. These condensed rings can have a substituent at any position, and examples of these substituents include the groups described above as the groups that can be substituted with an aliphatic group.

V _{1 to} V ₉ , V _{11 to} V ₁₃ , V _{21 to} V ₂₉ , V ₃₁
Each in ~V _33, fluorine atom as the halogen atom represented, a chlorine atom, a bromine atom, an iodine atom, a substituted as the amino groups include those unsubstituted, for example, an amino group, dimethylamino group, diphenylamino Amino group, methyl-
Examples of the alkylthio group include a methylthio group, an ethylthio group, and a benzylthio group.Examples of the arylthio group include substituted and unsubstituted ones, such as a phenylthio group and an m-fluorophenylthio group. And the lower alkyl group is a straight-chain or branched group having 5 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an isopropyl group. No. The lower alkoxyl group is a group having 4 or less carbon atoms, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and an iso-propoxy group. Including, for example, phenyl, 2-naphthyl, 1-naphthyl, o-tolyl, o-methoxyphenyl, m-chlorophenyl, m-bromophenyl, p-tolyl, p-ethoxyphenyl, etc. Groups include, substituted and unsubstituted heterocyclic groups,
For example, 2-furyl group, 5-methyl-2-furyl group, 2
-Thienyl group, 2-imidazolyl group, 2-methyl-1-
Imidazolyl group, 4-phenyl-2-thiazolyl group, 5
-Hydroxy-2-benzothiazolyl group, 2-pyridyl group, 1-pyrrolyl group and the like.

These groups can be substituted with groups such as a phenyl group, a halogen atom, an alkoxyl group and a hydroxyl group.

V ₁ and V ₃ , V ₂ and V ₄ , V ₃ and W ₅ , V ₄
And V _6, V ₅ and V _7, V ₆ and V _8, V ₇ and V _9, V ₁₁ and V _13, V
₂₁ and V ₂₃ , V ₂₂ and V ₂₄ , V ₂₃ and V ₂₅ , V ₂₄ and V ₂₆ , V ₂₅
And V ₂₇ , V ₂₆ and V ₂₈ , V ₂₇ and V _29, and a 5- to 7-membered ring formed by bonding between V ₃₁ and V ₃₃ include, for example,
Examples thereof include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a decalin ring. These rings can be substituted with a lower alkyl group, a lower alkoxyl group, or an aryl group described for R.

The methine groups represented by L _{1 to} L ₉ and L _{11 to} L ₁₅ each independently represent a substituted or unsubstituted methine group. Specific examples of the substituted group include a fluorine atom, a chlorine atom,
A substituted or unsubstituted lower alkyl group (e.g., methyl group, ethyl group, iso-propyl group, benzyl group, etc.),
A lower alkoxyl group (eg, methoxy group, ethoxy group, etc.), a substituted or unsubstituted aryloxy group (eg, phenoxy group, naphthoxy group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group,
p-tolyl group, o-carboxyphenyl group, etc.), -N
(U ₁ ) (U ₂ ), —SR _g or a substituted or unsubstituted heterocyclic group (eg, 2-thienyl group, 2-furyl group, N,
N′-bis (methoxyethyl) barbituric acid group).

[0125] wherein R _g is a lower alkyl group, an aryl group or a heterocyclic group described for R group described above, -SR _g
Specific examples of the group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a tolylthio group, and the like.

U ₁ and U ₂ each represent a substituted or unsubstituted lower alkyl group or aryl group, and U ₁ and U ₂ are connected to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring (for example, a pyrazole ring). , A pyrrole ring, a pyrrolidine ring, a morpholine ring, a piperidine ring, a pyridine ring, a pyrimidine ring, an indole ring, etc.). In addition, these methine groups can form a 5- to 7-membered ring by linking to methine groups adjacent to each other or to methine groups separated by one.

The formulas (1), (2), (1-1),
In the compounds represented by (2-1), (3) and (4),
When a group having a cation or anion charge is substituted, a counter ion is formed with an equivalent amount of an anion or cation so that the charge in the molecule is offset. For example, specific examples of the cation necessary for canceling the intramolecular charge represented by X ₁ , X ₁₁ , X ₂₁ , and X ₃₁ include a proton, an organic ammonium ion (for example, triethylammonium, Triethanolammonium, each ion such as pyridinium), inorganic cations (for example, each cation such as lithium, sodium, and potassium). Specific examples of the acid anion include, for example, a halogen ion (for example, a chlorine ion, a bromine ion,
Iodine ion), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion, hexafluorophosphate ion And the like.

One of these infrared spectral sensitizing dyes of the present invention is characterized by having a tricyclic fused heterocyclic nucleus in which a nitrogen atom of a benzoazole ring is bonded to a carbon atom at the peri position. Is particularly preferably a long-chain polymethine dye characterized by having a sulfinyl group substituted on the benzene ring of a benzoazole ring.

The following formulas (1), (2) and (1)
-1), (2-1), (3), and (4), representative compounds of the photosensitive dyes or spectral sensitizing dyes are shown below, but the present invention is not limited to these compounds. Absent

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[0131]

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[0135]

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[0136]

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[0137]

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[0138]

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The infrared-sensitive dyes described above are described, for example, by FM Hammer, The Chemistry of
Heterocyclic Compounds No. 18
Volume, The Cyanine Dyes and Re
rated Compounds (A. Weissbe
rger ed. Published by Interscience, Ne
w York 1964).

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

In the case of supersensitization, the photosensitivity becomes particularly high. If the reducing agent is not deactivated, the printout silver after development tends to be large, and the present invention is particularly effective. In the case of infrared sensitization, the infrared sensitizing dye further has a redox potential capable of reducing silver halide and organic silver salt to some extent. In the presence of a reducing agent that can reduce the organic silver salt, silver clusters that become fogged silver are easily formed. The formed silver clusters also act as catalyst nuclei to induce fogging, so that when stored in a dark place, the storage stability decreases,
Further, when exposed to a light place after development, a phenomenon such as an increase in printout silver occurs. Further, the sensitivity of the infrared-sensitive material extends to a heat radiation region outside the range of visible light, which is effective in increasing printout silver due to heat radiation even in a dark place. In particular, in the case of an infrared spectrally sensitized photosensitive material whose sensitivity has been enhanced by a supersensitizer, the effect is large.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in RD17643 (issued December 1978) No. 23.
Section J on page 1V, or Japanese Patent Publication No. 9-25500, 4
3-4933, JP-A-59-19032, and JP-A-59-19032.
192,242 and JP-A-5-341432.

In the present invention, a heteroaromatic mercapto compound represented by the general formula [6] is preferable as a supersensitizer.

Formula [6] Ar-SM In the formula, M is a hydrogen atom or an alkali metal atom;
r is a heteroaromatic or fused heteroaromatic ring having one or more nitrogen, sulfur, oxygen, selenium, or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole,
Benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine,
Purine, quinoline, quinazoline and the like. However, other heteroaromatic rings are also included.

The present invention also includes a disulfide compound which forms the above-mentioned mercapto compound when it is contained in a dispersion of an organic acid silver salt and / or silver halide grain emulsion. In particular, a disulfide compound represented by the following general formula can be mentioned as a preferred example.

Ar in the formula [7] Ar-SS-Ar has the same meaning as in the above formula [6].

The above heteroaromatic ring includes, for example, a halogen atom (for example, Cl, Br, I), a hydroxyl group, an amino group, a carboxyl group, and an alkyl group (for example, one or more carbon atoms, It may have a substituent selected from the group consisting of those having 4 carbon atoms and alkoxyl groups (for example, those having one or more carbon atoms, preferably those having 1 to 4 carbon atoms).

The mercapto-substituted heteroaromatics are listed below. However, the invention is not limited to these.

M-1 2-mercaptobenzimidazole M-2 2-mercaptobenzoxazole M-3 2-mercaptobenzothiazole M-4 5-methyl-2-mercaptobenzimidazole M-5 6-ethoxy-2- Mercaptobenzothiazole M-6 2,2'-dithiobis (benzothiazole) M-7 3-mercapto-1,2,4-triazole M-8 4,5-diphenyl-2-imidazolethiol M-9 2-mercaptoimidazole M-10 1-ethyl-2-mercaptobenzimidazole M-11 2-mercaptoquinoline M-12 8-mercaptopurine M-13 2-mercapto-4 (3H) -quinazolinone M-147-trifluoromethyl-4- Quinolinethiol M-15 2,3,5,6-tetrachloro- - pyridinethiol M-16 4-Amino-6-hydroxy-2-mercaptopyrimidine monohydrate M-17 2-amino-5-mercapto-1,3,4
Thiadiazole M-18 3-Amino-5-mercapto-1,2,4-
Triazole M-19 4-Hydroxy-2-mercaptopyrimidine M-20 2-Mercaptopyrimidine M-21 4,6-Diamino-mercaptopyrimidine M-22 2-Mercapto-4-methylpyrimidine hydrochloride M-23 3-Mercapto- 5-phenyl-1,2,4
-Triazole M-24 2-mercapto-4-phenyloxazole The supersensitizer according to the present invention contains 0.001 to 1.0 per mol of silver in the emulsion layer containing the organic silver salt and the silver halide grains.
It is preferable to use it in the molar range. Particularly preferably, the amount is in the range of 0.01 to 0.5 mol per mol of silver.

The binder suitable for the heat-developable photographic light-sensitive material of the present invention is transparent or translucent and generally colorless, and includes natural polymers, synthetic polymers and copolymers, and other film-forming media such as gelatin, gum arabic and polyvinyl. Alcohol, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylate, polymethacrylic acid, polyvinyl chloride, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile) ), Copoly (styrene-butadiene), polyvinylacetals,
For example, there are polyvinyl formal, polyvinyl butyral, polyesters, polyurethanes, phenoxy resin, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetates, cellulose esters, polyamides and the like, which may be hydrophilic or non-hydrophilic. However, among these binders, particularly preferred are water-insoluble polymers such as cellulose acetate, cellulose acetate butyrate and polyvinyl butyral, and among them, polyvinyl butyral is particularly preferred. Further, in the present invention, T
Those having a g (glass transition point) of 50 ° C. or more and 150 ° C. or less are preferable.

In the present invention, the binder amount of the photosensitive layer is preferably from 1.5 to 30 g / m ² . More preferably, it is 1.7 to 25 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

Examples of the crosslinking agent used in the present invention include various crosslinking agents conventionally used for photographic light-sensitive materials, for example, aldehyde-based, isocyanate-based, epoxy-based, and the like.
Acid anhydride, ethyleneimine, vinyl sulfone, sulfonic ester, acryloyl, carbodiimide crosslinking agents can be used, but the following are preferable, isocyanate compounds, epoxy compounds and acid anhydride compounds. It is.

The following general formula [8] which is one of the preferable ones
The isocyanate-based and thioisocyanate-based cross-linking agents represented by the following formulas will be described.

Formula [8] X = C = NL- (N = C = X) _v [wherein v is 1 or 2, and L is a (v + 1) -valent alkyl group, alkenyl group, cycloalkyl X is an alkyl group, an aryl group or an alkylaryl group, and X is an oxygen or sulfur atom. In the compound represented by the general formula [8], the aryl ring of the aryl group may have a substituent. Examples of preferred substituents include a halogen atom (eg, a bromine atom or a chlorine atom), a hydroxyl group, an amino group, a carboxyl group,
It is selected from an alkyl group and an alkoxyl group.

The above-mentioned isocyanate-based crosslinking agents are isocyanates having at least two isocyanate groups and adducts thereof (adducts). More specifically, aliphatic diisocyanates and fatty acids having a cyclic group Group diisocyanates, benzene diisocyanates, naphthalene diisocyanates, biphenyl isocyanates, diphenylmethane diisocyanates, triphenylmethane diisocyanates, triisocyanates, tetraisocyanates, adducts of these isocyanates and diisocyanates with these isocyanates 3
Adducts with polyhydric polyalcohols.

As specific examples, the isocyanate compounds described on pages 10 to 12 of JP-A-56-5535 can be used.

That is, ethane diisocyanate, butane diisocyanate, hexane diisocyanate, 2,2-
Dimethylpentane diisocyanate, 2,2,4-trimethylpentane diisocyanate, decane diisocyanate, ω, ω′-diisocyanate-1,3-dimethylbenzol, ω, ω′-diisocyanate-1,2-dimethylcyclohexane diisocyanate, ω, ω-diisocyanate-1,4-diethylbenzol, ω, ω ′
-Diisocyanate-1,5-dimethylnaphthalene,
ω, ω'-diisocyanate-n-propylbiphenyl, 1,3-phenylenediisocyanate, 1-methylbenzol-2,4-diisocyanate, 1,3-dimethylbenzol-2,6-diisocyanate, naphthalene-1,4-diisocyanate , 1,1'-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4 '
-Diisocyanate, 3,3'-dimethylbiphenyl-
4,4'-diisocyanate, diphenylmethane-4,
4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-diethoxydiphenylmethane-4,4 '
-Diisocyanate, 1-methylbenzol-2,4,
6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, triphenylmethane-4,4 ', 4'-triisocyanate , Tolylene diisocyanate, 1,5-naphthylene diisocyanate; dimer or trimer adduct of these isocyanates (for example, 2 mol of adduct of hexamethylene diisocyanate, hexamethylene diisocyanate 3)
Molar adduct, 2,4-tolylene diisocyanate 2
Molar adduct, 2,4-tolylene diisocyanate 3
An adduct of two or more different isocyanates selected from these isocyanates; and a dihydric or trivalent polyalcohol (preferably a polyalcohol having up to 20 carbon atoms). Examples thereof include adducts with ethylene glycol, propylene glycol, pinacol, trimethylolpropane, etc. (for example, adducts of tolylene diisocyanate and trimethylolpropane; adducts of hexamethylene diisocyanate and trimethylolpropane, etc.). Among these, an adduct of an isocyanate and a polyalcohol has a particularly high ability to improve interlayer adhesion, and to prevent delamination, image shift, and generation of bubbles. Such a polyisocyanate may be placed in any part of the photothermographic material. For example, in the support (especially when the support is paper, it can be included in the size composition), the photosensitive layer side of the support such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer, and an undercoat layer. Can be added to one or more of these layers.

As the thioisocyanate crosslinking agent used in the present invention, a compound having a thioisocyanate structure corresponding to the above isocyanates is also useful.

The amount of the crosslinking agent used in the present invention is in the range of 0.001 to 2 mol, preferably 0.005 to 0.5 mol, per 1 mol of silver.

The isocyanate compound and the thioisocyanate compound which can be contained in the present invention are:
Although it is preferable that the compound functions as the above-mentioned cross-linking agent, v may be zero (0) in the above-mentioned general formula (8), that is, a compound having only one of the functional groups may provide good results. . Hereinafter, specific examples will be listed, but the present invention is not limited thereto.

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Further, preferred crosslinking agents in the present invention are epoxy compounds having at least one epoxy group and acid anhydrides.

The epoxy compound used in the present invention may be any one having at least one epoxy group, and there is no limitation on the number, molecular weight, etc. of the epoxy group. The epoxy group is preferably contained in the molecule as a glycidyl group via an ether bond or an imino bond. The epoxy compound may be any of a monomer, an oligomer, a polymer and the like, and the number of epoxy groups present in the molecule is usually 1 to 10
About two, preferably two to four. When the epoxy compound is a polymer, it may be a homopolymer or a copolymer, and a particularly preferable range of the number average molecular weight Mn is about 2000 to 20,000.

The epoxy compound used in the present invention has the following general formula:

The compound represented by [9] is preferable.

[0172]

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General formula

In [9], the substituent of the alkylene group represented by R is preferably a group selected from a halogen atom, a hydroxyl group, a hydroxyalkyl group or an amino group. It is preferable that the linking group represented by R has an amide linking moiety, an ether linking moiety, and a thioether linking moiety. Examples of the divalent linking group represented by _{X -SO 2 -, - SO 2} NH -, - S -, - O-, or -
NR'- is preferred. Here, R 'is a monovalent substituent, and is preferably an electron withdrawing group.

Hereinafter, specific examples of the epoxy compound used in the present invention will be shown, but the present invention is not limited to these.

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These epoxy compounds may be used alone or in combination of two or more. The addition amount is not particularly limited, but is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / m ² , more preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² . It is.

In the present invention, the epoxy compound can be added to an optional layer on the photosensitive layer side of the support such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer, and an undercoat layer. It can be added to one or more layers. Also, it can be added to any layer on the opposite side of the support from the photosensitive layer. In the case of a photosensitive material having a photosensitive layer on both sides, any layer may be used.

The acid anhydride used in the present invention is a compound having at least one acid anhydride group represented by the following structural formula.

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The acid anhydride used in the present invention is not limited as long as it has at least one such acid anhydride group. The number and molecular weight of the acid anhydride group are not limited. The compound represented by is preferred.

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In the general formula [B], Z represents an atomic group necessary for forming a monocyclic or polycyclic ring system. These ring systems may be unsubstituted or substituted. Examples of the substituent include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxyl group (eg, methoxy, ethoxy, octyloxy), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxyl group, an aryloxy group (Eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group , A sulfonylamino group, an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group,
Includes sulfo groups and amino groups. As the substituent,
Those containing no halogen atom are preferred.

Specific examples of the acid anhydride are shown below, but the present invention is not limited thereto.

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These acid anhydrides may be used alone or in combination of two or more. The amount of addition is not particularly limited, but is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / m ² , and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m 2.
It is in the range of ² .

In the present invention, the acid anhydride can be added to any layer on the photosensitive layer side of the support such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer and an undercoat layer. It can be added to one layer or two or more layers. Especially, it is preferable to add to the same layer as the epoxy compound of the present invention. Further, it can be added to any layer on the opposite side of the support from the photosensitive layer. In the case of a type of photosensitive material having photosensitive layers on both surfaces, any layer may be used.

In the present invention, the organic silver salt is a reducible silver source, and is a silver salt of an organic acid or a heteroorganic acid, especially a long-chain (10 to 30 carbon atoms, preferably 15 to 25 carbon atoms).
Silver salts of aliphatic carboxylic acids and nitrogen-containing heterocyclic compounds are preferred. Organic or inorganic complexes in which the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions are also preferred. Examples of these suitable silver salts include RD17
029 and 29996, and include the following.

Silver salts of organic acids, for example, gallic acid, oxalic acid,
Silver salts such as behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, and aldehydes with hydroxy-substituted aromatic carboxylic acids Silver salts or complexes of polymer reaction products, for example, silver salts of reaction products of aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) Or complexes, silver salts or complexes of thiones, for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione, and 3-carboxymethyl-4-thiazoline-2
Silver salts or complexes such as -thione, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,2;
Complexes or salts of silver and a nitrogen acid selected from 4-triazole and benzotriazole, silver salts such as saccharin and 5-chlorosalicylaldoxime, and silver salts of mercaptides. Among them, preferred silver salts include silver behenate, silver arachidate and silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, or a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate, sodium arachidate, etc., the above-mentioned soap and silver nitrate are mixed by a controlled double jet method to produce an organic silver salt crystal. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably 0 μm or less and monodispersed.
The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. Average particle size is 0.05 μm to 10 μm, preferably 0.05 μm to
5 μm, particularly preferably 0.05 μm to 1.0 μm. The monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.

In the present invention, the tabular grains of the organic silver salt preferably have at least 60% of the total organic silver.
In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to make the organic silver salt into these shapes, the crystal of the organic silver salt is dispersed and pulverized with a ball mill or the like with a binder or a surfactant. Obtained by: Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained.

The heat-developable photographic light-sensitive material of the present invention forms a photographic image by heat-development processing, and includes a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, It is preferable that the photothermographic material is a heat-developable photographic material containing a color tone agent for suppressing the color tone of silver in a state of being dispersed in a usual (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but after exposure to high temperatures (for example,
(80 ° C. to 250 ° C.) for development. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

Examples of suitable toning agents used in the present invention are R.
D17029 discloses the following.

Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (e.g., N-hydroxy-1,8-naphthalimide); cobalt complexes (e.g., hexaamminetrifluoroacetate of cobalt); mercaptans (e.g., 3-mercapto-1,2,2,3). 4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles (e.g., N, N'-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole)); isothiuronium
onium) derivatives and certain photobleaches (eg, 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2
-(Tribromomethylsulfonyl) benzothiazole combination); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-
Dimethyloxyphthalazinone and 2,3-dihydro-
1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone and sodium benzenesulfinate or 8-methylphthalazinone and sodium p-trisulfonate); a mixture of phthalazine and phthalic acid Combinations; phthalazine (including phthalazine adducts) and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydrides (e.g., phthalic acid, 4-methylphthalic acid, -Nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine, naphthoxazine derivatives; benzoxazine-2,4
-Diones (for example, 1,3-benzoxazine-2,
4-dione); pyrimidines and asymmetric triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2, 3a, 5, 6
a-tetraazapentalene). Preferred toning agents are phthalazinone or phthalazine.

The photothermographic material of the present invention may contain an antifoggant. Mercury compounds known as effective antifoggants, for example, in US Pat. No. 3,589,903, are environmentally unfavorable. Therefore, non-mercury antifoggants have been studied for a long time. Non-mercury antifoggants include, for example, U.S. Pat. No. 4,546,075.
No. 4,452,885 and JP-A-59-57.
Preferred are antifoggants as disclosed in US Pat.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,99.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036] are preferably used.

As another example of the preferred antifoggant, JP-A-9-90550, paragraph [006]
2] to [0063]. Further, other suitable antifoggants are disclosed in US Pat.
No. 28,523 and European Patent Nos. 600,587, 605,981 and 631,176.

In addition to these materials, various additives may be added to the photosensitive layer, the non-photosensitive layer, or other forming layers according to the purpose. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. These additives and the other additives mentioned above are RD17029
(June 1978, pp. 9-15) can be preferably used.

Examples of the material of the support used for the photothermographic material include various polymer materials, glass, wool cloth, cotton cloth, paper, metal (for example, aluminum), and the like. What can be processed into a flexible sheet or roll is suitable. Therefore, as a support in the photothermographic material of the present invention,
Plastic films (eg, cellulose acetate film, polyester film, polyethylene terephthalate film, polyethylene naphthalate film,
Polyamide film, polyimide film, cellulose triacetate film, polycarbonate film, etc.) are preferable, and in the present invention, a biaxially stretched polyethylene terephthalate film is particularly preferable. The thickness of the support is about 50 to 300 μm, preferably 70 to 300 μm.
１８０180 μm.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be included in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.
In the present invention, the conductive compounds described in U.S. Pat. No. 5,244,773, columns 14 to 20, are preferably used.

There are no particular restrictions on the method of coating the necessary layers on the light-sensitive material of the present invention, such as a light-sensitive layer, a protective layer, and a back coat layer.
Methods such as dip coating, bar coating, curtain coating, and hopper coating can be used. Further, two or more of these layers may be applied simultaneously. As a solvent for the coating solution, an organic solvent such as methyl ethyl ketone (MEK), ethyl acetate, and toluene is preferably used.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. For example, a protective layer is provided on the photosensitive layer to protect the photothermographic layer, and a back coat layer is provided on the opposite surface of the support to prevent sticking between photosensitive materials or in a photosensitive material roll. Is preferably provided. Further, a filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light transmitted through the photothermographic layer, or the photosensitive layer may contain a dye or pigment. Good. As the dye, compounds described in JP-A-8-201959 are preferred. The photosensitive layer may be composed of a plurality of layers, or a high-sensitivity layer and a low-sensitivity layer may be provided for adjusting the gradation, and these layers may be combined. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature after exposure. The heating temperature is preferably from 80 ° C. to 200 ° C., and more preferably from 100 ° C. to 150 ° C. If the heating temperature is lower than 80 ° C., a sufficient image density cannot be obtained in a short time, and if the heating temperature is higher than 200 ° C., the binder is melted and adversely affects not only the image itself but also transportability such as transfer to a roller and a developing machine. Effect. By heating, a silver image is generated by an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This reaction process proceeds without any supply of a processing liquid such as water from the outside.

In the present invention, the photothermographic material preferably contains a certain amount of a solvent. Examples of these solvents include the following.

In the present invention, examples of the solvent include ketones such as acetone, isophorone, ethyl amyl ketone, methyl ethyl ketone, and methyl isobutyl ketone. Methyl alcohol as alcohols,
Examples include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, cyclohexanol, and benzyl alcohol. Glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, hexylene glycol and the like. Examples of ether alcohols include ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like. Examples of ethers include ethyl ether, dioxane, and isopropyl ether. Examples of the esters include ethyl acetate, butyl acetate, amyl acetate, and isopropyl acetate. Examples of the hydrocarbons include n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene and the like. Examples of chlorides include methyl chloride, methylene chloride, chloroform, dichlorobenzene and the like. Monomethylamine as amines,
Dimethylamine, triethanolamine, ethylenediamine, triethylamine and the like can be mentioned. Other examples include water, formamide, dimethylformamide, nitromethane, pyridine, toluidine, tetrahydrofuran, acetic acid and the like. However, it is not limited to these. These solvents can be used alone or in combination of several kinds.

These solvents may be separately contained in the light-sensitive material. However, since the heat-developable photographic light-sensitive material is usually prepared by coating an organic solvent-based coating solution, it was used for preparing the coating solution. It is preferable to adjust by changing conditions such as temperature conditions in a drying step or the like so that a certain amount of the organic solvent is contained. The content of the solvent can be measured by gas chromatography under conditions suitable for detecting the contained solvent.

The amount of the solvent contained in the light-sensitive material according to the present invention must be adjusted so as to be 5 to 1000 mg, preferably 100 to 500 mg in total amount (weight basis) per 1 m ² of the light-sensitive material. It is.

When the content is within the above range, a heat-developable photographic material having a low fog density while having high sensitivity can be obtained.

Exposure of the photothermographic material of the present invention can be applied to any light source in the infrared region. However, the exposure of the photothermographic material can be made to have a high laser power or to make the photosensitive material transparent. From the infrared semiconductor laser (780 nm,
820 nm) is more preferably used.

In the present invention, the exposure is preferably performed by laser scanning exposure, but it is preferable to use a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular. .

Here, the expression "will not be substantially vertical" means that the angle is closest to vertical during laser scanning, preferably 55 to 88 degrees, more preferably 60 to 86 degrees, and still more preferably. Means 65 ° to 84 °, most preferably 70 ° to 82 °.

The beam spot diameter on the exposed surface of the photosensitive material when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. Note that the lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of unevenness like interference fringes.

Further, the exposure in the present invention is preferably performed using a laser scanning exposure machine which emits a scanning laser beam which is a vertical multi. Image quality deterioration such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode.

[0221] For the vertical multiplication, a method of combining, using return light, or superimposing a high frequency is preferable.
In addition, the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more.
nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

[0222]

(Preparation of undercoated photographic support)

<Preparation of PET-subtracted photographic support> A commercially available biaxially stretched heat-fixed 175 μm thick optical density of 0.170
(Measured with a densitometer PDA-65 manufactured by Konica Corp.) 8 W / m ^{2 on} both sides of a blue colored PET film
・ A corona discharge treatment is performed for one minute, and the undercoating coating liquid a-1 shown below is applied to one surface so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The surface was coated with the following undercoating coating solution b-1 so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Co-weight of butyl acrylate (30% by weight), t-butyl acrylate (20% by weight), styrene (25% by weight), and 2-hydroxyethyl acrylate (25% by weight) Combined latex liquid (solid content 30%) 270 g C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water << Subtraction coating solution b-1 >> Butyl acrylate (40 wt. %), Styrene (20% by weight), glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g C-1 0.6 g hexamethylene-1,6-bis (ethylene urea) 0 0.8 g Finished to 1 liter with water Subsequently, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
The lower coating layer B-2 is coated with the following coating liquid b-2 on the lower coating layer B-1 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Subbing Upper Layer >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower upper layer coating solution b-2 >> (C-4) 60 g Latex solution containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0225]

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[0226]

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(Preparation of Photosensitive Silver Halide Emulsion A) Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and potassium bromide, potassium iodide and iridium chloride in a molar ratio (98/2) equimolar to silver nitrate were added to silver 1
370 ml of an aqueous solution containing 1 × 10 ^-4 mole per mole,
The pAg was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5.0 with NaOH, and the average particle size was 0.06 μm and the coefficient of variation of the particle size was 12
%, And a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
5.9 and a pAg of 7.5 to obtain a photosensitive silver halide emulsion A.

(Preparation of Powdered Organic Silver Salt A) 111.4 g of behenic acid and 83.8 of arachidic acid were added to 4720 ml of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at high speed with pAg7, and the mixture was sufficiently stirred. Next, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While the temperature of the organic acid sodium solution was maintained at 55 ° C., the photosensitive silver halide emulsion A (containing 0.038 mol of silver) and 450 ml of pure water were added and stirred for 5 minutes. Next, 76M of a 1M silver nitrate solution
was added over 2 minutes, stirred for another 20 minutes, and the water-soluble salts were removed by filtration. Then, the conductivity of the filtrate was 2
Washing with deionized water and filtration were repeated until the solution reached μS / cm, centrifugal dehydration was performed, and then drying was performed at 37 ° C. under a heated nitrogen stream until the weight was not lost, to obtain a powdered organic silver salt A. .

(Preparation of Photosensitive Emulsion Dispersion) Polyvinyl butyral powder (Butvar B manufactured by Monsanto)
-79) 14.57 g of methyl ethyl ketone (MEK)
The mixture was dissolved in 1457 g, and 500 g of the powdered organic silver salt A was gradually added to the mixture while stirring with a dissolver-type homogenizer, followed by thorough mixing. Thereafter, a media type dispersing machine (gettzmann) filled with 80% of 1 mm Zr beads (manufactured by Toray)
The emulsion was dispersed at a peripheral speed of 13 m and a residence time of 3 minutes in a mill to prepare a photosensitive emulsion dispersion.

<Preparation of Infrared Sensitizing Dye Liquid> Among the compounds of the general formulas (1) to (4) which are infrared sensitizing dyes, S-
43, 350 mg, 2-chlorobenzoic acid 13.96 g,
Then, 2.14 g of 5-methyl-2-mercaptobenzimidazole was dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

<Preparation of stabilizer liquid>
g and 0.5 g of potassium acetate were dissolved in 8.5 g of methanol to prepare a stabilizer solution.

<Preparation of developer solution> As a developer, 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl)-
17.74 g of 2-methylpropane was dissolved in MEK and 10
The final developer solution was 0 ml.

<Preparation of Antifoggant Solution> The following antifoggant 2 was dissolved in 5.81 g of MEK to make a final antifoggant solution in 100 ml.

<< Preparation of Coating Solution for Photosensitive Layer >> The above-mentioned photosensitive emulsion dispersion (50 g) and 15.11 g of MEK were kept at 21 ° C. while stirring, and 390 μl of the following antifoggant 1 (10% methanol solution) was added. Stirred for hours. Further, 996 μl of zinc bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes.

Next, 1.416 ml of the infrared sensitizing dye solution and 667 μl of the stabilizer solution were added, and the mixture was stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes.

While keeping the temperature at 13 ° C., polyvinyl butyral (Butvar B-79, Monsanto)
After adding 13.31 g and stirring for 30 minutes, the following additives were added at intervals of 15 minutes while stirring was continued.

Phthalazine: 305 mg Tetrachlorophthalic acid: 102 mg 4-Methylphthalic acid: 137 mg Infrared dye 1: 37 mg After the above was added and stirred for 15 minutes, an antifoggant solution: 5.47 ml A developer solution: 14.06 ml Hexamethylene diisocyanate 10% MEK solution: 1.60 ml was sequentially added and stirred to obtain a photosensitive layer coating solution.
Drying was performed at 75 ° C. for 5 minutes. Note that the drying step was performed under a nitrogen atmosphere without surroundings in order to prevent adverse effects due to oxygen and the like.

<Back side coating> Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² Matting agent: monodispersity 15% Average particle size 10 μm monodisperse silica 30 mg / m ² <Photosensitive layer side coating> 2 g / m of coated silver
² was applied.

<Surface Protective Layer> A solution having the following composition was applied on the photosensitive layer.

Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Matting agent: monodispersity 10%, average particle size 4 μm monodispersed silica Amount shown in Table 1 The matting agent in the photosensitive layer coating solution was as shown in Table 1. Change the photosensitive material sample No. 1 to 8 were produced.

[0241]

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[0242]

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[0243]

[Table 1]

<< Exposure and Development Processing: Density Measurement >> From the emulsion surface side of the photosensitive material prepared as described above, an exposure machine using a semiconductor laser having a wavelength of 800 nm to 820 nm and formed into a multimode in a vertical direction by superposition of high frequency as an exposure source. Gave exposure by laser scanning. At this time, an image was formed with the angle between the exposure surface of the photosensitive material and the exposure laser beam being 75 degrees.
(Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was 90 degrees.)
Thereafter, using an automatic developing machine having a heat drum, photosensitive materials having different sizes shown in Table 2 were subjected to heat development at 120 ° C. for 15 seconds so that the protective layer and the drum surface were in contact with each other.
At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. Evaluation of density unevenness of the image portion finished to a uniform density was performed by a densitometer. As a result of the film density unevenness measurement, the film was exposed to a density of 1.0, and densities at 10 points were measured, and the average of the density differences was obtained.

<Evaluation of Sharpness> The SMPT pattern image was exposed by the above-mentioned laser exposure apparatus, and the thin line image thus developed was visually evaluated on a Shakasten in four steps.

1: Poor sharpness, unusable for practical use 2: Clearly poor sharpness 3: Slightly poor sharpness, but discriminable 4: High sharpness, high discrimination << Solvent content in film Measurement >> 4 as film area
6.3 cm ² was cut out, finely chopped to about 5 mm, stored in a special vial, sealed with a septum and an aluminum cap, and set in a Hewlett-Packard headspace sampler model HP7694. Gas chromatography (GC) connected to a headspace sampler is a flame ionization detector (FI)
597 made by Hewlett-Packard equipped with D)
It was type 1. The main measurement conditions were a headspace sampler heating condition: 120 ° C. for 20 minutes, a GC introduction temperature: 150 ° C., a column: DB-624 manufactured by J & W, a temperature rise: 45 ° C. for 3 minutes → 100 ° C. (8 ° C. / Min) to obtain a gas chromatogram. Solvents to be measured were MEK and methanol, and after storing a certain amount of each diluted with butanol in the solvent on the left in a dedicated vial, the chromatogram was prepared using the peak area of the chromatogram obtained in the same manner as above. The calibration curve was used to obtain the solvent content in the film.

[0247]

[Table 2]

Example 2 In the same manner as in Example 1, an undercoat layer A-1 and an undercoat layer A-2 were coated on a commercially available biaxially stretched heat-fixed blue 175 μm thick blue colored PET film. Was applied, and the undercoat layers B-1 and B-2 were applied to the back side to prepare a photographic support.

Also, a photosensitive silver halide emulsion A and a powdered organic silver salt A were prepared in the same manner as in Example 1 to prepare a photosensitive emulsion dispersion.

Using these materials, photosensitive material No. 1 was prepared in the same manner as in Example 1 except that the amount of polysiloxane shown in Table 3 was added to the surface protective layer in Example 1. 2-1
~ 2-8 were produced.

[0251]

[Table 3]

In the same manner as in Example 1, density unevenness of the film and sharpness of the image were evaluated. Table 4 shows the evaluation results.
It was shown to.

[0253]

[Table 4]

As is clear from Table 4, the sample according to the present invention is superior to the comparative sample in terms of the storage stability over time of the undeveloped photosensitive material and the image storage stability after development processing, while having high sensitivity.

Example 3 (Preparation of photosensitive silver halide emulsion B) 7.5 g of ossein gelatin having an average molecular weight of 100,000 and 10 mg of potassium bromide were dissolved in 900 ml of water, and the temperature was adjusted to 35 ° C and the pH was adjusted to 3.0.
370 ml of an aqueous solution containing 74 g of silver nitrate
And an aqueous solution containing 1 × 10 ⁻⁴ mol per mol of silver of potassium bromide and potassium iodide, and an equimolar ratio of silver nitrate (98/2), while maintaining the pAg at 7.7. It was added over 10 minutes by the double jet method. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added and Na was added.
Adjust the pH to 5 with OH and average particle size 0.06μ
m, coefficient of variation of particle size 12%, [100] face ratio 8
7% of cubic silver iodobromide grains were obtained. The emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment.
By adjusting to 5, a photosensitive silver halide emulsion B was obtained.

(Preparation of powdered organic silver salt B) 111.4 g of behenic acid and 83.8 of arachidic acid were added to 4720 ml of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 M aqueous sodium hydroxide solution was added, and 6.9 ml of concentrated nitric acid was added.
Upon cooling to 55 ° C., a sodium organic acid solution was obtained. While maintaining the temperature of the organic acid sodium solution at 55 ° C., the silver halide emulsion (containing 0.038 mol of silver) and 450 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of a 1 M silver nitrate solution was added over 2 minutes, and an additional 20 ml.
And stirred to remove water-soluble salts by filtration. afterwards,
Water washing with deionized water and filtration were repeated until the conductivity of the filtrate reached 2 μS / cm, and centrifugal dehydration was performed.
Drying with warm air was carried out at a temperature of 0 ° C. until there was no loss in weight, whereby a powdered organic silver salt B was obtained.

(Preparation of Photosensitive Emulsion Dispersions 1-4) Polyvinyl butyral powder (Butva, Monsanto)
r B-79) 14.57 g of methyl ethyl ketone 14
The resultant was dissolved in 57 g, and 500 g of powdered organic silver salt B was gradually added while stirring with a dissolver-type homogenizer and mixed well. Then add 1mm Zr beads (Toray) to 80
The photosensitive emulsion dispersion liquid 1 was prepared by performing dispersion at a peripheral speed of 13 m and a residence time of 0.5 minute in a mill using a media-type disperser (manufactured by gettzmann) filled with%.

Photosensitive emulsion dispersion liquid 2 was obtained in exactly the same manner as in preparation of photosensitive emulsion dispersion liquid 1, except that the residence time in the mill was changed to 3 minutes. Further, in the preparation of the photosensitive emulsion dispersion liquid 1, the photosensitive emulsion dispersion liquid 3 was prepared by performing one-pass dispersion at 8000 psi using a high-pressure homogenizer (manufactured by APV) instead of a media type disperser. Photosensitive emulsion dispersion 4 was obtained in exactly the same manner as in preparation of photosensitive emulsion dispersion 3, except that the dispersion was repeated five times.

<Preparation of Infrared Sensitizing Dye Solution>
350 mg S-43, 13.9 2-chloro-benzoic acid
6 g and 2.14 g of 5-methyl-2-mercaptobenzimidazole were dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

[Preparation of Coating Solution for Photosensitive Layer] The above-mentioned photosensitive emulsion B
(500 g) and 100 g of MEK while stirring.
It was kept at ° C.

Pyridinium hydrobromide perbromide (PHP, 0.45 g) was added and stirred for 1 hour. Further, calcium bromide (10% methanol solution 3.25m
l) was added and stirred for 30 minutes.

Next, sensitizing dye Nos. A mixed solution of S-43, 4-chloro-2-benzoylbenzoic acid, and a supersensitizer (5-methyl-2-mercaptobenzimidazole) (mixing ratio 1: 250: 20, 0.1 in sensitizing dye) % Methanol solution, 7 ml) and stirred for 1 hour, then the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes.

While keeping the temperature at 13 ° C., polyvinyl butyral powder (Butvar B-7 manufactured by Monsanto) was used.
9) Alternatively, after adding 48 g of the compound shown in Table 5 and sufficiently dissolving, the following additives are added.

Developer (1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane) 15 g Desmodur N3300 (Mobay Inc., aliphatic isocyanate) 1.10 g Phthalazine 1.5 g Tetrachlor Phthalic acid 0.5 g 4-Methylphthalic acid 0.5 g After preparing a photosensitive layer coating solution, the temperature was kept at 13 ° C., and coating was performed by the following method.

The following layers were sequentially formed on a support to prepare a sample. In addition, each drying was performed at 75 ° C. for 5 minutes.

<Coating on Back Side> (Preparation of Coating Solution on Back Side) 830 g of methyl ethyl ketone
While stirring the cellulose acetate butyrate (E
Astman Chemical, CAB381-2
0) 84.2 g, polyester resin (Bostic,
(VitelPE2200B) 4.5 g was added and dissolved. 0.30 g of infrared dye-1 was added to the dissolved solution. Further, as shown in Table 1, the compound of the general formula (1) was added and sufficiently stirred until dissolved. Finally,
Silica (WR Grace) dispersed in methyl ethyl ketone at a concentration of 1 wt% with a dissolver type homogenizer.
(Syloid 64X6000) was added and stirred to prepare a coating solution for the back surface.

(Coating of back surface)
The coating liquid on the back surface was applied and dried by an extruder coater so that the dry film thickness became 3.5 μm. Drying temperature 100
<Coating on the photosensitive layer side> After coating on the back surface, apply the photosensitive layer coating solution and the surface protective layer coating solution having the following composition to the coating layer. 2.
The photosensitive layer coating solution was applied so as to have a thickness of 0 g / m ² and a thickness of 100 μm when the surface protective layer was applied.

<Preparation of coating solution for surface protective layer> Acetone 175 ml Methanol 15 ml Cellulose acetate butyrate 8.0 g Phthalazine 1.0 g 4-methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g 1% (W / W) based on monodisperse silica binder having an average particle size of 4 μm Compound of general formula (I) Amount shown in Table 5

[0269]

[Table 5]

<< Method of Measuring Surface Element Composition >> The results (peak ratio) are shown in Table 6 by using an ESCA750 type X-ray photoelectron spectrometer manufactured by Shimadzu Corporation.

<< Measurement of Solvent Content in Film >> A film area of 46.3 cm ² was cut out, finely chopped to about 5 mm, stored in a dedicated vial, sealed with a septum and an aluminum cap, and then manufactured by Hewlett-Packard Company. It was set on a headspace sampler HP7694. Table 6 shows the results measured by gas chromatography connected to a headspace sampler.

<< Exposure and Development Processing >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, an image was formed with the angle between the exposure surface of the photosensitive material and the exposure laser beam being 75 degrees. (Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared with the case where the angle was set to 90 degrees.) Then, the protective layer of the photosensitive material was formed using an automatic developing machine having a heat drum. And heat development at 120 ° C. for 15 seconds. At that time, exposure and development were performed at 23 ° C and 50 ° C.
Performed in a room conditioned to% RH. The obtained image was evaluated using a densitometer. The results of the measurement were evaluated in terms of sensitivity (the reciprocal of the ratio of the exposure amount giving a density 1.0 higher than the unexposed portion) and fog, and are shown in Table 6 as relative values with the sensitivity of the photosensitive material 6 being 100.

<Evaluation of Image Preservation Property> Two samples subjected to the same processing as in the sensitometry evaluation were subjected to the test at 25 ° C. and 55 ° C.
% For 7 days, and the other one at 25 ° C and 55% RH
After exposure to natural light for 7 days, the density of the fogged portions was measured. The results are shown in Table 6 where the increase in fog after storage was ΔDm.
Indicated by in.

Increase in fog = fog when exposed to natural light-fog when stored under light shielding <Evaluation of sharpness>
The T-line pattern image was exposed, and the developed thin line image was visually evaluated on a Shakasten in four stages.
Shown in

1: Poor sharpness, unusable for practical use 2: Clearly poor sharpness 3: Slightly poor sharpness, but discriminable 4: High sharpness, high discrimination

[0276]

[Table 6]

[0277]

According to the present invention, a heat-developable photographic light-sensitive material having high sensitivity, excellent sharpness and excellent image storability has been obtained. or,
A method for processing a heat-developable photographic light-sensitive material having excellent uniformity in film density was obtained even when photographic materials of different sizes were continuously developed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03D 13/00 G03D 13/00 A

Claims (14)

[Claims] 1. A method in which two or more heat-developable photographic materials having different sizes are continuously processed automatically by a heat-developer, wherein the surface matte degree of at least one side of the heat-developable photographic light-sensitive material is 2 or more.
A method for processing a heat-developable photographic light-sensitive material, which is from 0 mmHg to 300 mmHg. 2. The photothermographic material according to claim 1, wherein said photothermographic material has a dynamic friction coefficient of 0.5 or less when two or more photothermographic materials having different sizes are continuously processed automatically by a photothermographic machine. A method for processing a photothermographic material. 3. The method for processing a photothermographic material according to claim 1, wherein the photothermographic material is exposed to an infrared laser. 4. The heat development according to claim 1, wherein the exposure is carried out by a laser scanning exposure device in which a scanning laser beam for recording an image on the heat-developable photographic material is a vertical multi-scan. Processing method of photographic photosensitive material. 5. The method according to claim 1, wherein an exposure is performed by a laser scanning exposing machine in which an angle formed by a scanning laser beam when recording an image on the photothermographic material is not substantially vertical. 5. The method for processing a photothermographic material according to 2, 3, or 4. 6. The heat-developable photographic light-sensitive material has a temperature of 80.degree.
The method for processing a photothermographic material according to claim 1, wherein the photothermographic material is developed by heating at a temperature of not more than ° C. 7. 7. The heat-developable photographic light-sensitive material contains 40 to 45 solvents.
7. The toner according to claim 1, wherein the toner is developed by heating in a state containing 00 ppm.
6. The method for processing a photothermographic material according to item 1. 8. A photothermographic material comprising an organic silver salt, a photosensitive silver halide and a reducing agent on a support,
It contains a fluorine-based surfactant represented by the following general formula (F), and when its elemental composition is examined by X-ray photoelectron spectroscopy,
F1S peak intensity / C1S peak intensity ratio is 0.01 to
A heat-developable photographic light-sensitive material, which falls within the range of 1.0. General formula (F) Rf-AX [wherein, Rf represents an alkyl group, an alkenyl group, or an aryl group containing at least three fluorine atoms. A represents a divalent linking group, and X represents a water-soluble group. ] 9. A photothermographic material comprising an organic silver salt, photosensitive silver halide particles and a reducing agent on a support, a binder having a Tg of 50.degree. C. or more and 150.degree. C. or less, and a surface element composition. When examined by X-ray photoelectron spectroscopy,
F1S peak intensity / C1S peak intensity ratio is 0.01 to
A heat-developable photographic light-sensitive material, which falls within the range of 1.0. 10. An image recording method, comprising exposing the photothermographic material according to claim 8 to an infrared laser. 11. The image recording method according to claim 10, wherein a scanning laser beam for recording an image on the heat-developable photographic photosensitive material is exposed by a laser scanning exposure device that is a vertical multi-scan. 12. The method according to claim 10, wherein the exposure is performed by a laser scanning exposing machine in which an angle formed by a scanning laser beam when recording an image on the photothermographic material is not substantially vertical. The image recording method described in 1. 13. An image forming method, wherein the photothermographic material according to claim 8 is developed by heating at a temperature of 80 ° C. or more and 250 ° C. or less. 14. An image forming method, wherein the photothermographic material according to claim 8 or 9 is developed by heating while containing 40 to 4500 ppm of a solvent.