JP2002229152A - Heat developiong photosensitive material, image recording method and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developing photosensitive material, an image recording method and an image forming method which realize high sensitivity, low fog, high covering power and improved preservability of silver images and silver tone after the development. SOLUTION: The heat developing photosensitive material has a layer containing at least non-photosensitive organic silver salts, photosensitive silver halides, a reducing agent which can reduce silver ions by heat, a binder, a crosslinking agent, and sensitizing dyes on a supporting body. The photosensitive material satisfies the following conditions. The conditions are (1) the molar number A [mol] and the average particle volume V [μm3] of the photosensitive silver halides and the molar number B [mol] of the non-photosensitive organic silver salts satisfy the relation of 250<=(A/B)<=1500 and (2) the amount D [mol] of the sensitizing dyes added per one mol of silver and C=(A/B)/V satisfy the relation of 4×10-3×C+5<=D×105<=8×10-3×C+5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material which forms an image by thermal development, etc., and has high sensitivity, low fog, high covering power, and improved silver image preservability and silver tone after development. The present invention relates to a heat-developable photosensitive material, an image recording method and an image forming method thereof.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, a waste liquid caused by wet processing of an image forming material has been a problem in terms of workability and the like. There is a strong demand for a reduction in the amount of processing waste liquid. Therefore, a technique relating to a photothermographic material (heat-developable photosensitive material) that enables efficient exposure with a laser image setter or a laser imager and can form a high-resolution and clear image has attracted attention.

As this technique, a heat-developable photographic light-sensitive material for forming a photographic image using a heat-development processing method is disclosed in, for example, D.A.
Morgan and B.A. Shelley
y) U.S. Pat. Nos. 3,152,904;
457,075 or D.C. H. Crostaver (Klo
"Thermally Processed Silver System (Thermal Processed S)
ilver Systems) ”(Imaging Processes and Materials (Imaging)
Processes and Materials) N
Eblette Eighth Edition, Sturge,
V. Walworth, A .; Shepp, pp. 279, 1989) and the like.

In these heat-developable photographic materials, the photosensitive silver halide grains contained in the photosensitive layer are used as an optical sensor, an organic silver salt is used as a supply source of silver ions, and usually 80 to 80 depending on a built-in reducing agent. A technique is known in which an image is formed by performing heat development at about 250 ° C., and thereafter, no fixing is performed. In order to make this technology more efficient, organic silver that is easy to dispose properly in the photosensitive layer and has little adverse effect on light scattering is necessary to achieve both a smooth supply of silver ions to the silver halide and prevention of deterioration of transparency due to light scattering. Much effort has been put into improving the particle shape.

For example, for the above purpose, attempts have been made to simply atomize the particles by dispersing or pulverizing them with high energy using a disperser or the like. Particles were damaged, which increased fog, lowered sensitivity and the like, and caused problems such as deterioration of image quality.

Accordingly, there is a need for a technique for maintaining sensitivity and image quality (without employing a technique for increasing the amount of silver), which is capable of obtaining high light sensitivity and image density and reducing fog. Had been.

On the other hand, the photothermographic material contains organic silver salt particles, photosensitive silver halide particles, and a reducing agent. There is also a problem that fogging or photo-decomposed silver (print-out silver) is likely to occur during the storage period after the heat development. In particular, in the photothermographic material, after exposure, 80
Because heat development is only performed at ~ 250 ° C and fixing is not performed, the silver image may be exposed to heat or light during long-term storage under conditions where silver halide, organic silver salts and a reducing agent remaining in unexposed areas are present. Problems such as discoloration occur.

That is, the presence of a reducing agent in the photothermographic material makes it easier for heat fog to be generated by the reaction with the organic silver salt, and the light in a wavelength region different from the exposure wavelength for image recording. A system containing silver halide grains and an organic silver salt, because it functions as a hole trap or a reaction other than the original function of reduction of silver ions by a reducing agent caused by exposure after development with light containing In this case, there is a phenomenon that the printout silver is inevitably increased, and this is considered as a part of the above problem.

In addition to the above-mentioned causes, it is conceivable that fog nuclei which cause fogging may be formed in the production process of the photothermographic material.

In addition to the above-described problems such as fogging, it is also found that it is difficult to obtain an image having a preferable color tone, and it is considered that the solution from this viewpoint should be solved at the same time.
A technique for solving these problems is disclosed in Japanese Patent Laid-Open No. 6-208.
192, JP-A-8-267934, U.S. Pat.
No. 14,311 and the documents cited in these patent documents, etc., although these disclosed technologies have a certain degree of effect, they are still not enough to satisfy the level required in the market. Not something.

[0011]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide:
A photothermographic material having high sensitivity, low fog, high covering power, and improved silver image storability and silver tone after development,
An object of the present invention is to provide an image recording method and an image forming method.

[0012]

The above objects of the present invention have been attained by the following means a) to e).

A) On a support, at least:
In a photothermographic material comprising a layer containing a non-photosensitive organic silver salt, a photosensitive silver halide, a reducing agent capable of reducing silver ions by heat, a binder, a crosslinking agent and a sensitizing dye, the following conditions are used. A photothermographic material, characterized in that: Condition (1): When the number of moles of the photosensitive silver halide is A [mol], the average grain volume is V [μm ³ ], and the number of moles of the non-photosensitive organic silver salt is B [mol], Satisfy the relationship.

250 ≦ (A / B) / V ≦ 1500 Condition (2): When (A / B) / V is C and the content of sensitizing dye per mole of silver is D [mol]. Satisfies the following relationship.

4 × 10 ⁻³ × C + 5 ≦ D × 10 ⁵ ≦ 8 ×
10 ⁻³ × C + 5 b) In the photothermographic material, the compound represented by the general formula (1)
A photothermographic material comprising at least one compound represented by the formula (I) and satisfying the following relationship when the content of the compound per mol of silver is E.

4 × 10 ⁻³ × C + 4 ≦ E × 10 ⁴ ≦ 8 ×
10 ⁻³ × C + 4 c) Exposure to the photothermographic material of a) or b) above using a laser exposing machine in which the angle between the exposure surface of the photothermographic material and the scanning laser beam is not substantially perpendicular. An image recording method for a photothermographic material, comprising:

D) The method for recording an image of a photothermographic material according to c) above, wherein the exposure by the laser exposure device is performed by a laser beam scanning exposure device which is a vertical multi.

E) An image forming method characterized in that the photothermographic material according to a) or b) is thermally developed at a temperature of 80 ° C. or more and 200 ° C. or less.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The non-photosensitive organic silver salt in the present invention is a reducible silver source, and is a silver salt of an organic acid or a heteroorganic acid, particularly, a long-chain (10-30, preferably 15-25) aliphatic carboxylic acid. Silver salts of acids and nitrogen-containing heterocyclic compounds are preferred. The ligand has a total stability constant of 4.0 to 1 for silver ions.
Also preferred are the organic or inorganic complexes described in RD (Research Disclosure) Nos. 17029 and 29963 having a value of 0.0. Preferred examples thereof include the following.

Silver salts of organic acids (for example, silver salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver (for example, 1- (3 -Carboxypropyl)
Thiourea, 1- (3-carboxypropyl) -3,3-
Dimethylthiourea, etc.); silver salts or complexes of polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted aromatic carboxylic acids (eg, salicylic acid, Benzoic acid, 3,
Silver salts or complexes of reaction products of 5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, etc.); silver salts or complexes of thiones (for example, 3- (2-carboxyethyl) -4)
-Hydroxymethyl-4-thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione), imidazole, pyrazole, urazole, 1,
Complexes or salts of nitrogen acids with silver selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptan derivatives. Among the organic silver salts described above, a silver salt of a fatty acid is preferably used,
More preferably used are silver behenate, silver arachidate and / or silver stearate.

The above-mentioned organic silver salt can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, but a forward mixing method, a reverse mixing method, a simultaneous mixing method and the like are preferably used.
Further, a controlled double jet method or the like as described in JP-A-9-127643 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.) is prepared by adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid, and then controlled double jet. According to the method, the soap and silver nitrate are mixed to produce a crystal of an organic silver salt. At that time, silver halide grains may be mixed. Although the organic silver salt according to the present invention can be used in various shapes, tabular grains are preferred. In particular, it is a tabular organic silver salt particle having an aspect ratio of 3 or more, and has a maximum area. For this purpose, particles having an average needle-like ratio of the tabular organic silver salt particles measured from the main plane direction of 1.1 or more and less than 10 are preferable. In addition, a more preferable needle ratio is 1.1 or more and less than 5.0. In the present invention, having tabular organic silver salt particles having an aspect ratio of 3 or more means that
The tabular organic silver salt particles have a total number of 50 organic silver salt particles.
%. Furthermore, in the organic silver salt particles according to the present invention, tabular organic silver salt particles having an aspect ratio of 3 or more preferably account for 60% or more of the total number of organic silver salt particles, and more preferably 70% or more (number). And particularly preferably 80% or more (number). In the present invention, the tabular grains having an aspect ratio of 3 or more are particles having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between an average particle diameter and an average thickness, which is represented by the following formula.

AR = average particle diameter (μm) / average thickness (μm) The aspect ratio of the tabular organic silver salt particles according to the present invention is preferably from 3 to 20, and more preferably from 3 to 10.
It is. The reason for this is that if the aspect ratio is too low, the organic silver salt particles tend to be densest, and if the aspect ratio is too high, the organic silver salt particles tend to overlap each other, Therefore, light scattering and the like are likely to occur, and as a result, the transparency of the photothermographic material is reduced. Therefore, the above range is considered to be a preferable range.

In order to determine the average particle size described above, the dispersed organic silver salt particles are diluted and dispersed on a grid with a carbon support film, and the particles are analyzed with a transmission electron microscope (manufactured by JEOL Ltd., 2000).
FX type), and photographed directly at a magnification of 5000 times. The negative was captured as a digital image by a scanner, and the average particle diameter was calculated by measuring 300 or more particle diameters (equivalent circle diameter) using appropriate image processing software.

The above average thickness was calculated by a method using a TEM (transmission electron microscope) as shown below.

First, the photosensitive layer applied on the support is attached to an appropriate holder with an adhesive, and the thickness is 0.1 to 0.
Make ultra-thin sections of 2 μm. The prepared ultra-thin section is
Using a transmission electron microscope (hereinafter, referred to as a TEM) while supporting it on a copper mesh, transferring it onto a carbon film hydrophilized by glow discharge, and cooling it to −130 ° C. or lower with liquid nitrogen, use a transmission electron microscope (magnification: 5,000 to 40). Observe the brightfield image at 2,000x magnification, and the image is film, imaging plate,
Quickly record on a CCD camera. At this time, as the visual field to be observed, it is preferable to appropriately select a portion where there is no break or looseness in the section.

As the carbon film, it is preferable to use a carbon film supported by an organic film such as ultra-thin collodion or formvar. More preferably, the carbon film is formed on a rock salt substrate and obtained by dissolving and removing the substrate. This is a carbon-only film obtained by removing the film by an organic solvent and ion etching. The acceleration voltage of the TEM is preferably 80 to 400 KV, particularly preferably 80 to 20 KV.
0 KV.

It is preferable that a TEM image recorded on a suitable medium is decomposed into at least 1024 pixels × 1024 pixels, preferably 2048 pixels × 2048 pixels or more, and subjected to image processing by a computer. In order to perform image processing, it is preferable that an analog image recorded on a film is converted into a digital image by a scanner or the like, and shading correction, contrast / edge enhancement, and the like are performed as necessary. Thereafter, a histogram is prepared, and a portion corresponding to organic silver is extracted by a binarization process.

The thickness of the extracted organic silver salt particles is set to 300
More than one piece was measured manually with appropriate software, and the average value was determined.

The average value of the acicular ratio of the tabular organic silver salt grains can be determined by the following method. First, the photosensitive layer containing the tabular organic silver salt particles is swollen with an organic solvent capable of dissolving the photosensitive layer binder, separated from the support, and subjected to ultrasonic washing, centrifugation, and supernatant removal using the solvent. Repeat 5 times. The above steps are performed under safelight.

Subsequently, the mixture was diluted with MEK (methyl ethyl ketone) so that the organic silver solid content concentration was 0.01%.
After ultrasonic dispersion, the mixture is dropped on a polyethylene terephthalate film hydrophilized by glow discharge and dried.

The film on which the particles are mounted has a thickness of 3 ° at an angle of 30 ° with respect to the film surface by a vacuum evaporation apparatus.
After obliquely depositing Pt-C of nm by electron beam, it is preferable to use it for observation.

For details of the electron microscopy technique and the sample preparation technique, see “The Electron Microscopy Society of Japan, Kanto Chapter / Medical and Biological Electron Microscopy” (Maruzen), “The Electron Microscopy Society of Japan, Kanto Section / Electronics”. Microscopic biological sample preparation method ”(Maruzen) can be referred to.

The prepared sample was subjected to an acceleration voltage of 2 KV using a field emission scanning electron microscope (hereinafter referred to as FE-SEM).
The secondary electron image is observed at a magnification of 5000 to 20000 times at 4 to 4 KV, and the image is stored in an appropriate recording medium. For the above processing, it is convenient to use a device that can AD-convert the image signal from the electron microscope main body and record it directly as digital information on the memory. It can also be used by converting it into a digital image with a scanner or the like and applying shading correction, contrast / edge enhancement, etc. as necessary.

For an image recorded on an appropriate medium, it is preferable to decompose one image into at least 1024 pixels × 1024 pixels, preferably 2048 pixels × 2048 pixels or more, and perform image processing by a computer.

As a procedure of the image processing described above, first, a histogram is prepared, and a portion corresponding to organic silver salt particles having an aspect ratio of 3 or more is extracted by a binarization process. The unavoidably agglomerated particles are cut by a suitable algorithm or manual operation to perform contour extraction. Thereafter, the maximum length (MX LNG) and the minimum width (WIDTH) of each particle are measured for at least 1000 particles, and the acicular ratio is determined for each particle by the following formula. The maximum length of a particle refers to the maximum value when two points in the particle are connected by a straight line. The minimum width of a particle means a value when a distance between the parallel lines becomes a minimum value when two parallel lines circumscribing the particle are drawn.

Acicular ratio = (MX LNG) ÷ (WIDTH) Thereafter, an average value of the acicular ratios of all the measured particles is calculated. When the measurement is performed in the above procedure, it is preferable that the correction of the length per pixel (scale correction) and the correction of the two-dimensional distortion of the measurement system are sufficiently performed using a standard sample in advance. As a standard sample, Uniform Latex Particles (DULP) commercially available from Dow Chemical Co., USA is suitable, and polystyrene particles having a coefficient of variation of less than 10% with respect to a particle size of 0.1 to 0.3 μm are suitable. Preferably, specifically, the particle size is 0.2
Lots with 12 μm and standard deviation 0.0029 μm are available.

For details of the image processing technology, reference can be made to “Image processing application technology (Industrial Research Committee) edited by Hiroshi Tanaka”.
The image processing program or device is not particularly limited as long as the above operation can be performed, and an example is Luzex-III manufactured by Nireco.

The organic silver salt particles according to the present invention are preferably monodisperse particles.
To 30%, and by using monodispersed particles in this range, an image having a high density can be obtained. Here, the monodispersion is defined by the following equation.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The average particle size of the organic silver salt particles described above is 0.01 to 0.8.
μm is preferable, and more preferably 0.05 to 0.5 μm
m, and the average particle diameter (equivalent circle diameter) represents the diameter of a circle having the same area as an individual particle image observed with an electron microscope.

The method for obtaining the organic silver salt particles having the above-mentioned shape is not particularly limited, but includes a mixed state when forming an organic acid alkali metal salt soap and / or a mixed state when adding silver nitrate to the soap. And to optimize the proportion of silver nitrate that reacts with the soap,
For dispersion and pulverization, disperse with a media disperser or a high-pressure homogenizer, etc. At this time, the binder concentration should be 0.1 to 10% of the organic silver weight. In addition to the above, preferable conditions include stirring at a peripheral speed of 2.0 m / sec or more using a dissolver during liquid preparation.

It is preferable that the tabular organic silver salt particles according to the present invention are preliminarily dispersed together with a binder, a surfactant and the like, if necessary, and then dispersed and pulverized with a media disperser or a high-pressure homogenizer. For the preliminary dispersion, a general stirrer such as an anchor type or a propeller type, a high-speed rotary centrifugal radiation type stirrer (dissolver), and a high-speed rotary shear type stirrer (homomixer) can be used.

Examples of the media dispersing machine include a rolling mill such as a ball mill, a planetary ball mill, and a vibrating ball mill, a bead mill as a medium stirring mill, an attritor,
Other basket mills and the like can be used,
Various types can be used as the high-pressure homogenizer, such as a type that collides with a wall, a plug, or the like, a type in which liquids are divided into a plurality of pieces and then the liquids collide at high speed, and a type that passes through a thin orifice.

As ceramics used for ceramic beads used at the time of media dispersion, for example, A
l ₂ O ₃ , BaTiO ₃ , SrTiO ₃ , MgO, ZrO,
_{BeO, Cr 2 O 3, SiO} 2, SiO 2 -Al 2 O 3, Cr
₂ O ₃ -MgO, MgO-CaO, MgO-C, MgO-
Al ₂ O ₃ (spinel), SiC, TiO ₂ , K ₂ O, Na
₂ O, BaO, PbO, B ₂ O ₃ , SrTiO ₃ (strontium titanate), BeAl ₂ O ₄ , Y ₃ Al ₅ O ₁₂ , Zr
O ₂ -Y ₂ O ₃ (cubic zirconia), 3BeO-Al ₂ O
₃ -6SiO ₂ (Synthesis emerald), C _{(diamond), Si 2 O-nH 2} O, ticker silicon, yttrium stabilized zirconia, zirconia toughened alumina, and the like are preferable. Yttrium-stabilized zirconia and zirconia reinforced alumina (these zirconia-containing ceramics are hereinafter abbreviated as zirconia) are particularly preferably used because, for example, the generation of impurities due to friction with beads and a disperser during dispersion is small. In the apparatus used when dispersing the tabular organic silver salt particles according to the present invention,
It is preferable to use ceramics such as zirconia, alumina, silicon nitride, and boron nitride or diamond as a material of the member that contacts the organic silver salt particles, and it is particularly preferable to use zirconia.

The concentration of the binder at the time of the above-mentioned dispersion is preferably 0.1 to 10% of the weight of the organic silver salt particles. Is preferably not exceeded. In addition, a preferable operation condition of the main dispersion is, for example, when a high-pressure homogenizer is used as the dispersing means, 29.42 MPa
a to 98.06 MPa, and the number of operation times is preferably 2 or more as preferable operation conditions. When a media dispersing machine is used as the dispersing means, the peripheral speed is from 6 m / sec to 13 m / sec.
/ Sec is preferred.

In addition, zirconia can be used for a part of beads and members used at the time of dispersion, and this can be mixed into the dispersion emulsion at the time of dispersion, and it has been confirmed that photographic performance is improved by this. is there. Zirconia fragments may be added later to the dispersion emulsion, or may be added in advance during the preliminary dispersion. Although a specific method is not particularly limited, as an example, if MEK is circulated through a bead mill filled with zirconia beads, a high-concentration zirconia solution can be obtained. . Next, the photosensitive silver halide according to the present invention will be described. The photosensitive silver halide according to the present invention functions as an optical sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, the average grain size of the photosensitive silver halide grains is preferably small, and the average grain size is 0.1 μm.
Hereinafter, more preferably 0.01 μm to 0.1 μm, particularly preferably 0.02 μm to 0.08 μm. Here, the particle size refers to the diameter (equivalent circle diameter) of a circle having the same area as an individual particle image observed with an electron microscope. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. The particle size is more preferably 30 or less, and particularly preferably 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Miller index [1
The ratio of the [00] plane is determined by utilizing the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tan
i. Imaging Sci. , 29, 165 (1
985).

Another preferred form of silver halide is tabular grains. The term “tabular grain” as used herein refers to a grain having an aspect ratio = r / h of 3 or more when the thickness in the vertical direction is h μm where the square root of the projected area of the grain is r μm. Among them, the aspect ratio is preferably 3 or more and 5 or more.
0 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. 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. 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. The photographic emulsion used in the present invention is P.I. Chimie et P by Glafkides
hysique Photographique (Pa
ul Montel, 1967); F. Du
Photographic Emulsio by fin
n Chemistry (The Focal Pre
ss, 1966); L. Zelikman e
Making and Coating P by tal
photographic Emulsion (The
Focal Press, 1964) and the like. That is, the acid method,
Neutral method, ammonia method and the like may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the general formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
Represents 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. Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir), and osmium (Os).

The following are specific examples of transition metal complex ions, but the present invention is not limited to these.

[0052] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3-6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^{2 -} 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^2- 27: [Ir (NS) Cl _5] ^2- these metal ions may be a metal complex or metal complex ions one kind, be used in combination metal of the same kind of metal or different two or more Good. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol. Compounds providing these metals are 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 chemical sensitization It may be added at any stage before or after, particularly preferably at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably at the stage of growth. Add in stages.

In the addition, it may be added in several divided portions, may be uniformly contained in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

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 metal ions or complex ions in advance during the preparation of 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 surface of the particles, 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.

In the present invention, the photosensitive silver halide grains may or may not be desalted after grain formation, but when desalting is carried out, it is known in the art such as a noodle method and a flocculation method. Can be desalted by washing with water. The silver halide grains according to the present invention may be chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, and noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction, as well known in the art. A sensitization method can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and US Pat. No. 2,448,0
No. 60 and British Patent No. 618,061 can be preferably used. Specific compounds of the reduction sensitization method include, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds,
A silane compound, a polyamine compound, or the like can be used. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation. About the method and procedure of this chemical sensitization, for example,
U.S. Pat. No. 4,036,650, British Patent 1,51
No. 8,850, JP-A-51-22430, and JP-A-51-7
Nos. 8319 and 51-81124.
Further, when a part of the organic silver salt is converted into photosensitive silver halide by a silver halide forming component, US Pat.
As described in U.S. Pat. No. 0,482, a low molecular weight amide compound may be used in order to achieve sensitization.

In the present invention, in addition to the photosensitive silver halide grains, it is preferable that a halogen-containing compound is allowed to act on an organic silver salt to form silver halide grains by conversion of the organic silver salt.

The silver halide forming components include inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Specific examples thereof are described in US Pat. 0
No. 39, No. 3,457,075, No. 4,003
Inorganic halides such as silver metal halides and ammonium halides described in detail in U.S. Pat. No. 749, British Patent Nos. 1,498,956 and JP-A Nos. 53-27027 and 53-25420. Onium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2
Halogenated hydrocarbons such as -methylpropane; N-halogen compounds such as N-bromosuccinimide, N-bromophthalimide and N-bromoacetamide; and others such as triphenylmethyl chloride, triphenylmethyl bromide,
Bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.

It is particularly preferred to use at least one onium salt having a halide or polyhalide anion. Particularly preferred oniums are organic-phosphonium, organic-sulfonium, and organic-nitrogen onium cations, with heterocyclic nitrogen oniums (eg, pyridinium), quaternary phosphonium, and tertiary sulfonium cations being preferred. Preferred halide anions are chloride, bromide, and iodide anions. Preferred polyhalide anions contain chlorine, bromine, and iodine atoms.

In the photothermographic material of the present invention, the number of moles of the photosensitive silver halide is A mole, and the average grain volume is V μm.
^{3. When} the non-photosensitive organic silver salt is B mol, it is preferable that the following formula is satisfied.

250 ≦ (A / B) / V ≦ 1500 The above-mentioned A mole is the number of moles of photosensitive silver halide grains contained per 1 m ^{2 of the} photothermographic material. It can be measured from a photothermographic material. That is, a sample of the photosensitive material is, for example, M
After stripping with a solvent such as EK and ultrasonically dispersing, pure water is added to the stripping solution and centrifuged. Organic silver is the interface between the solvent layer of MEK and the like and the aqueous layer, and silver halide is the aqueous layer. The silver halide is then washed with a solvent and extracted. This silver halide is dissolved in a KCN solution, and silver is quantified by an ICP emission spectrometer SPS-4000 (manufactured by Seiko Instruments Inc.), and the number of moles can be calculated.

For the B mole, a sample of the light-sensitive material is decomposed by, for example, sulfuric acid and nitric acid, and the IC is treated in the same manner as described above.
It can be calculated by quantifying silver by P emission spectroscopy and subtracting the silver content of silver halide. The above-mentioned average grain volume V μm ³ indicates the average of the volumes of the above-mentioned photosensitive silver halide grain groups. Can be calculated by measuring

The above relational expression according to the present invention preferably
400 ≦ (A / B) / V ≦ 1400, and more preferably 500 ≦ (A / B) / V ≦ 1300.
The photothermographic material of the present invention includes, for example, JP-A-63-15
No. 9841, No. 60-140335, No. 63-231
No. 437, No. 63-259,651 and No. 63-3042
No. 42, 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 include, for example, RD No. 17
No. 643, paragraph IV-A (p. 23, December 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, Japanese Patent Application Laid-Open No. 60-16224 discloses an argon ion laser light source.
7, U.S. Pat. No. 2,486,635, U.S. Pat.
No. 1,331, West German Patent No. 936,071, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-open No. Sho 50-6 / 1991 discloses simple merocyanines and helium neon laser light sources described in
No. 2425, No. 54-18726, No. 59-1022
Trinuclear cyanine dyes described in JP-A No. 29-29, JP-A-7-28
No. 48-42 describes merocyanines, LED light sources and infrared semiconductor laser light sources described in US Pat.
Nos. 172, 51-9609 and 55-39818
JP-A-62-284343, JP-A-2-1051
JP-A-59-191332 discloses thiacarbocyanines and infrared semiconductor laser light sources described in No. 35;
Tricarbocyanines described in JP-A-60-80841, JP-A-59-192242, JP-A-3-67.
No. 242, dicarbocyanines containing a 4-quinoline nucleus described in general formulas (IIIa) and (IIIb) are advantageously selected. In addition, the wavelength of the infrared laser light source is 75
0 nm or more, and more preferably 800 nm or more.
-182639, 5-341432, Tokuhei 6-
No. 52387, No. 3-10931, U.S. Pat.
Sensitizing dyes described in JP-A-41-866 and JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone, and a combination of sensitizing dyes is often used particularly for supersensitization. In addition to 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 photothermographic material of the present invention, when (A / B) / V is represented by C and the content of the sensitizing dye per mol of silver is represented by D mol, the following formula is preferably satisfied. .

4 × 10 ⁻³ × C + 5 ≦ D × 10 ⁵ ≦ 8 ×
10 ^-3 × C + 5 The D mole of the sensitizing dye is represented by a value obtained by dividing the mole number of the sensitizing dye by the mole number of all silver including silver halide and organic silver.

In the above relational expression, preferably, 5 ×
10 ⁻³ × C + 5 ≦ D × 10 ⁵ ≦ 8 × 10 ⁻³ × C + 5, and 6 × 10 ⁻³ × C + 5 ≦ D × 10 ⁵ ≦ 8 × 10 ⁻³ × C
+5 is more preferred. Next, general formula (1) according to the present invention will be described.

[0067]

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(Wherein, H ₃₁ Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group, T ₃₁ represents a divalent linking group or a linking group comprising an aliphatic hydrocarbon group, and J ₃₁ represents oxygen Represents a divalent linking group or linking group containing at least one atom, sulfur atom or nitrogen atom, wherein Ra, Rb, Rc and Rd each represent a hydrogen atom, an acyl group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic ring; Represents a group, or Ra and Rb, Rc and R
d, a bond between Ra and Rc or between Rb and Rd can form a nitrogen-containing heterocyclic group. M ₃₁ represents an ion necessary to neutralize the molecular charge, k ₃₁ represents the number of ions necessary for neutralizing the molecular charge. ) Examples of the divalent linking group consisting of an aliphatic hydrocarbon group represented by T _31, linear, branched or cyclic alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12), an alkenyl group (preferably having 2 to 20, more preferably 2 to 16, and still more preferably 2 to 12), an alkynyl group (preferably having 2 to 2 carbon atoms).
0, more preferably 2 to 16, even more preferably 2 to 1
2) and may have a substituent. For example, as the aliphatic hydrocarbon group, a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms)
6, more preferably 1 to 12), an alkenyl group (preferably having 2 to 20, more preferably 2 to 16, and still more preferably 2 to 12), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2-16, more preferably 2
To 12), and the aryl group has 6 to 20 carbon atoms.
Is a monocyclic or condensed aryl group (for example, phenyl, naphthyl and the like, preferably phenyl), and the heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic group (for example, 2 -Thiazolyl, 1-piperazinyl, 2-
Pyridyl, 3-pyridyl, 2-furyl, 2-thienyl,
2-benzimidazolyl, carbazolyl, etc.)
The hetero ring in these groups may be a single ring or may form a condensed ring with another ring. Each of these groups may have a substituent at an arbitrary position. For example, an alkyl group (including a cycloalkyl group and an aralkyl group, preferably having 1 carbon atom)
-20, more preferably 1-12, particularly preferably 1-8, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-heptyl, n- Octyl, n-decyl, n-
Undecyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, phenethyl and the like. ), An alkenyl group (preferably having 2 carbon atoms)
-20, more preferably 2-12 carbon atoms, particularly preferably 2-8 carbon atoms, for example, vinyl, allyl, 2-
Butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl), and an aryl group (preferably). Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 6 carbon atoms.
12, for example, phenyl, p-tolyl, o-aminophenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, ethylamino, dimethylamino, diethylamino, diphenylamino , Dibenzylamino, etc.), an imino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylimino, ethylimino, propylimino. Phenylimino, etc.) alkoxy group (preferably having 1 to 20 carbon atoms;
More preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, and butoxy. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy). An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom;
To 16, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl Group (preferably having 7 to 20 carbon atoms,
More preferably, it has 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably a prime number 1)
-20, more preferably 1-16, particularly preferably 1-10, for example, acetoxy, benzoyloxy and the like. ), An acylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), and sulfonyl. Amino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 1 carbon atom)
-20, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio), and an arylthio group (preferably C6-C20, more preferably C6-
16, particularly preferably having 6 to 12 carbon atoms, for example,
Phenylthio and the like. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably having 1 to 12 carbon atoms, for example, methanesulfonyl, tosyl and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms,
For example, methanesulfinyl, benzenesulfinyl and the like can be mentioned. ), Ureido group (preferably having 1 to carbon atoms)
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, diethylphosphoric amide, phenylphosphoric amide and the like can be mentioned. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, sulfino, carboxyl, phosphono, phosphino, nitro, hydroxamic acid Hydrazino group, heterocyclic group (for example, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, carbazolyl, pyridyl, furyl, piperidyl, morpholino and the like).

Among the above groups, groups capable of forming a salt such as a hydroxy group, a mercapto group, a sulfo group, a sulfino group, a carboxyl group, a phosphono group, a phosphino group, and the like may be salts. These substituents may be further substituted.
When there are two or more substituents, they may be the same or different. As the substituent, preferably, an alkyl group, an aralkyl group, an alkoxy group, an aryl group, an alkylthio group,
Acyl group, acylamino group, imino group, sulfamoyl group, sulfonyl group, sulfonylamino group, ureido group,
Amino group, halogen atom, nitro group, heterocyclic group, alkoxycarbonyl group, hydroxy group, sulfo group, carbamoyl group, carboxyl group, more preferably alkyl group, alkoxy group, aryl group, alkylthio group,
Acyl group, acylamino group, imino group, sulfonylamino group, ureido group, amino group, halogen atom, nitro group, heterocyclic group, alkoxycarbonyl group, hydroxy group, sulfo group, carbamoyl group, carboxyl group, more preferably Alkyl group, alkoxy group, aryl group, alkylthio group, acylamino group, imino group, ureido group, amino group, heterocyclic group, alkoxycarbonyl group, hydroxy group, sulfo group, carbamoyl group, and carboxyl group. The amidino group includes those having a substituent, and examples of the substituent include an alkyl group (each group such as methyl, ethyl, pyridylmethyl, benzyl, phenethyl, carboxybenzyl, and aminophenylmethyl), and an aryl group (phenyl, p-tolyl, naphthyl,
each group such as o-aminophenyl and o-methoxyphenyl), a heterocyclic group (2-thiazolyl, 2-pyridyl, 3-
Pyridyl, 2-furyl, 3-furyl, 2-thieno, 2-
Groups such as imidazolyl, benzothiazolyl and carbazolyl).

[0070] oxygen atom represented by J _31, examples of the divalent linking group containing a sulfur atom or a nitrogen atom one or more, for example, include the following. Also, a combination of these may be used.

[0071]

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Here, Re and Rf are each the same as R
This is synonymous with the contents defined for a to Rd. The aromatic hydrocarbon group represented by H ₃₁ Ar is preferably a group having 6 to 6 carbon atoms.
30, more preferably a monocyclic or condensed aryl group having 6 to 20 carbon atoms, for example, phenyl,
Naphthyl and the like are particularly preferable, and phenyl is particularly preferable. Examples of the aromatic heterocyclic group represented by H ₃₁ Ar include N, O
And a 5- to 10-membered unsaturated heterocyclic group containing at least one atom of S, and the heterocyclic ring in these groups may be a single ring, or may be a condensed ring with another ring. It may be formed. The heterocycle in such a heterocyclic group is preferably a 5- to 6-membered aromatic heterocycle, and a benzo-fused ring thereof, more preferably a 5- to 6-membered aromatic heterocycle containing a nitrogen atom, and It is a benzo-fused ring, more preferably a 5- to 6-membered aromatic heterocycle containing 1 to 2 nitrogen atoms, and the benzo-fused ring.

Specific examples of the heterocyclic group include, for example, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
Triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole,
Examples include groups derived from benzimidazole, benzoxazole, benzothiazole, benzothiazoline, benzotriazole, tetrazaindene, carbazole, and the like. Preferably as a heterocyclic group, imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, benzothiazoline, benzotriazole, Tetrazaindene, a group consisting of carbazole, more preferably imidazole, pyridine, pyrazine, quinoline, phenazine, tetrazole, thiazole, benzoxazole, benzimidazole, benzothiazole, benzothiazoline, benzotriazole,
And groups derived from carbazole.

The aromatic hydrocarbon group and the aromatic heterocyclic group represented by H ₃₁ Ar may have a substituent. Examples of the substituent include the same as those described as the substituent for T _31. And the preferred range is also the same. These substituents may be further substituted, and when there are two or more substituents, each may be the same or different. The group represented by H ₃₁ Ar is preferably an aromatic heterocyclic group.

[0075] Ra, Rb, Rc, aliphatic hydrocarbon groups represented by Rd, aryl group and heterocyclic group, an aliphatic hydrocarbon group At a the T _31, as an example of the aryl group and heterocyclic group The same can be mentioned, and the preferred range is also the same. The acyl group represented by Ra, Rb, Rc, and Rd is an aliphatic or aromatic group having 1 to 12 carbon atoms, and specific examples include acetyl, benzoyl, formyl, and pivaloyl. Ra and Rb, Rc
And a nitrogen-containing heterocyclic group formed by bonding between Rd and Rb or between Rb and Rd, a 3- to 10-membered saturated or unsaturated heterocyclic group (for example, a piperidine ring, a piperazine ring, an acridine ring, A cyclic group such as a pyrrolidine ring, a pyrrole ring, and a morpholine ring).

[0076] Specific examples of the acid anion as ion necessary to compensate for intramolecular charge, represented by M _31, for example, a halogen ion (e.g. chloride, bromide,
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 and the like.

Specific examples of the compound represented by formula (1) are shown below, but the present invention is not limited thereto.

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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The compound represented by formula (1) of the present invention may be a commercially available compound, or may be synthesized by a known method. For example, edited by The Chemical Society of Japan, New Experimental Chemistry Course, Vol. 14 (III), pp. 1739-1741 (197
It can be synthesized by the method described in 8).

The compound represented by formula (1) of the present invention can be added to a photothermographic material in a photosensitive layer or a non-photosensitive layer, but is preferably a photosensitive layer.

The amount of the compound represented by the general formula (1) of the present invention varies depending on the desired purpose, but is preferably 10 ^-4 to 1 mol, more preferably 10 ^{-3 to} 0.3 mol, more preferably 10 ^-3 mol per mol of Ag. Although it is preferable to add 10 ^-3 to 0.1 mol, as described above, it is preferably contained in the photothermographic material in a range satisfying the following relationships.

That is, in the photothermographic material of the present invention,
When (A / B) / V is C (A, B and V are as defined above) and the content of the compound represented by the general formula (1) per mol of silver is E, It is preferable to satisfy the following expression.

4 × 10 ⁻³ × C + 4 ≦ E × 10 ⁴ ≦ 8 ×
10 ⁻³ × C + 4 In the above relation, the following case is more preferred, and 5 × 1
0 ⁻³ × C + 4 ≦ E × 10 ⁴ ≦ 8 × 10 ⁻³ × C + 4 Further, 6 × 10 ⁻³ × C + 4 ≦ E × 10 ⁴ ≦ 8 × 10 ⁻³ ×
The case of C + 4 is more preferable.

The compounds of the general formula (1) may be used alone or in combination of two or more.

The compound of the general formula (1) of the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl It can be used by dissolving it in sulfoxide, methyl cellosolve and the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method. When dispersing the solid fine particles, a dispersing aid may be used.

The photothermographic material of the present invention preferably contains an antifoggant. Preferred antifoggants are disclosed in U.S. Pat. Nos. 3,874,946 and 4,75.
No. 6,999, and -C (X
1) A heterocyclic compound having one or more substituents represented by (X2) and (X3) (where X1 and X2 each represent a halogen atom, and X3 represents hydrogen or a halogen atom). Other suitable antifoggants include paragraphs [0030] to [00] of JP-A-9-288328.
36], JP-A-9-90550
No. 5,028,523 and European Patent Nos. 600,587, 605,981, 631,176, etc. Can be used.

The light-sensitive material of the present invention contains a reducing agent. Examples of suitable reducing agents are described in US Pat. No. 3,770,4.
No. 48, No. 3,773, 512, No. 3,593,
No. 863, and RD Nos. 17029 and 29963. Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (e.g., Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (e.g., anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (E.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxam) ); Sulfonamides anilines (e.g., 4-(N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amidooxins; Azines (for example, a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid); Polyhydroxybenzene and hydroxylamine in combination, reductone or hydrazine; Hydroxanoic acids; Azines and sulfonamidophenol Α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,3-dione; Chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-
Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t)
-Butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

In the photothermographic material of the present invention, it is desirable to use an additive called a color tone agent, a color tone imparting agent or an activator toner (hereinafter referred to as a color tone agent) together with the above-mentioned components. The color tone agent participates in the oxidation-reduction reaction between the organic silver salt and the reducing agent, and has a function of making the resulting silver image dark, particularly black. Examples of suitable toning agents for use in the present invention are disclosed in RD 17029 and include:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt); mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaching combinations (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); 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 + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 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, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic,
Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) ), Poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic. In order to protect the surface of the photothermographic material and prevent abrasion, a non-photosensitive layer may be provided outside the photosensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers. In the present invention, the amount of the binder in the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the speed of thermal development.
More preferably, it is 1.7 to 8 g / m ² . 1.5g
If it is less than / 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, epoxy-based, ethyleneimine-based, vinyl Sulfone-based, sulfonate-based, acryloyl-based, and carbodiimide-based cross-linking agents can be used. Preferred in the present invention are isocyanate-based compounds, epoxy compounds, and acid anhydrides. In addition, Japanese Patent Application No. 2000-07
It is also preferable to use a silane compound represented by the general formula (1) or the general formula (2) disclosed in 7904.

The photothermographic material of the present invention preferably has at least one layer on a support, and at least one layer is a photosensitive layer. The support may be composed of only a photosensitive layer, but it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In this case, a non-photosensitive layer may be further provided as another layer.

The materials according to the present invention (non-photosensitive organic silver salt, photosensitive silver halide, reducing agent, sensitizing dye, etc.) can be contained in the same layer or in different layers in combination with each other.

On the other hand, as another preferred embodiment, it is preferable that the non-photosensitive layer in the above case contains a binder having a higher glass transition temperature than the binder of the photosensitive layer.
Here, the binder is selected from the various binders described above, and the glass transition temperature is measured by a usual measurement method using DSC or the like.

In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer may be formed on the same side as the photosensitive layer and / or an antihalation dye layer, so-called backing layer, may be formed on the opposite side. Alternatively, a dye or a pigment may be included in the photosensitive layer. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range.
No. 59-182436, U.S. Pat.
No. 263, No. 4,594,312, European Patent Publication 5
33,008, 652,473, JP-A-2-21
Nos. 6140, 4-348339, 7-19143
Compounds described in Nos. 2, 7-301890 and the like are preferably used. The filter dye layer, antihalation dye layer, and backing layer may also serve as the non-photosensitive layer described above. These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin. The photosensitive layer according to the present invention may be a single layer or a plurality of layers, and preferably has a multilayer structure such as a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation. In particular, in the present invention, it is preferable that a plurality of photosensitive layers contain photosensitive silver halides having different sensitivities, since the particle size distribution of the developed silver can be controlled.

It is preferable that all coating solutions used for coating the photothermographic material of the present invention are filtered before coating. In the filtration, it is preferable to pass a filter medium having an absolute filtration accuracy or a quasi-absolute filtration accuracy of 5 to 50 μm at least once.

The photothermographic material of the present invention can be coated by a sequential multilayer coating method in which coating and drying of each layer are repeated.
Roll coating methods such as reverse roll coating and gravure roll coating, blade coating, wire bar coating, and die coating are used. In addition, before drying the already applied layer using multiple coaters, apply the next layer and simultaneously dry multiple layers, or use an extrusion die coater with slide coating, curtain coating or multiple slits,
A simultaneous multilayer coating method in which a plurality of coating liquids are laminated and applied is also used. Of these, the latter is more preferable in that the occurrence of coating failure due to foreign substances brought in from the outside can be prevented. Furthermore, when using the simultaneous multi-layer coating method, in order to prevent mixing between the layers, the viscosity at the time of applying the coating liquid of the uppermost layer is 0.1 Pa · s or more, and the viscosity at the time of applying the coating liquid of the other layer is set. Preferably, the viscosity is 0.03 Pa · s or more. In addition, when the solids dissolved in the coating liquid of each layer are laminated in a liquid state with the adjacent layer, if it is hardly soluble or insoluble in the organic solvent of the adjacent layer, it precipitates at the boundary surface and turbidity or turbidity of the coating film Therefore, it is preferable that the organic solvent most contained in the coating liquid of each layer is the same type (the content of the organic solvent commonly contained in each coating liquid in each liquid is larger than other organic solvents). .

It is preferable to dry as soon as possible after the multi-layer coating, and it is preferable to reach the drying step within 10 seconds in order to avoid interlayer mixing caused by flow, diffusion, density difference and the like. As a drying method, a hot air drying method, an infrared drying method, or the like is used, and a hot air drying method is particularly preferable. The drying temperature at that time is preferably 30 to 100 ° C. The photothermographic material of the present invention may be cut into a target size immediately after coating and drying, and then packaged, or may be wound into a roll and cut.
It may be stored temporarily before packaging. The winding method is not particularly limited, but winding by tension control is generally 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 formed by the scanning laser beam and the exposed surface of the photothermographic material does not become substantially perpendicular.

Here, "not 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 °.

When the laser beam is scanned on the photothermographic material, the beam spot diameter on the exposed surface of 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. It is also preferable that the exposure in the present invention is performed using a laser scanning exposure device that emits a scanning laser beam that 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.

For the vertical multiplication, a method such as combining, using return light, or superimposing a high frequency is preferable.
Note that 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. The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature after exposure. The development temperature is 80 ° C or more and 20
0 ° C. or lower is preferable, and 100 ° C. or higher is more preferable.
50 ° C. or less. When the developing temperature is 80 ° C. or higher, it is possible to obtain a sufficient image density in a short time. Is preferred. The photothermographic material according to the invention generates a silver image by an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent when heated. This reaction process can proceed without external supply of a processing liquid such as water. Further, the development time is preferably from 5 seconds to 20 seconds, and more preferably from 10 seconds to 18 seconds. The above-mentioned development temperature is preferably the temperature of the photothermographic material. However, if the temperature cannot be directly measured, the temperature of the place where thermal development is performed may be considered as this temperature.

As the support, known materials used as the support can be used. For example, as a plastic film, polyethylene terephthalate,
Polyethylene naphthalate, polyimide, polyamide,
Examples thereof include polycarbonate, polysulfone, polyphenylene oxide, and cellulose esters. Particularly, polyethylene terephthalate and polyethylene naphthalate are preferred. In order to improve the adhesiveness between the plastic film and the coating layer, it is preferable to apply an easy adhesion treatment or an undercoating layer to the coating surface. The easy adhesion treatment includes corona discharge treatment, flame treatment, plasma treatment,
UV irradiation treatment and the like can be mentioned. Examples of the undercoat layer include layers containing gelatin and latex.
Further, a water penetration preventing layer such as vinylidene chloride may be provided as an undercoat layer. Further, as the composite support, the above materials may be appropriately bonded and used.

When a plastic film support is used, it is preferred that the support be annealed under low tension in order to improve dimensional characteristics. For example, Japanese Patent Publication No. 60-21616, U.S. Pat.
9,684, RD19809, JP-A-8-21154
No. 7, No. 10-10676, No. 10-10677,
No. 11-47676, No. 11-65025, No. 11
138628, 11-138648, 11-
No. 221892, No. 11-333922, No. 11-3
It is preferable to appropriately combine known methods described in 33923 and the like.

[0108] During the heat treatment of the support, preferably tension during subbing layer coating 0.4~80N / cm ^2, more preferably 2~60N / cm ^2, more preferably 10 to 50 N / cm ^2.

[0109]

The present invention will be described below with reference to examples, but embodiments of the present invention are not limited to these examples.
Unless otherwise specified, “%” in Examples is “% by mass”.
Is shown. The “mol / L concentration” is represented by “M”.

Example 1 << Preparation of Photosensitive Silver Halide Emulsion 1 >> A1 Phenylcarbamoyl gelatin (average molecular weight 100,000) 88.3 g Compound (A) (10% methanol solution) 10 ml Potassium bromide 0.32 g 5429 ml with water B1 0.67N silver nitrate aqueous solution 2635ml C1 Potassium bromide 51.55g Potassium iodide 1.47g Finish with water 660ml D1 Potassium bromide 154.9g Potassium iodide 4.41g Iridium chloride (1% solution) 0.93ml E1 0.4N Potassium bromide aqueous solution The following silver potential control amount F1 56% acetic acid aqueous solution 16.0 ml G1 1.72 g of anhydrous sodium carbonate Finished to 151 ml with water Compound (A): HO (CH ₂ CH ₂ O) n- [CH _{(CH 3) CH 2 O]} 17 - (CH 2 CH 2 O) mH m + n = 7-B Nos. 58-58288, solution to a solution (A1) with a mixing and stirring machine shown in Nos. 58-58289 (B1)
Of the solution (C1) at 45 ° C. and pAg8.
While controlling to 09, addition was performed by a simultaneous mixing method over a period of 4 minutes and 45 seconds to form nuclei.

After a lapse of 7 minutes, the remainder of the solution (B1) and the entire amount of the solution (D1) were added over 14 minutes and 15 seconds by a double jet method while controlling the temperature at 45 ° C. and the pAg at 8.09. During the mixing, the pH of the reaction solution was 5.6.

After stirring for 5 minutes, the temperature was lowered to 40 ° C., the whole amount of the solution (F1) was added, and the silver halide emulsion was precipitated. The supernatant was removed, leaving 2000 ml of sedimentation,
After adding 10 L of water and stirring, the silver halide was precipitated again. The supernatant was removed, leaving 1500 ml of the sedimented portion, and 10 L of water was further added. After stirring, the silver halide was sedimented. After removing the supernatant liquid leaving 1500 ml of the sedimented portion, the solution (G1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and water was added so as to be 1161 g per mole of silver.

This emulsion has an average grain size equivalent to a circle of 0.1.
Cubic silver iodobromide grains having a grain size variation coefficient of 074 μm, a grain size variation coefficient of 12% and a [100] face ratio of 92% were obtained. << Preparation of Photosensitive Silver Halide Emulsion 2 >> A photosensitive silver halide emulsion 2 was obtained in the same manner as in the above-mentioned photosensitive silver halide emulsion 1 except that the liquid temperature was 39 ° C.

This emulsion had an average grain size of 0.0
Cubic silver iodobromide grains having a particle size of 62 μm, a coefficient of variation in grain size of 12%, and a [100] face ratio of 93% were obtained. << Preparation of photosensitive silver halide emulsion 3 >> A photosensitive silver halide emulsion 3 was obtained in the same manner as in the photosensitive silver halide emulsion 1 except that the liquid temperature was 30 ° C.

This emulsion had an average grain size of 0.0
Cubic silver iodobromide grains having a grain size of 50 μm, a coefficient of variation in grain size of 15%, and a [100] face ratio of 93% were obtained. << Preparation of Powdered Organic Silver Salt 1 >> 130.8 g of behenic acid, 67.7 g of arachidic acid, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Then, a 1.5 M aqueous sodium hydroxide solution 540.2
After adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the above fatty acid sodium solution at 55 ° C., 43.0 g of the above-mentioned photosensitive silver halide emulsion 1 and 450 ml of pure water were added, and the mixture was stirred for 5 minutes.

Next, 702.6 ml of a 1 M silver nitrate solution was added to 2
And the mixture was stirred for 10 minutes to obtain an organic silver salt particle dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing vessel, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and draining are repeated until the conductivity of the waste water becomes 2 μS / cm, and the drainage is performed. Powdered organic silver salt 1 was obtained.

The number of moles of the photosensitive silver halide is represented by A [mol],
When the average particle volume is V [μm] and the number of moles of the non-photosensitive organic silver salt is B [mol], the value of (A / B) / V may be determined from the photosensitive material, but is substantially The equivalent value at the time of adjusting the photosensitive material was 245. The same applies hereinafter. << Preparation of Powdered Organic Silver Salt 2 >> Powdered organic silver salt 2 was prepared in the same manner as in powdered organic silver salt 1 except that 43.0 g of photosensitive silver halide emulsion 2 was added instead of photosensitive silver halide emulsion 1.
Was prepared. The value of (A / B) / V was 424. << Preparation of Powdered Organic Silver Salt 3 >> Powdered organic silver salt 3 was prepared in the same manner as in powdered organic silver salt 1, except that 43.0 g of photosensitive silver halide emulsion 3 was added instead of photosensitive silver halide emulsion 1.
Was prepared. The value of (A / B) / V was 825. << Preparation of Powdered Organic Silver Salt 4 >> 123.2 g of behenic acid, 64.1 g of arachidic acid, 41.3 g of stearic acid and 2.2 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Then, a 1.5 M aqueous sodium hydroxide solution 540.2
After adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the above fatty acid sodium solution at 55 ° C., 86.0 g of the above-mentioned photosensitive silver halide emulsion 1 and 450 ml of pure water were added and stirred for 5 minutes.

Next, 665.6 ml of a 1 M silver nitrate solution was added to 2 parts.
And the mixture was stirred for 10 minutes to obtain an organic silver salt particle dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts.
After that, washing with deionized water and draining are repeated until the conductivity of the wastewater becomes 2 μS / cm, and after centrifugal dehydration, drying is performed at 40 ° C. with a hot-air circulating dryer until there is no weight loss. Powder organic silver salt 4 was obtained. (A / B) / V
Was 513. << Preparation of Powdered Organic Silver Salt 5 >> 109.5 g of behenic acid, 57.0 g of arachidic acid, 36.7 g of stearic acid and 1.9 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Then, a 1.5 M aqueous sodium hydroxide solution 540.2
After adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the above fatty acid sodium solution at 55 ° C., 181.2 g
Of the above photosensitive silver halide emulsion 1 and 450 ml of pure water were added and stirred for 5 minutes.

Next, 591.7 ml of a 1 M silver nitrate solution was added to 2
And the mixture was stirred for 10 minutes to obtain an organic silver salt particle dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts.
After that, washing with deionized water and draining are repeated until the conductivity of the wastewater becomes 2 μS / cm, and after centrifugal dehydration, drying is performed at 40 ° C. with a hot-air circulating dryer until there is no weight loss. Powder organic silver salt 5 was obtained. (A / B) / V
Was 1220. << Preparation of Powdered Organic Silver Salt 6 >> 103.3 g of behenic acid, 53.4 g of arachidic acid, 34.4 g of stearic acid and 1.8 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Then, a 1.5 M aqueous sodium hydroxide solution 540.2
After adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. 227.0 g while maintaining the temperature of the above fatty acid sodium solution at 55 ° C.
Of the above photosensitive silver halide emulsion 1 and 450 ml of pure water were added and stirred for 5 minutes.

Next, 554.7 ml of a 1M silver nitrate solution was added to 2 parts.
And the mixture was stirred for 10 minutes to obtain an organic silver salt particle dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts.
After that, washing with deionized water and drainage are repeated until the conductivity of the wastewater becomes 2 μS / cm, centrifugal dehydration is performed, and then drying is performed at 40 ° C. using a hot-air circulating drier until the weight does not decrease. Powder organic silver salt 6 was obtained. (A / B) / V
Was 1668. << Preparation of Preliminary Dispersion >> 14.57 g of polyvinyl butyral powder (Eslec BL-5, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 1457 g of methyl ethyl ketone, and VMA-GETZ was dissolved.
Mannmann dissolver DISPERMAT CA-4
Preliminary dispersion liquid 1 was prepared by gradually adding 1,500 g of a powdered organic silver salt while stirring with a 0M type and thoroughly mixing.

With respect to powdered organic silver salts 2 to 6, preliminary dispersions 2 to 6 were prepared in the same manner. << Preparation of Photosensitive Emulsion Dispersion >> Preliminary dispersion liquid 1 was pumped with a pump so that the residence time in a mill was 10 minutes.
Media type disperser DISPERMAT filled with zirconia beads with a diameter of 80 m (Toray Torayceram) with an internal volume of 80%
The emulsion was supplied to SL-C12EX model (manufactured by VMA-GETZMANN) and dispersed at a mill peripheral speed of 13 m / s to prepare a photosensitive emulsion dispersion liquid 1.

With respect to the preliminary dispersions 2 to 6, photosensitive emulsion dispersions 2 to 6 were prepared in the same manner. << Preparation of Stabilizer Liquid >> 1.0 g of Stabilizer 1 and 0.31 g of potassium acetate were dissolved in 4.97 g of methanol to prepare a stabilizer liquid. << Preparation of Infrared Sensitizing Dye Liquid 1 >> 45.3 mg of the infrared sensitizing dye 1 and 14.3 g of the stabilizer 2 were dissolved in 117.5 g of MEK in a dark place to prepare the infrared sensitizing dye liquid 1. Prepared. << Preparation of Infrared Sensitizing Dye Liquid 2 >>
An infrared sensitizing dye liquid 2 was prepared in the same manner as the infrared sensitizing dye liquid 1 except that the amount was changed to mg. << Preparation of Infrared Sensitizing Dye 3 >>
Infrared sensitizing dye liquid 3 was prepared in the same manner as in infrared sensitizing dye liquid 1 except that the amount was changed to g. << Preparation of Supersensitizer Solution >> 50.1 mg of supersensitizer 1 was dissolved in 8.8 g of methanol to prepare a supersensitizer solution. << Preparation of additive liquid a >> 27.98 g of reducing agent A-3, 1.
54 g of 4-methylphthalic acid, 0.48 g of infrared dye 1
Was dissolved in 110 g of MEK to obtain an additive liquid a. << Preparation of additive liquid b >> 3.56 g of antifoggant 2,3.
43 g of phthalazine was dissolved in 40.9 g of MEK to prepare an additive solution b. << Preparation of Photosensitive Layer Coating Solution 1 >> Under an inert gas atmosphere (nitrogen 9
7%), the above-mentioned photosensitive emulsion dispersion liquid 1 (50 g) and 15.11 g of MEK were kept at 25 ° C. while stirring, and 390 μm of antifoggant 1 (10% methanol solution) was added.
was added and stirred for 1 hour. In addition, calcium bromide (1
(0% methanol solution) (494 μl) was added and stirred for 20 minutes. Subsequently, 167 ml of a stabilizer solution was added and stirred for 10 minutes, and then 3.95 g of the infrared sensitizing dye solution 1 was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 25 minutes. While keeping the temperature at 13 ° C, 0.7
After adding 0 g of the supersensitizer solution and stirring for 5 minutes, polyvinyl butyral (Eslec BL manufactured by Sekisui Chemical Co., Ltd.)
-5) After adding 13.31 g and stirring for 30 minutes, tetrachlorophthalic acid (9.4 mass% MEK solution) 1.08
4 g was added and stirred for 15 minutes. While further stirring, 12.43 g of additive solution a, 1.6 ml of Desm
OdurN3300 / Mobay's aliphatic isocyanate (10% MEK solution), 4.27 g of additive solution b was sequentially added and stirred to obtain photosensitive layer coating solution 1. << Preparation of Coating Solutions 2 to 29 for Photosensitive Layer >> Except for changing the addition amounts of the photosensitive emulsion dispersion, the infrared sensitizing dye solution and the supersensitizer solution as shown in Table 1a (Table 1), In the same manner as in coating liquid 1, photosensitive layer coating liquids 2 to 29 were obtained. << Preparation of Matt Agent Dispersion >> Cellulose Acetate Butyrate (Eastman Chemical Company, 7.5 g)
CAB171-15) was dissolved in 42.5 g of MEK,
Among them, calcium carbonate (Specialty M
internals, Super-Pflex200) 5
g, and 8000 r was added with a dissolver-type homogenizer.
The dispersion was performed at pm for 30 minutes to prepare a matting agent dispersion. << Preparation of Coating Solution for Surface Protective Layer >> While stirring 865 g of MEK (methyl ethyl ketone), cellulose acetate butyrate (Eastman Chemical Company, CA)
B171-15): 96 g, polymethylmethacrylic acid (Rohm & Haas Co., Paraloid A-21): 4.5
g, vinyl sulfone compound (HD-1): 1.5 g, benzotriazole: 1.0 g, F-based activator (Asahi Glass Co., Ltd.
Surflon KH40): 1.0 g was added and dissolved.
Next, 30 g of a matting agent dispersion was added and stirred to prepare a coating solution for the surface protective layer.

[0123]

Embedded image

<< Coating >> The viscosity of the coating solution for the photosensitive layer and the coating solution for the surface protective layer was adjusted to 0.228 Pa · s and 0.184 Pa · s by adjusting the amount of the solvent. After filtration, the mixture was discharged from a slit of an extrusion die coater, laminated, and simultaneously coated on a support. Eight seconds later, drying was performed for 5 minutes using hot air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C., and then an ambient temperature and humidity were 23 ° C., 50% RH, and a tension of 196 N / m.
(20 kg / m) to form a photothermographic material. The coated silver amount of the photosensitive layer of the obtained photosensitive material was 1.9 g / m ² , and the surface protective layer had a dry film thickness of 2.5 g / m ² .
μm. << Sensitometry >> The coated sample is 3.5 cm × 1
After cutting to 5 cm and exposing with a laser sensitometer equipped with a 810 nm diode, the photographic material was processed (heat developed) at 120 ° C. for 15 seconds, and the obtained image was evaluated with a densitometer. The measurement results were as follows: fog, sensitivity (1.
0, the reciprocal of the ratio of the amount of exposure that gives a high density) and Dmax. Table 1b (Table 2) shows relative sensitivities with the sensitivity of 1 as 100. << Image Preservation >> Two samples treated in the same manner as in the sensitometric evaluation were stored at 25 ° C. and 55% for 7 days while being shielded from light, and the other was exposed to natural light at 25 ° C. and 55% for 7 days. After that, the density of both fog portions was measured. Table 1 shows the results.
b.

The image storability was evaluated by increasing fog (Δfog) = (fog when exposed to natural light) − (fog when preserved from light). << Silver Tone >> For evaluation of silver tone, the density after development was 1.
A sample exposed and developed to 1 ± 0.05 was prepared. This sample was subjected to color temperature of 7700 Kelvin and illuminance of 1160
Irradiation was performed for 10 hours, 100 hours, and 1000 hours using a light source of 0 lux, and the color tone of silver was evaluated based on the following criteria. The number of ranks that has no problem in quality assurance is 4 or more. Evaluation Criteria 5: Pure black tone and no yellowishness 4: Not pure black but almost no yellowishness 3: Partially slightly yellowish 2: Partial yellowishness 1 : At first glance, yellowish color is felt. Table 1b shows the results.

[0126]

[Table 1]

[0127]

[Table 2]

Example 2 A part of the photosensitive material prepared as described above (see Table 2a (Table 3)) was exposed by laser scanning with an exposing machine using a semiconductor laser having a wavelength of 810 nm as an exposure source from the emulsion side. Given to photosensitive material. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam.
(Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.) The results are shown in Table 2b (Table 4).

[Table 3]

[0129]

[Table 4]

Example 3 From the emulsion side of the photosensitive material prepared as described above (see Table 3a (Table 5)), a wavelength of 800 nm
Exposure was performed by laser scanning with an exposure machine using a semiconductor laser in a vertical multi-mode of up to 820 nm as an exposure source. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam. (Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.) The results are shown in Table 3b (Table 6).

[Table 5]

[0131]

[Table 6]

Example 4 A portion of the light-sensitive material prepared as described above was exposed to light in the same manner as in Example 1, and processed (developed) for 15 seconds while changing the developing temperature as shown in Table-4. evaluated. The sample of the present invention showed little change in sensitometry in the developing temperature range of 80 ° C. to 200 ° C., but the samples other than the present invention showed a large decrease in sensitivity and Dmax at low temperatures and a significant increase in fog at high temperatures. there were.

[0133]

According to the present invention, there is provided a photothermographic material, an image recording method and an image forming method which have high sensitivity, low fog, high covering power, and improved silver image storability and silver tone after development. Can be.

Claims (5)

[Claims] 1. A support comprising at least a layer containing a non-photosensitive organic silver salt, a photosensitive silver halide, a reducing agent capable of reducing silver ions by heat, a binder, a crosslinking agent and a sensitizing dye. The photothermographic material according to claim 1, wherein the photothermographic material satisfies the following conditions. Condition (1): When the number of moles of the photosensitive silver halide is A [mol], the average grain volume is V [μm ³ ], and the number of moles of the non-photosensitive organic silver salt is B [mol], Satisfies the following relationship. 250 ≦ (A / B) / V ≦ 1500 Condition (2): When the above (A / B) / V is C and the content of the sensitizing dye per mol of silver is D [mol], Satisfy the relationship. 4 × 10 ⁻³ × C + 5 ≦ D × 10 ⁵ ≦ 8 × 10 ⁻³ × C +
5 2. The photothermographic material according to claim 1, wherein at least one of the compounds represented by the following general formula (1) is used.
And the content of the compound per mole of silver
A photothermographic material characterized by satisfying the following relationship: 4 × 10 ⁻³ × C + 4 ≦ E × 10 ⁴ ≦ 8 × 10 ⁻³ × C +
4 (Wherein, H ₃₁ Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group, T ₃₁ represents a divalent linking group or a linking group comprising an aliphatic hydrocarbon group, and J ₃₁ represents an oxygen atom, a sulfur atom, Represents a divalent linking group or linking group containing at least one atom or nitrogen atom, wherein Ra, Rb, Rc and Rd are each a hydrogen atom,
Represents an acyl group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, or represents Ra and Rb, Rc and Rd, Ra and Rc
Alternatively, Rb and Rd can be bonded to form a nitrogen-containing heterocyclic group. M ₃₁ represents an ion necessary to neutralize the molecular charge, k ₃₁ represents the number of ions necessary for neutralizing the molecular charge. ) 3. The photothermographic material according to claim 1, which is exposed by a laser exposing machine in which an angle between an exposure surface of the photothermographic material and a scanning laser beam does not become substantially perpendicular. An image recording method for a photothermographic material, comprising: 4. The method for recording an image on a photothermographic material according to claim 3, wherein the exposure by the laser exposure device is an exposure by a laser beam scanning exposure device which is a vertical multi. 5. An image forming method, wherein the photothermographic material according to claim 1 is heat-developed at 80 ° C. or more and 200 ° C. or less.