JPH06332134A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To provide the heat developable color photosensitive material which fogs less, has a high sensitivity and is excellent in color sepn. without degrading its green preservable stability. CONSTITUTION:The photosensitive silver halide emulsions of the heat developable color photosensitive material having at least the photosensitive silver halide emulsions, binders and dyestuff donative compds. on a base have the peak of spectral sensitivity with >=700nm IR light and is spectrally sensitized by sensitizing dyestuff forming a J-band. The heat developable color photosensitive material has at least one layer of the layers contg. the photosensitive silver halide emulsions in which >=70% of the total surface area of the surface constituting the emulsion particles is (100) faces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material which has less fog, high sensitivity and excellent color separation.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art.
For example, pages 242 to 255 of "Basics of Photographic Engineering", Non-silver photography (edited by Corona Publishing Co., Ltd. in 1982), US Pat.
No. 00626 and the like.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is disclosed in US Pat. Nos. 3,761,270 and 4,021,240.
No. etc. Also, a method of forming a positive color image by a photosensitive silver dye bleaching method is disclosed in US Pat. No. 4,235.
957 and the like. Further, recently, a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element has been proposed. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. For details, see US Pat.
No. 483914, No. 4503137, No. 455929
No. 0, JP-A-58-149046 and JP-A-60-13.
3449, 59-218443, and 61.
No. 238056, European Patent Publication 220746A2
Issue, open technical report 87-6199, European Patent Publication 21066.
0A2 and the like.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is reduced by heat development in the presence of a reducing agent or a precursor thereof, depending on the exposure amount of silver halide. A method has been proposed in which the agent is oxidized and the diffusible dye is released by reduction with the reducing agent left unoxidized. Also, European Patent Publication 2207
No. 46A, Technical Report 87-6199 (Vol. 12, No. 22)
As a compound that releases a diffusible dye by a similar mechanism, a compound that releases a diffusible dye by reductive cleavage of an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) is used. A heat developable color light-sensitive material is described.

Conventional color light-sensitive materials are usually blue, green,
The color CRT (cathode ray tube) has red spectral sensitization, and in order to obtain an image by using image information once converted into an electric signal in such a color light-sensitive material.
Is generally used as an exposure light source, but a CRT has a problem that it is not suitable for obtaining a large size print.

Further, as a writing head capable of obtaining a large size print, a light emitting diode (LED) is used.
Semiconductor lasers (LD) have been developed, but none of these optical writing heads that efficiently emit blue light have been developed. So, for example, when using LEDs, near infrared (800 nm), red (670 nm)
It is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red and yellow by a light source combining three LEDs of yellow and yellow (570 nm). A recording system is described in "Nikkei New Material", September 14, 1987, pages 47 to 57, and is partially put into practical use.

Also, 880 nm, 820 nm and 760 nm
JP-A-61-137149 discloses a system for recording on a color light-sensitive material having three light-sensitive layers each having a spectral sensitivity at each wavelength with a light source in which three LDs exhibiting the above-mentioned light emission are combined.
It is described in Japanese Patent Publication No. Generally, in a multi-layer color light-sensitive material, when each color of yellow, magenta, and cyan is exposed to three different spectral regions to develop colors, the respective colors are not mixed,
Color development is an important technique for color reproduction. In particular, when using LEDs or LDs as an exposure light source, it is unavoidable to design three spectral sensitivities in a narrow spectral range (red end or infrared region), and how the spectral sensitivities of each are exceeded. The key to improving color separation is to reduce wrap.

In order to ensure color separation, US Pat.
No. 6119892 proposes to increase each spectral sensitivity of a light-sensitive material having three spectral sensitivities as the wavelength becomes shorter and to add a filter dye to an intermediate layer. However, increasing the spectral sensitivity as the wavelength becomes shorter,
There is a drawback that it causes an increase in fog and deteriorates the stability over time, and in infrared sensitization, it is difficult to achieve high sensitivity due to desensitization due to addition of a dye and low color sensitization efficiency. there were.

In order to solve these drawbacks, Japanese Patent Application Laid-Open No. Hei 4
JP-A-146431 and JP-A-5-45828 use a J-band type infrared sensitizing dye having a sharp spectral sensitivity to reduce fog, high sensitivity, excellent color separation, and raw color. We have proposed a color light-sensitive material with good storage stability.

[0010]

However, in this color light-sensitive material, the J-band type sensitizing dye has a large change in absorption due to J-band formation depending on the shape of the silver halide grains to be adsorbed. However, since the sensitivity greatly changes, there is no heat-developable color light-sensitive material with high fog, high sensitivity and excellent color separation without deteriorating the raw storage stability, and its development is desired. Was there.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable color light-sensitive material which is free from fog, has less fog, has high sensitivity and is excellent in color separation.

[0012]

The present inventor has conducted extensive studies in order to achieve the object of the present invention. As a result, the J-band is effectively formed especially on the (100) plane of silver halide grains. On the basis of such findings,
In a heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound, the light-sensitive silver halide emulsion has a spectral sensitivity peak to infrared light of 700 nm or more, and J −
It is spectrally sensitized by a band-forming sensitizing dye, and is 7% of the total surface area of the faces constituting the emulsion grains.
The above object of the present invention was achieved by a heat-developable color light-sensitive material characterized by having at least one layer containing a photosensitive silver halide emulsion in which 0% or more is (100) plane.

In a preferred embodiment of the present invention, the photosensitive silver halide grains have an average grain size of 0.3.
It is a cube of μm or less, and the ratio of the number of moles of halide ions and silver ions at the time of forming the emulsion grains is in the range of 90: 100 to 110: 100.
In the present invention, at least one silver halide emulsion contained in the photosensitive silver halide emulsion layer having a peak of spectral sensitivity to infrared light of 700 nm or more is spectrally dispersed by a sensitizing dye forming a J-band. Sensitized, and 70% or more of the total surface area of the surface constituting the emulsion grains need only be (100) surface, and the heat-developable color light-sensitive material can be spectrally analyzed for infrared light of 700 nm or more. When a plurality of light-sensitive silver halide emulsion layers having a peak of sensitivity are provided, the light-sensitive silver halide emulsions contained in all the light-sensitive silver halide emulsion layers form a J-band. It is spectrally sensitized with a sensitizing dye, and 70% or more of the total surface area of the surface constituting the emulsion grains is (1
(00) face is not always necessary, and at least one layer thereof, preferably a silver halide contained in a photosensitive silver halide emulsion layer having a peak of spectral sensitivity to infrared light of 700 to 780 nm. The emulsion is spectrally sensitized by a sensitizing dye forming a J-band, and 70% or more of the total surface area of the faces constituting the emulsion grains is (1
00) is enough.

The heat-developable color light-sensitive material according to the present invention comprises
Basically, it has a photosensitive silver halide, a binder, a dye-donating compound (which may also serve as a reducing agent as described later), etc. on the support, and further, if necessary, An organic metal salt oxidizing agent and the like can be included. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, the presence of a colored dye-donating compound in the lower layer of the silver halide emulsion can prevent a decrease in sensitivity. The reducing agent is preferably incorporated in the heat-developable color light-sensitive material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later. However, by incorporating a reducing agent in the light-sensitive material, an effect of accelerating color image formation can be obtained.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having different spectral regions are used in combination. To use. For example, a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer, or a combination of a red-sensitive layer, a first infrared layer and a second infrared layer. There are combinations etc. Each of the light-sensitive layers can take various arrangement orders known in a normal type color light-sensitive material. Further, each of these photosensitive layers,
You may divide | segment into 2 or more layers as needed. The kind of the dye-donor compound (yellow, magenta, cyan) combined with each of these photosensitive layers is arbitrary when reproducing a color image from image information converted into an electric signal as in the present invention. There are no restrictions like ordinary color light-sensitive materials.

The photothermographic material according to the present invention may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. The silver halide used in the heat-developable color light-sensitive material of the present invention will be described below.

In the present invention, any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride, and silver chloroiodobromide can be used as the silver halide having a spectral sensitivity of 700 nm or more. However, silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing 30 mol% or less of silver iodide are preferable. In the present invention, 7 out of the total surface area of the faces constituting the emulsion grains of the silver halide emulsion having a spectral sensitivity of 700 nm or more.
0% or more is the (100) plane. This is because the J-band formation of the J-band type sensitizing dye is particularly remarkable on the (100) plane. On a (111) plane other than the (100) plane, the J-band type sensitizing dye adsorbs to silver halide grains, but forms an absorption band (M-band etc.) other than the J-band, as a result,
It is not preferable because it causes broadening of the absorption peak and desensitization associated therewith.

In the present invention, the higher the (100) face ratio, the easier the J-band is formed. Therefore, a silver halide emulsion having a spectral sensitivity of 700 nm or more has a cubic grain shape. It is preferable. In the present invention, the silver halide emulsion having a spectral sensitivity of 700 nm or more preferably has an average grain size of 0.3 μm or less. In particular, it is preferable to have an average particle size in the range of 0.10 to 0.25 μm. If the average particle size is 0.3 μm or more, fogging may occur, which is not preferable. On the other hand, when the average grain size is 0.3 μm or less, the grains are likely to dissolve during or after the formation of the silver halide grains, and as a result, the cubic shape of the silver halide grains becomes apparently round, The ratio of the (100) plane may easily decrease. As a method for preventing this, it has been proved effective to set the ratio of the number of moles of halide ions to silver ions at the time of grain formation to 90: 100 to 110: 100. If the ratio of halide ions is higher than this ratio, dissolution of silver halide grains is likely to occur, and conversely, if the ratio of halide ions is low, cubic silver halide grains tend to be difficult to form. . Any of these may lead to a reduction in the ratio of the (100) plane effective for J-band formation, which is not preferable.

The ratio of (100) faces of emulsion grains can be determined as follows. Specific emulsions ((100) and (11)
1) on the surface, when a J-band is adsorbed, a dye exhibiting spectral absorption with different peak wavelengths) is added, and the diffuse infinite reflectance at each absorption peak is obtained by conversion using the Kubelka-Munk equation, Further, it is plotted against the dye addition amount to obtain the saturated adsorption amount on each surface. Using this value, the ratio of the (100) plane and the ratio of the (111) plane can be obtained. For more information, see Journal of
Imaging Science 29: 165-171 (1985).

In the present invention, the silver halide emulsion having a spectral sensitivity of 700 nm or more may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, so-called multi-structured particles having different halogen compositions inside and inside the particle may be used. Of the multi-structure grains, those having a double structure may be referred to as a core-shell emulsion. In the present invention, the silver halide emulsion having a spectral sensitivity of 700 nm or more is preferably a multi-structured grain, more preferably a core-shell emulsion. However, the silver halide emulsion of the present invention is not limited to this.

In the present invention, the silver halide emulsion having a spectral sensitivity of 700 nm or more is preferably a monodisperse emulsion, and the coefficient of variation described in JP-A-3-110555 is preferably 20% or less. . It is more preferably 16% or less, and further preferably 10% or less. However, the present invention is not limited to monodisperse emulsions.

In the present invention, it is also possible to use a silver halide emulsion other than the above in a mixture with the silver halide emulsion having a spectral sensitivity of 700 nm or more in the same layer or in a separate layer. These silver halide emulsions may be octahedral other than cubic, tabular with a high aspect ratio, potato-shaped, or any other shape. The particle size may also be 0.3 μm or more. Specifically, US Pat. No. 4,500,626, column 50, and US Pat. No. 4,628,021.
No., Research Disclosure (RD) 17029 (1978), JP-A-62-251.
Any of the silver halide emulsions described in JP-A-59 can be used.

In the process of preparing the silver halide emulsion of the present invention, when so-called desalting for removing excess salt is carried out, a known method of washing with Nudell by gelling gelatin is used as a means therefor. However, it is also possible to use inorganic salts composed of polyanions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acyl). The precipitation method (flocculation) using a modified gelatin, an aromatic carbamoylated gelatin, etc. may be used. It is preferable to use a sedimentation method using a sedimentation agent (a) or a sedimentation agent (b) represented by the following formula, particularly a compound represented by the sedimentation agent (b). It is not limited to the case where desalting is performed by using. Further, desalting may be performed by an ultrafiltration method without using a sedimentation agent. It is not always necessary to remove excess salt.

[0024]

[Chemical 1] The silver halide emulsion according to the present invention has various purposes.
Heavy metals such as iridium, rhodium, platinum, cadmium, zinc, taryuyu, lead, iron and chromium may be contained. These compounds may be used alone, or
You may use it in combination of 2 or more type. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. Further, when it is contained, it may be contained uniformly in the particles, or may be contained by being localized on the surface or inside of the particles.

In the present invention, when iridium is contained in the silver halide emulsion, the preferable addition amount of iridium is 10 ^-9 to 10 ^-4 mol, and more preferably 10 ^-8 to 10 mol per mol of silver halide. ^-6 mol. In the case of core-shell emulsion,
Iridium may be added. As the iridium compound, K ₂ IrCl ₆ or K ₃ IrCl ₆ is preferably used.

In the present invention, when rhodium is contained in the silver halide emulsion, the preferable addition amount of rhodium is 10 ^-9 to 10 ^-6 mol per mol of silver halide. Further, in the present invention, when iron is contained in the silver halide emulsion, the preferable addition amount of iron is 10 ⁻⁷ to 10 ⁻³ mol, and more preferably 10 ⁻⁶ to 10 ⁻ , per mol of silver halide. ³ mol.

In the present invention, when a heavy metal is contained in a silver halide emulsion, some or all of these heavy metals are fine particles such as silver chloride, silver chlorobromide, silver bromide and silver iodobromide. By pre-doping the emulsion, and then adding this fine grain emulsion to the surface of the silver halide emulsion,
A method of locally doping is also preferably used. In the present invention, in the step of forming silver halide grains,
As a silver halide solvent, a rhodan salt, NH _3, and a tetra-substituted thioether compound represented by a compound represented by the following formula, an organic thioether derivative described in JP-B-47-11386, or JP-A-53-144319. The sulfur-containing compounds described in 1) and the like can be used.

[0028]

[Chemical 2] In the present invention, in the step of forming silver halide grains, JP-B-46-7781 and JP-A-60-222.
Nitrogen-containing compounds such as those described in JP 842, JP-A 60-122935 and the like can be added. In the present invention, it is advantageous to use gelatin as the binder of the protective colloid and other hydrophilic colloids used in the preparation of the silver halide emulsion, but other hydrophilic colloids can also be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, A wide variety of synthetic hydrophilic polymeric substances such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin that can be used in the present invention include lime-processed gelatin, acid-processed gelatin, britain, society of the scientific,
Photography of Japan (Bull. Soc. Sci. Ph
ot., Japan), No. 16: Page 16 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

For other conditions for producing silver halide emulsions, see P. Glafkides.
Author, "Chemie et Physique Photographique" [Paul Montel, published by Paul Montel, 1967], GF
GF Duffin, “Photographic Emulsion
Chemistry) "(The Focal Pr
Published by ess, 1966), VL Zelikman et al, "Making and
Coating Photographic Emulsion (Maki
and Coating Photographic Emulsion) "(The Focal Press, published by The Focal Press, 1964)
See the description such as. That is, any of the acidic method, the neutral method, and the ammonia method may be used, and as the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. .

In the present invention, a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Further, in the present invention, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (Japanese Patent Laid-Open No. Sho 5).
No. 5-142329, No. 55-158124, US Pat. No. 3,650,757, etc.).

In the present invention, the surface of the silver halide grain may be replaced with a halogen which forms a hardly soluble silver halide grain during or after grain formation. Further, in the present invention, any known stirring method may be used as the stirring method for the reaction liquid. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily. The preferred pH range is 2.2 to 6.0, more preferably 3.0 to 5.5.

The silver halide emulsion used in the present invention is
It may be spectrally sensitized with methine dyes and other sensitizing dyes. Sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-60-140335,
The sensitizing dyes described in RD17029 (1978) pages 12 to 13 and the like can be mentioned.

As a sensitizing dye which gives a peak of spectral sensitivity to infrared light of 700 nm or more and which forms a J-band used in the present invention, European Patent Publication No. 50 is used.
No. 2508, No. 452853, JP-A-5-45828.
The heptamethine cyanine dyes (especially, those having a benzothiazole nucleus or a naphthothiazole nucleus) disclosed in Japanese Patent Publication No. JP-A No. 1993-242242 can be preferably used.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization. Along with a sensitizing dye, a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, US Pat.
615641, compounds described in JP-A-63-23145, etc.) may be included in the emulsion.

In the present invention, in any of the above addition methods, the total addition amount of the sensitizing dye may be added at once, or may be added in several divided portions. Further, the sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or a halide. The sensitizing dye may be added after being dissolved in an organic solvent or water (which may be alkaline or acidic) having compatibility with water, such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide, and acetone. However, two or more of these may be used in combination. It may also be added in the form of dispersion in a water / gelatin dispersion system or in the form of freeze-dried powder. Further, a surfactant may be used and added in the form of dispersed powder or solution.

The sensitizing dye used in the silver halide emulsion used in the present invention is, for example, JP-A-3-29674.
The sensitizing dyes described in JP-A No. 5 and JP-A No. 4-31854, and the like may be used. In the present invention, the amount of the sensitizing dye used is 100 g of silver used for producing a silver halide emulsion.
Therefore, 0.001 g to 20 g is suitable, and 0.01 to 2 g is preferable.

In addition, the following compounds may be included in the present invention. This compound is often used for supersensitization, improvement of storage stability, and suppression of change in sensitivity of coating solution with time. The heat-developable color light-sensitive material of the present invention has more effective effects.

[0039]

[Chemical 3] In the above formula, A represents a divalent aromatic residue. R ₁₁ , R
₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, a hydroxy group,
Alkyl group, alkoxy group, aryloxy group, halogen atom, heterocyclic nucleus, heterocyclylthio group, alkylthio group, arylthio group, amino group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or non-substituted It represents a substituted aralkylamino group, heterocyclylamino group, aryl group, heterocyclyloxy group, or mercapto group. However, A, R ₁₁ ,
At least one of R ₁₂ , R ₁₃ and R ₁₄ has a sulfo group.

W ₁ and W ₂ are each --CH = or-
Represents N =. However, at least _one of W ₁ and W ₂ represents -N =. The above compounds are known as supersensitizers for sensitizing dyes in general light-sensitive materials for wet development processing (US Pat. No. 2875058,
U.S. Pat. No. 3,695,888, JP-A-59-19224.
See Japanese Patent Publication No. 2 and 59-191032. ),
It is also a compound known as a supersensitizer in heat-developable color light-sensitive materials (see JP-A-59-180550).

Details and specific examples of the above compounds are described in JP-A-63-23145. In the present invention, the sensitizing dye may be added at any time basically. That is, at the beginning of silver halide emulsion grain formation (may be added before nucleation), during or after formation, or at the beginning, midway, or after the desalting step, during gelatin redispersion, chemical increase It may be before, after, during the feeling, or at the time of preparing the coating solution. Preferably, a sensitizing dye is added during and after the formation of silver halide grains, or before and after chemical sensitization. The addition after chemical sensitization means that the sensitizing dye is added after all the chemicals necessary for chemical sensitization are added.

In the present invention, US Pat.
No. 56, a sensitizing dye is present in a reaction system of a soluble silver salt (eg, silver nitrate) and a halide (eg, potassium bromide) prior to the formation of silver halide grains. U.S. Pat. No. 4,225,666
As described in the above publication, it may be present in the above reaction system after the nucleation of silver halide grains and before the completion of the silver halide grain formation step. Further, the sensitizing dye may be present in the reaction solution at the same time as the formation of silver halide grains, that is, at the same time when the soluble silver salt and the halide are mixed, and the emulsion thus prepared is contained. Photosensitive materials are excellent in storage stability and gradation under high temperature conditions.

In the present invention, the addition amount of the sensitizing dye is generally 10 ^-8 to 10 ^-2 per mol of silver halide.
It is about molar. The concentration of the sensitizing dye addition solution, the solvent, the addition time (either batch addition or addition over time), temperature, pH, etc. are not particularly limited. Also,
Both methods of addition on the liquid surface and addition in the liquid can be used. These conditions are described in detail in JP-A-3-110555.

The silver halide emulsion used in the present invention can be used without being chemically sensitized, but it is more preferable to chemically sensitize to increase the sensitivity. The chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or a combination thereof. In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium and tellurium, or chemical sensitization with a noble metal such as palladium and iridium may be combined with the chemical sensitization.

In the present invention, 4-hydroxy-6-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound represented by methyl- (1,3,3a, 7) -tetraazaindene is also preferably used. A preferred range of the amount of the inhibitor added is 10 ^-1 to 10 ^-5 mol per mol of silver halide. In the present invention, the pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 9.
It is 5.

Examples of the sulfur sensitizer used in the present invention include active gelatin and compounds containing sulfur capable of reacting with silver. Examples thereof include thiosulfur salts, allylthiocarbamide, thiourea, allylisothiocyanate, Cystine,
p-Toluenethiosulfonic acid, rhodan, mercapto compounds and the like are used. Others, US Pat. No. 1574
No. 944, No. 2410689, No. 2278947.
Nos. 2,728,668, 3,656,955 and the like can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ² or 10 g / m ² in terms of silver. The silver halide emulsion may be used as it is after ripening, but it is usually used after being chemically sensitized. In the emulsion for a conventional type light-sensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination in the present invention.
These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form such organic silver salt oxidizing agents include US Pat.
No. 26, columns 52 to 53 and the like include benzotriazoles, fatty acids and other compounds. In addition, JP-A-60-
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP113235, and silver acetylene described in JP-A-61-249044 are also useful.

Two or more kinds of organic silver salt oxidizing agents may be used in combination, and 0.01 to 10 moles, preferably 0.01 to 1 mole, may be used per mole of photosensitive silver halide. it can. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver. Various antifoggants or photographic stabilizers can be used in the present invention. An example is R
D17643 (1978) pages 24 to 25, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442,
Alternatively, mercapto compounds and their metal salts described in JP-A-59-111636, JP-A-62-879.
The acetylene compounds described in JP-A-57 are used.

As the reducing agent used in the present invention, a reducing agent known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described below can also be used (in this case, other reducing agents can be used in combination). Also, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A No. 60-140335, pages 17-18, No. 57-40245, and No. 56.
No. 138736, No. 59-178458,
59-53831, 59-182449, 59-182450, 60-11955.
5 gazette, the same 60-128436 gazette, the same 60-12.
No. 8437, No. 60-128438, No. 60
-128439, 60-198540,
No. 60-181742, No. 61-259253, No. 62-244044, and No. 62-1312.
No. 53, No. 62-131254, No. 62-1
The reducing agents and reducing agent precursors described on pages 78 to 96 of Japanese Patent No. 31255, No. 62-131256, and European Patent No. 220,746A2 are cited.

In the present invention, US Pat.
As disclosed in No. 69, various reducing agents can be used in combination. In the present invention, when a diffusion resistant reducing agent is used, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide, an electron transfer agent and / Or a combination of electron transfer agent precursors can be used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or the precursor thereof has higher mobility than the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

As the diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent, among the reducing agents described above,
Any material that does not substantially move in the layer of the silver halide light-sensitive material may be used, and preferably hydroquinones, sulfonamide phenols, sulfonamide naphthols,
Examples thereof include compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later.

In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, and particularly preferably 0.1 to 10 mol, based on 1 mol of silver. In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or vice versa, that is, a dye-donating property A compound is included.

As an example of the dye-donating compound which can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of couplers and color developers for forming dyes with these couplers are given by TH James.
"The Theory of the Photographic Process" 4th Edition, pages 291-334 and 354-361, JP-A-58
-123533 gazette, the same 58-149046 gazette,
58-149047, 59-111148, 59-124399, 59-1748.
35, 59-231539, 59-2.
No. 31540, No. 60-2950, No. 60-
No. 2951, No. 60-14242, No. 60-
No. 23474, No. 60-66249, etc. are described in detail.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Here, Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. Corresponding to or opposite to the photosensitive silver salt having a latent image in (Dye-Y) n-Z causes a difference in diffusivity of the compound, or releases Dye,
Represents a group having a property of causing a difference in diffusivity between the released Dye and (Dye-Y) n-Z,
n represents 1 or 2, and when n is 2, two Dye-Y
May be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds (1) to (3). It should be noted that the following items (1) to (4) correspond to the development of silver halide and form a diffusible dye image (positive dye image). An image (negative dye image) is formed.

Compounds US Pat. Nos. 3,134,764, 33,628,3597,200, 3,454,545 and 34,829.
No. 72, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

Compounds As described in US Pat. No. 4,503,137, which releases a diffusible dye in an alkaline environment,
A non-diffusible compound that loses its ability when reacted with silver halide. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, etc., and intramolecular rewinding reaction of an isoxazolone ring described in US Pat. No. 4,199,354 etc. Examples include compounds that release diffusible dyes.

Compounds US Pat. No. 4,559,290, European Patent No. 220746
A2, US Pat. No. 4,783,396, Open Technical Report 87-
As described in 6199 etc., a non-diffusible compound which reacts with a reducing agent left unoxidized by development to release a diffusible dye. For example, US Pat. No. 41
39389, 4139379 and JP-A-59-18.
Compounds that release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,531 and US Pat. No. 42,321.
07, JP-A-59-101649 and JP-A 61-8.
8257, RD24025 (1984) and the like, compounds that release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 30085
88A, JP-A-56-142530, U.S. Pat. Nos. 4,343,893, 4619884, and the like, compounds which cleave a single bond to release a diffusible dye after reduction, U.S. Pat. No. 4,450,223. And nitro compounds that release a diffusible dye after electron acceptance as described in US Pat. No. 4,609,610 and the like, and compounds that release a diffusible dye after electron acceptance as described in US Pat. No. 4,609,610. In addition, as a more preferable compound, European Patent No. 2
No. 20746A2, JP-A-87-6199, US Pat. No. 4,783,396, JP-A-63-201653 and JP-A-63-201654, wherein an N—X bond (X is oxygen, sulfur) Or a compound having a nitrogen atom) and an electron-withdrawing group, JP-A-1-268.
No. 42, a compound having SO ₂ —X (X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A-63-
A compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in Japanese Patent No. 271344.
To have been in one molecule described in JP-63-271341 discloses C-X 'bond (X' is X as defined or or -SO ₂ - represents a)
And a compound having an electron-withdrawing group. In addition, compounds described in JP-A-1-161237 and JP-A-1-161342, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron-accepting group, should also be used. You can Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (3), (7) to (10), (12), (1) described in EP 220746A2 or US Pat. No. 4,783,396.
3), (15), (23) to (26), (31), (3
2), (35), (36), (40), (41), (4
4), (53) to (59), (64), (70), and compounds (11) to (2) described in JP-A-87-6199.
3) and the like are preferable.

Compound A non-diffusible compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and which releases a diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 13
30524, JP-B-48-39165, U.S. Pat. Nos. 3,434,940, 4,474,867, and 448.
And those described in No. 3914 and the like.

Compound A non-diffusible compound (DRR compound) that is reducible to a silver halide or an organic silver salt, and releases a diffusible dye when its partner is reduced. Since this type of compound does not require the use of another reducing agent, there is no problem of image contamination due to an oxidative decomposition product of the reducing agent, which is preferable. Typical examples thereof are US Pat. Nos. 3,928,312 and 4,053,312.
No. 4,055,428, No. 4,336,322, JP-A Nos. 59-65839, 59-69839,
53-3819, 51-104343, RD17465, U.S. Pat. No. 3725062,
No. 3,728,113, No. 3,434,939, JP-A-58.
-116537, 57-179840,
Examples thereof include those described in US Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. , (10) to (1
3), (16) to (19), (28) to (30), (3
3) to (35), (38) to (40), (42) to (6)
4) is preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and the general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
, April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617), and the like can also be used.

Hydrophobic additives such as a dye-donor compound and a diffusion resistant reducing agent can be incorporated into the layer of the silver halide light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-
83154, 59-178451, and 5
9-178452, 59-178453, 59-178454, 59-17845.
5, a high boiling point organic solvent as described in JP-A-59-178457 and the like, a boiling point of 50 ° C. to 1 as required.
It can be used in combination with an organic solvent having a low boiling point of 60 ° C. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. In addition, 1 cc or less for 1 g of binder, and further
0.5cc or less, especially 0.3cc or less is suitable.

In the present invention, Japanese Patent Publication No. 51-39853
The dispersion method using a polymer described in JP-A No. 51-59943 can also be used. In the present invention,
When a hydrophobic additive is used, fine particles can be dispersed and contained in a binder in addition to the above method.
When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants listed on pages 37 to 38 of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating the development and stabilizing the image at the same time can be used in the light-sensitive material. For specific compounds that are preferably used,
U.S. Pat. No. 4,500,626, columns 51-52. In the present invention, for the purpose of improving sharpness,
Non-diffusible filter dyes can be included. If necessary, a filter dye having absorption in the infrared region can be used. For details of such filter dyes, Japanese Patent Application No. 2-137885, Japanese Patent Application Laid-Open Nos. 4-217243, 4-276744,
It is described in Japanese Patent Laid-Open No. 5-45834.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be used in the form of being separately coated on a support separate from the light-sensitive material, or may be used in the form of being coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256, pages 32 to 41. Mordant, JP-A-62-24404
Examples thereof include those described in JP-A No. 3 and JP-A No. 62-244036. Also, US Pat.
A dye-receptive polymer compound as described in No. 079 may be used.

If necessary, the dye-fixing element may include a protective layer,
Auxiliary layers such as a peeling layer and a curl preventing layer can be provided. In particular, it is useful to provide a protective layer. In the present invention, hydrophilic binders are preferably used as the binder of the constituent layers of the silver halide light-sensitive material and the dye fixing element. Examples thereof include those described on pages 26 to 28 of JP-A No. 62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable,
For example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds are mentioned. To be Furthermore, superabsorbent polymers described in JP-A-62-245260 Publication, i.e. -COOM or -SO ₃ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal or a copolymer of these vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L manufactured by Sumitomo Chemical Co., Ltd. -5H) can also be used. These binders can be used in combination of two or more kinds.

When a system in which a small amount of water is supplied for thermal development is adopted, water can be absorbed quickly by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specific examples of the polymer latex include JP-A Nos. 62-245258 and 62-136.
Any of the polymer latices described in JP-B No. 648, JP-A No. 62-110066 and the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, curling is prevented. The effect is obtained.

In the present invention, a high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing element, as a plasticizer, a slipping agent, or as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. Specific examples thereof include pages 25 and 62-245 of JP-A-62-253159.
Examples thereof include those described in Japanese Patent No. 253. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. An example is "modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in Technical Document P6-18B, especially carboxy-modified silicone (trade name X-2
2-3710) is effective. In addition, JP-A-62-2
Silicone oils described in JP-A-15953 and JP-A-63-46449 are also effective.

In the present invention, an anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber or a metal complex of a certain kind. Examples of the antioxidant that can be used in the present invention include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
Further, the compounds described in JP-A-61-159644 can be effectively used.

As the ultraviolet absorber usable in the present invention, a benzotriazole compound (US Pat. No. 35
No. 33794, etc.), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (JP-A No. 46-2784 etc.), other JP-A Nos. 54-48535 and 62-136641. , No. 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 can also be effectively used.

As the metal complex usable in the present invention, US Pat. Nos. 4,241,155 and 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
JP-A-62-174741, JP-A-61-88256.
27-29, 63-199248,
The compounds described in JP-A-1-75568, JP-A-1-74272 and the like can be mentioned.

Examples of useful anti-fading agents in the present invention are described in JP-A No. 62-215272, pages 125 to 137. In the present invention, the anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or supplied to the dye-fixing element from the outside such as a light-sensitive material. You may do it.

In the present invention, the above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other. In the present invention, the light-sensitive material and the dye fixing element include
Optical brighteners may be used. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light-sensitive material. For example, K. Veenkatarama
n Volume "The Chemistry of Synthetic Dyes" Volume V Volume 8
Compounds described in Chapter, JP-A-61-143752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrarizone compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with the anti-fading agent.

In the present invention, the hardener used in the constituent layers of the light-sensitive material and the dye fixing element is described in US Pat. No. 4,678.
Column 41 of 739, JP-A-59-116655, JP-A-62-245261, and JP-A-61-18942.
Examples include hardeners described in Japanese Patent Publication No. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

In the present invention, in the constituent layers of the light-sensitive material and the dye-fixing element, a coating aid, a peeling property improving property, a slip property improving property,
Various surfactants can be used for the purpose of preventing static charge and promoting development. Specific examples of the surfactant are disclosed in JP-A-62-1
No. 1,734,463, No. 62-183457, etc. In the present invention, the constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As a typical example of the organic fluoro compound, Japanese Patent Publication No. 57-
Columns 8 to 17 of 9053, JP-A-61-2094.
No. 4, JP-A-62-135826, and the like, or a fluorine-containing surfactant such as a fluorine-based surfactant, an oil-like fluorine-containing compound such as a fluorine oil, or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Compounds.

In the present invention, a matting agent can be used in the light-sensitive material and the dye fixing element. As the matting agent, in addition to the compounds described on page 29 of JP-A-61-88256, such as silicon dioxide, polyolefin, or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63. The compounds described in JP-A-274944 and JP-A-63-274952 are mentioned. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness and preventing Newton's rings but also for the purpose of making the surface of the dye fixing element (image surface) non-glossy.

In the present invention, the constituent layers of the light-sensitive material and the dye-fixing element may further contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described on pages 26 to 32 of JP-A No. 61-88256. In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a photosensitizer. It has functions such as accelerating the transfer of dye from the material layer to the dye fixing layer. From the physicochemical functions, base or base precursor, nucleophilic compound, high boiling organic solvent (oil), thermal solvent, surface active It is classified into agents, compounds that interact with silver or silver ions, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For details of these, see US Pat. No. 4,678,739.
No. 38 to 40 of the issue.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat.
No. 511493, JP-A No. 62-65038, and the like. In a system in which heat development and transfer of a dye are simultaneously carried out in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye fixing element in order to enhance the storability of the light-sensitive material.

In addition to the above, European Patent Publication 210660
No. 4,740,445, and combinations of sparingly soluble metal compounds and compounds capable of complex-forming reaction with metal ions constituting the sparingly soluble metal compounds (referred to as complex-forming compounds), and JP-A-61-232451. Compounds that generate a base by electrolysis described in Japanese Patent Publication No. JP-A No. 2003-242242 can also be used as the base precursor. The former is especially effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive material and the dye fixing element.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. . Here, the development terminator means that after proper development, the base is promptly neutralized or reacted with a base,
It is a compound that lowers the base concentration in the film and stops development, or a compound that interacts with silver and silver salts to suppress development. Specific examples thereof include an acid precursor that releases an acid by heating, an electrophilic compound that causes a substitution reaction with a coexisting base by heating, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Further details are described on pages 31 to 32 of JP-A-62-253159.

In the present invention, as the support for the light-sensitive material and the dye fixing element, those having physical properties capable of withstanding the processing temperature are used. Generally, paper and synthetic polymer film are used. Specifically, films made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, Film method synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper)
Further, metals, cloths, glasses and the like can be used. These support materials can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to this, 29 to 31 of JP-A-62-253159.
The support described on the page can be used. The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents.

As a method for exposing and recording an image on a photosensitive material, a light emitting diode for transmitting image information via an electric signal,
There are a method of exposing by exposing various lasers and the like, a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display and exposing directly or through an optical system. Specifically, JP-A-2-129625, Japanese Patent Application Nos. 3-338182, 4-0093388, and 4-
The exposure method described in No. 281442 or the like can be used.

As a light source for recording an image on a photosensitive material,
Conventional light emitting diode, laser light source, CRT
Light sources such as those described in US Pat. No. 4,500,626 at column 56 can be used.

[0088]

【Example】

Example 1 A photosensitive silver halide emulsion was prepared as follows. Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 2 are added to an aqueous solution having the composition shown in Table 1 which is well stirred. For 13 minutes
Simultaneously added, 10 minutes later, (II of the composition shown in Table 2
Solution I and solution IV were added over 33 minutes.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Chemical 4] In addition, 13 minutes have passed since the addition of the (III) solution was started,
150cc of 0.35% aqueous solution of sensitizing dye over 27 minutes
Was added.

[0092]

[Chemical 5] Wash with water and adjust the pH to 4.1 using the precipitating agent (a) by a conventional method.
After desalting with, the pH was adjusted to 6.0 and pAg was adjusted to 7.9 by adding 22 g of lime-treated ossein gelatin.
It was chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are shown in Table 3. The yield of the obtained emulsion is 630 g.
It was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0093]

[Chemical 6]

[0094]

[Table 3]

[0095]

[Chemical 7]

[0096]

[Chemical 8] Photosensitive silver halide emulsion (2) [Emulsion for third layer (750 nm photosensitive layer)] Solution (I) and (II) having the composition shown in Table 5 is added to an aqueous solution having the composition shown in Table 4 which is well stirred. For 18 minutes
Simultaneously added, and 10 minutes after that, (II of the composition shown in Table 5
Solution I and solution IV were added over 24 minutes.

[0097]

[Table 4]

[0098]

[Table 5] Wash with water by a conventional method and adjust the pH to 3. with the precipitating agent (b).
Calcium-treated lime-processed ossein gelatin after desalting in 9 (calcium content 150PPM or less) 2
Add 2 g and redisperse at 40 ° C. to give 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene was 0.3
9 g was added to adjust the pH to 5.9 and pAg to 7.8. Then, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 6. At the end of the chemical sensitization, a sensitizing dye was added as a methanol solution (solution having the composition shown in Table 7). Furthermore, after chemical sensitization, the temperature was lowered to 40 ° C., 200 g of a gelatin dispersion of a stabilizer was added, and the mixture was stirred well. The yield of the obtained emulsion was 938 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6% and an average grain size of 0.25 μm.
It was m. Further, the molar ratio of halide ion to silver ion was 106: 100.

[0099]

[Table 6]

[0100]

[Chemical 9]

[0101]

[Table 7]

[0102]

[Chemical 10]

[0103]

[Chemical 11] Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 9 is added to an aqueous solution having the composition shown in Table 8 which is well stirred. For 18 minutes
Simultaneously added, and 10 minutes after that, (III) having the composition shown in Table 9 was added.
Solution and Solution (IV) were added over 24 minutes.

[0104]

[Table 8]

[0105]

[Table 9] After washing with water and desalting with a precipitating agent (a) at a pH of 3.8 by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and pAg to 7.8. Then, it was chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 10. The yield of the obtained emulsion was 680 g, and it was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0106]

[Table 10] A gelatin dispersion of colloidal silver was prepared as follows. In an aqueous solution having the composition shown in Table 11 which is well stirred,
The liquid having the composition shown in Table 12 was added over 24 minutes. Then, after washing with water using the precipitating agent (a), 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3.
The average particle size of the obtained colloidal silver gelatin dispersion is
At 0.02 μm, the yield was 512 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0107]

[Table 11]

[0108]

[Table 12] A hydrophobic additive gelatin dispersion was then prepared as follows. Gelatin dispersions of a yellow dye-donor compound, a magenta dye-donor compound and a cyan dye-donor compound were prepared according to the formulations shown in Table 13.
That is, each oil phase component is heated and dissolved at about 70 ° C.,
The solution was made into a uniform solution, and the aqueous phase component heated to about 60 ° C. was added to the solution, followed by stirring and mixing, followed by dispersion with a homogenizer at 10,000 rpm for 10 minutes. Water was added to this and stirred to obtain a uniform dispersion. Furthermore, a gelatin dispersion of a cyan dye-donating compound was added to an ultra loca module (ultra loca module manufactured by Asahi Kasei Corporation: ACV-305.
0) was used to repeat dilution with water and concentration, and Table 1
The amount of ethyl acetate was reduced to 17.6 times the amount of ethyl acetate of 3.

[0109]

[Table 13]

[0110]

[Chemical 12]

[0111]

[Chemical 13]

[0112]

[Chemical 14]

[0113]

[Chemical 15]

[0114]

[Chemical 16]

[0115]

[Chemical 17]

[0116]

[Chemical 18]

[0117]

[Chemical 19]

[0118]

[Chemical 20] A gelatin dispersion of reducing agent was prepared according to the recipe in Table 14. That is, each oil phase component is heated and dissolved at about 60 ° C., and an aqueous phase component heated to about 60 ° C. is added to this solution,
After stirring and mixing, use a homogenizer for 10 minutes to 1000
Dispersion was carried out at 0 rpm to obtain a uniform dispersion. Furthermore, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0119]

[Table 14]

[0120]

[Chemical 21] A stabilizer gelatin dispersion was prepared according to the formulation in Table 15. That is, each oil phase component was dissolved at room temperature, an aqueous phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added to this and stirred to obtain a uniform dispersion.

[0121]

[Table 15]

[0122]

[Chemical formula 22] A gelatin dispersion of zinc hydroxide was prepared according to the formulation in Table 16. That is, after mixing and dissolving each component, with a mill,
Glass beads having an average particle size of 0.75 mm were used and dispersed for 30 minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.2
The one with 5 μm was used. )

[0123]

[Table 16] Then, a gelatin dispersion of the matting agent added to the protective layer was prepared as follows. P to methylene chloride
The liquid in which MMA was dissolved was added to gelatin together with a small amount of a surfactant, and the mixture was stirred and dispersed at high speed. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain a uniform dispersion having an average particle size of 4.3 μm.

Using the materials prepared as described above, Table 1
The photothermographic material 100 shown in No. 7 was produced.

[0125]

[Table 17]

[0126]

[Table 18]

[0127]

[Chemical formula 23]

[0128]

[Chemical formula 24]

[0129]

[Chemical 25]

[0130]

[Chemical formula 26]

[0131]

[Chemical 27] Then, the photosensitive silver halide emulsion (2A) was added to an aqueous solution of the composition shown in Table 4 which was well stirred in the preparation of the photosensitive silver halide emulsion (2), and (I) of the composition shown in Table 5 was used.
And Solution (II) were prepared in exactly the same manner as in Photosensitive Silver Halide Emulsion (2) except that the solution and (II) were added simultaneously over 24 minutes. Here, the molar ratio of halide ions to silver ions was 106: 100.

Using the thus-prepared material, the light-sensitive silver halide emulsion in the third layer of the light-sensitive material 100 was replaced by the light-sensitive silver halide emulsion (2A), and the same operation as in the light-sensitive material 100 was conducted. , A photosensitive material 101 was produced. Then, the photosensitive silver halide emulsion (2B) was added to a solution (I) having the composition shown in Table 5 in an aqueous solution having the composition shown in Table 4 which was well stirred in the preparation of the photosensitive silver halide emulsion (2). And (II) solution were added simultaneously over 9 minutes, in exactly the same manner as the photosensitive silver halide emulsion (2),
Prepared. Here, the molar ratio of halide ions to silver ions was 106: 100.

Using the thus-prepared material, the light-sensitive silver halide emulsion in the third layer of the light-sensitive material 100 is replaced by the light-sensitive silver halide emulsion (2B), and the same operation as in the light-sensitive material 100 is performed. , A photosensitive material 102 was produced. Then, the photosensitive silver halide emulsion (2C) was prepared in the same manner as in the preparation of the photosensitive silver halide emulsion (2) except that the addition amount of NaCl contained in the solution (II) shown in Table 5 was changed to 5.42 g. Was prepared in exactly the same manner as the photosensitive silver halide emulsion (2). Here, the ratio of the number of moles of halide ions and silver ions was 112: 100.

A light-sensitive material 103 was prepared in the same manner as the light-sensitive material 100 except that the photosensitive silver halide emulsion in the third layer of the light-sensitive material 100 was replaced with the emulsion (2C) using the material thus prepared. Generated. Then, the photosensitive silver halide emulsion (2D) is included in the solution (IV) shown in Table 5 in the preparation of the photosensitive silver halide emulsion (2).
A photosensitive silver halide emulsion (2) was prepared in exactly the same manner except that the amount of NaCl added was changed to 1.8 g and the amount of KBr added was changed to 46.7 g. Here, the ratio of the number of moles of halide ions and silver ions was 112: 100.

Using the thus-prepared material, the light-sensitive silver halide emulsion in the third layer of the light-sensitive material 100 is replaced with the light-sensitive silver halide emulsion (2D), and the same operation as in the light-sensitive material 100 is performed. The photosensitive material 104 was produced. These light-sensitive materials 100 to 104 were exposed under standard conditions using PG-3000 for PG-3000 as a dye fixing material with a digital color printer FUJIX PICTOROGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd. Processed. The exposure and processing conditions are shown in Table 19. However, regarding exposure, the emission time of the laser is modulated every 2.5 cm on the photosensitive material so that the exposure amount is 1/10, and
The characteristic curve of the light-sensitive material was obtained.

[0136]

[Table 19] Sensitivity of each sample obtained as above, fog,
The color separation property was evaluated, and the results are shown in Table 2.
It was shown at 0. Here, the sensitivity is represented by the reciprocal of the exposure amount that gives a reflection density of 1.0, and is shown by the relative sensitivity when the sensitivity of the photosensitive material 100 is 100. Fog was indicated by the reflection density of cyan in the unexposed area. The color separation property is a visual judgment as to whether or not color mixture of the third layer occurs due to the color development of the first layer when exposed to light having a wavelength suitable for developing the third layer. did. The data on the emulsion grains of each sample are all those of the photosensitive silver halide emulsion of the third layer, and the grain shape was observed by an electron microscope photograph at a magnification of 10,000 times.

[0137]

[Table 20] As shown in Table 20, the photosensitive materials 100 and 101 according to the examples of the present invention are the photosensitive materials 102 and 1 according to the comparative example.
Compared to 03 and 104, less fog and higher sensitivity,
Further, it was found that the color separation property was excellent. Also,
In the light-sensitive materials 100 and 101 according to the examples of the present invention, no decrease in raw storage stability was observed.

The present invention is not limited to the above examples, and various modifications can be made within the scope of the invention described in the claims, and those modifications are also included in the scope of the present invention. It goes without saying that it is one.

[0139]

According to the present invention, it is possible to provide a heat-developable color light-sensitive material which has less fog, high sensitivity, and excellent color separation without deteriorating the raw storage stability.

Claims (2)

[Claims] 1. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, wherein the light-sensitive silver halide emulsion has an infrared radiation of 700 nm or more. Has a peak of spectral sensitivity and is spectrally sensitized by a sensitizing dye forming a J-band, and 70% or more of the total surface area of the faces constituting the emulsion grains is the (100) face. A heat-developable color light-sensitive material having at least one layer containing a light-sensitive silver halide emulsion. 2. The photosensitive silver halide grains are cubes having an average grain size of 0.3 μm or less, and the molar ratio of halide ions to silver ions at the time of forming the emulsion grains is 90: The heat-developable color light-sensitive material according to claim 1, which is in the range of 100 to 110: 100.