JP2791687B2 - Thermal development color photosensitive material - Google Patents

Description

The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material having high illuminance sensitivity and low low illuminance sensitivity.

2. Description of the Related Art As one method of exposing a photographic light-sensitive material, a so-called scanner method in which a hard copy image is formed by performing scanning exposure using various light sources on a silver halide photographic light-sensitive material based on an image information signal. Image recording methods are known.
There are various types of recording apparatuses that use a scanner-type image recording method, and a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light emitting diode, and the like have been conventionally used as a recording light source. However, it has a practical disadvantage that it is weak and has a short life.
To compensate for these drawbacks, there is a laser printer that exposes with high illuminance using a coherent laser light source such as a He-Ne laser, an argon laser, or a He-Cd laser as a light source of a scanner system. Also, an image recording apparatus using a small, high-output semiconductor laser as an exposure source has been put to practical use.

Conventional photographic light-sensitive materials can be used for the image recording apparatus of the scanner type, regardless of whether they are negative or positive. However, the conventional photographic light-sensitive material has a drawback in that the process is complicated because a processing solution is required for the developing process, and is not always suitable for making a hard copy of an electronic image. On the other hand, a photothermographic material can easily and quickly obtain an image because the developing step is performed by dry processing using heat, and is suitable for a scanner exposure method.

The photothermographic material and the image forming method are described in, for example,
Nos. 4921 and 43-4924, "Basics of Photographic Engineering", pp. 553 to 555 of Current Salt Photography Edition (published by Corona in 1879), and Research Disclosure Magazine, June 1978, pp. 9 to 15 ( RD-17029).

There are two types of photothermographic materials: one that obtains a black-and-white image and one that obtains a color image. In particular, in recent years, development of a heat-developable color photographic material that obtains a color image using various dye-providing substances has been attempted.

There are various types of heat-developable color light-sensitive materials. For example, a color image is obtained by releasing or forming a diffusible dye by thermal development and then transferring the dye (hereinafter, this method is referred to as a transfer method). Requires an image receiving member for transfer, but is excellent in terms of image stability, sharpness, simplicity and speed of processing, and the like. The heat-developable color light-sensitive material and image forming method of this transfer method are described in, for example, JP-A-59-12431, JP-A-59-159159, and JP-A-59-181345.
No. 59-229556, No. 60-2950, No. 61-52643, No. 61
-61158, 61-61157, 59-180550, 61-13
Nos. 2952, 61-139842 and U.S. Pat.
Nos. 2, 4,590,154 and 4,584,267 are described in each specification and the like.

[Problems to be Solved by the Invention] In a scanner-type image recording apparatus, exposure per pixel is performed in a short time of about 1 millisecond or less.
In order to increase the recording speed, the exposure time may be shorter than 1 microsecond. Therefore, the heat-developable color light-sensitive material used for this purpose is required to have high sensitivity (high illuminance sensitivity) to short-time high-illuminance exposure.

However, in general, a photosensitive material having high illuminance sensitivity has a high sensitivity to low illuminance long-time exposure (low illuminance sensitivity), and the brightness of a safelight used when loading a photographic material is limited. Has occurred.

Further, the heat-developable color light-sensitive material is developed at a much higher temperature than a conventional color light-sensitive material (for example, color photographic paper), and thus has a disadvantage that fog is easily generated. In particular, when a high level of chemical sensitization is applied, fogging tends to occur. For this reason, in order to obtain high sensitivity with a heat-developable color photosensitive material, it is necessary to adjust the maximum wavelength of the spectral sensitivity to the wavelength of the exposure source as much as possible.

In general, a heat-developable color photosensitive material incorporates a reducing agent and / or a reducing agent precursor (hereinafter, “reducing agent” means a reducing agent and / or a reducing agent precursor) that causes a development reaction by heating. Therefore, the storage stability of the spectral sensitizing dye during storage is low, and the spectral sensitizing dye that can be used is limited.

Usually, a safe light used when handling a photosensitive material is selected so as not to substantially transmit light in the photosensitive wavelength range of the photosensitive material. Difficult to take widely.

For example, a light-emitting diode or a He-Ne laser preferably used as a red light source has an emission maximum at a wavelength shorter than 680 nm, but when the spectral sensitivity maximum wavelength of the photosensitive material is adjusted to this, yellow light around 600 nm is used. The increased sensitivity limits the use of yellow safelights (eg Konica Safelight Glass No. 9B). For this reason, it is highly desired that the heat-developable color light-sensitive material has high sensitivity particularly to high illuminance short-time exposure such as scanner exposure and low sensitivity to low illuminance long-time exposure by safelight transmitted light. As a result, even if the safelight transmitted light slightly overlaps the photosensitive wavelength range, fog and sensitivity fluctuation can be prevented from occurring.

Further, in order to prevent fogging due to stray light in the exposure / heat developing apparatus, the above-described photosensitive material is desired.

In particular, in a transfer type photothermographic material, an optical sensor, particularly an infrared sensor, is often used in order to adjust the supply timing of the photosensitive material and the image receiving material. When the wavelength of the sensor overlaps with the photosensitive wavelength of the photosensitive material, the photosensitive material is not directly irradiated, but may be strayed to the photosensitive material in the apparatus. From the viewpoint of preventing fog and sensitivity fluctuation caused by such stray light, a heat-developable color photosensitive material having high illuminance sensitivity and low illuminance sensitivity as described above has been desired.

In view of the above-mentioned conventional problems, an object of the present invention is to provide a scanner system which has excellent suitability for scanning exposure and can be handled under a safe light, and furthermore, fog and sensitivity due to stray light in an exposure / heat developing apparatus. An object of the present invention is to provide a heat-developable color light-sensitive material that hardly causes fluctuation.

[Means for Solving the Problems] In order to achieve the above object, the present invention provides a method for producing
A heat-developable color light-sensitive material comprising at least a photosensitive silver halide particle, a reducing agent, a dye-donating substance and a binder, has a photosensitive layer containing a silver halide emulsion sensitized with gold and sulfur and containing iridium ions. Further, the photosensitive layer is the sensitivity of the reciprocal of the exposure amount that gives an optical density 0.3 higher than the fog density, the sensitivity when exposed in 0.3 microseconds is S _H , the sensitivity when exposed in 30 seconds is S _L When
S _H / S _L ≧ 2.0.

Here, the optical density is a reflection density when an image is formed on a reflective support, and a transmission density when an image is formed on a transmissive support.

 Hereinafter, the present invention will be described in detail.

In the present invention, S _H / S _L ≧ 2.0, provided that S _H
When / S _L <2.0, both the suitability for scanner scanning exposure and the stability of safelight cannot be satisfied. It is preferred the difference between S _H and S _L is large, i.e., particularly preferably from S _H / S _L ≧ 4.0, further preferably S _H / S _L ≧ 8.0.

S _H and S _L is S red-sensitive layer maximum wavelength in a wavelength shorter than 680nm and spectral sensitivity stand viewpoint using conventional Preferably used are optionally yellow safelight (eg Konica safelight glass Nanba9B) It is preferable that _H / S _L ≧ 4.0.

In the scanning exposure method of the scanner system, the exposure time per pixel is usually 10 milliseconds to 10 nanoseconds. Therefore, it is preferable that the sensitivity change is small in this range.
Specifically, when the sensitivity at 1 millisecond exposure is S _M , S _H
It is preferred that / S _M ≧ 0.5.

In determining S _H , S _L and S _M , it is necessary that the spectral wavelength distributions of the exposure light sources can be regarded as being equal or substantially equal. Using a monochromatic light or a light source similar to it
Measuring S _H , S _L and S _M is a preferred method. For example, S _H and S _M can be determined by scanning exposure with a laser.

S _L and S _M can be obtained by exposing the beam of the laser beam by a beam expander and exposing the beam to a known shutter.

As a simpler method, a known white light source (for example, a xenon lamp, a halogen lamp, a tungsten lamp, or the like) is combined with an interference filter to produce pseudo-monochromatic light, which can be used as an exposure source.

The use of monochromatic light or pseudo-monochromatic light for sensitivity measurement is preferable in that the exposure dose can be easily measured, but of course, a light source with a wavelength distribution such as white light, blue light, red light, green light, and infrared light May be used.

The characteristics of the heat-developable color light-sensitive material of the present invention can be obtained mainly by imparting characteristics to the silver halide emulsion contained in the photosensitive layer.

The silver halide that can be used in the present invention is optional, and examples thereof include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. Those containing at least mol% are preferred. More preferably, it is a silver halide containing 70 mol% or more of silver bromide. The photosensitive silver halide can be prepared by any method commonly used in the photographic art.

Further, an emulsion containing grains having a multilayer structure in which the halogen composition of the grains differs between the surface and the inside can be used. For example, core / shell type silver halide grains in which the halogen composition changes stepwise, or silver halide emulsions having continuously changing grains can be used.

The shape of the photosensitive silver halide is cubic, spherical,
Either an octahedron, a dodecahedron, a tetrahedron, or the like, which has a distinctive crystal habit, or an octahedron, a dodecahedron, or the like may be used. Examples of this type of silver halide include those described in JP-A-60-215948.

In the present invention, it is preferable to use silver halide grains in which 30% or more of the grain surface area is constituted by (100) planes. More preferably, the (100) plane is at least 60%.

Also, for example, JP-A-58-111933, JP-A-58-111934,
No. 58-108526, Research Disclosure 22534
And the like, each of which has two parallel crystal planes and each of these crystal planes has a larger area than the other crystal planes of the particle, and has an aspect ratio, i.e., particle size. A silver halide emulsion containing tabular silver halide grains having a diameter to thickness ratio of 5: 1 or more can also be used.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surface is not fogged in advance can be used. For an internal latent image type silver halide whose surface is not fogged in advance, for example, US Pat.
2,592,250, 3,206,313, 3,317,322, 3,51
1,622, 3,447,927, 3,761,266, 3,703,584
No. 3,736,140 and the like. An internal latent image type silver halide grain whose surface is not fogged in advance is, as described in each of the above specifications, a silver halide grain whose sensitivity inside the grain is higher than the sensitivity of the surface of the silver halide grain. is there. U.S. Pat.Nos. 3,271,157,
No. 3,447,927 and 3,531,291, silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or halogen containing a dopant described in U.S. Pat. A silver halide emulsion in which the grain surfaces of silver grains are weakly chemically sensitized, or a silver halide emulsion comprising grains having a laminated structure described in JP-A-50-8524 and JP-A-50-38525.
In addition, silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549 can be used.

The silver halide in the photosensitive emulsion may be coarse or fine, but the grain size is preferably about 0.005 μm to about 1.5 μm, more preferably about 0.01 μm to about 1.5 μm. 0.5 μm. However, in the present invention, “particle size” refers to the length of one side of a cube having the same volume. The particle size distribution may be wide (polydisperse emulsion) or narrow (monodisperse emulsion), but monodisperse emulsions are preferred for the purposes of the present invention.

Particularly, silver halide grains having a variation coefficient of the grain size distribution of 20% or less are preferable. Here, the coefficient of variation is And is a measure of monodispersity.

In general, high- and low-illumination exposure characteristics of silver halide photographic light-sensitive materials must be improved by changing the chemical sensitization (sulfur sensitization, gold sensitization, reduction sensitization, etc.) applied to the silver halide emulsion. Can be. However, in a photothermographic material, development activation energy is given by heating at the time of development, and it is easy to cause deterioration of image quality such as generation of fog. Therefore, only a very limited range of chemical sensitization can be performed.

In order to achieve the object of the present invention, it is preferable to perform chemical sensitization using a gold sensitizer, and another chemical sensitization method may be used in combination. Particularly preferably, chemical sensitization is carried out using a sulfur sensitizer and a gold sensitizer in combination.

The oxidation number of gold of the gold sensitizer used is arbitrary and may be +1 or +3, and various gold compounds can be used. Examples of typical gold sensitizers include chloroauric acid, chloroaurate, potassium chloroaurate, auric trichloride,
Examples thereof include potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, and pyridyltrichlorogold. In particular, chloroauric acid or a salt thereof is preferably used.

The amount of the gold sensitizer to be added varies depending on various conditions, but as a guide, about 1 μmol to 1 mmol per 1 mol of silver halide,
Preferably 1.5 to 500 μmol, more preferably 2 to 200 μmol
mol.

Any sulfur sensitizer that can be used in combination with the gold sensitizer can be used.

For example, thiosulfate, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like can be mentioned. Also, inorganic sulfur disclosed in JP-A-63-301039 can be used. Other U.S. Patent Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,728,668, No. 3,5
01,313, 3,656,955, German Patent 1,4
No. 22,869, JP-A-56-24937, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions, such as pH, temperature, and the size of silver halide grains. As a guide, about 1 μmol to 1 mmol, preferably 0.2 to 500 μmol, per mol of silver halide is used. It is.

When a gold sensitizer and a sulfur sensitizer are used in combination, the molar ratio of the gold sensitizer to the sulfur sensitizer is preferably 0.05 to 20, more preferably 0.1 to 0.2.
1-15 are more preferred.

As described above, since a heat-developable color light-sensitive material is liable to fog, a silver halide emulsion can be subjected to only a low level of chemical sensitization. That is, the photosensitive nucleus is small and weak. In such a silver halide emulsion, the initial latent image nucleus and the sub-latent image nucleus are easily destroyed, so that low-sensitivity exposure does not lead to the formation of a latent image and has low sensitivity.

When gold sensitization is performed in such a state, the sub-latent image nucleus is intensified with gold and can be developed, so that the sensitivity to high illuminance exposure increases, and the object of the present invention is achieved.

The gold-sulfur sensitization according to the present invention is preferably performed in the presence of thiocyanate ions. Thiocyanate ions, KSCN, can be added in the form of _{NaSCN, NH 4 SCN, Zn (} SCN) 2, Ca (SCN) 2 , such as any compound. It is particularly preferred that the gold sensitizer and the thiocyanate compound are mixed before the gold sensitizer is added with the silver halide emulsion.

In the present invention, high illuminance sensitivity can be further improved by including iridium ions in the silver halide emulsion.

In order to contain iridium ions in the present invention,
When preparing a silver halide emulsion, a water-soluble iridium compound (for example, hexachloroiridium (III) or hexachloroiridium (IV) [for example, K ₂ IrCl ₆ , K ₃
IrCl ₆ , Li ₃ IrCl ₆ , Na ₃ IrCl ₆ , (NH ₄ ) ₂ IrCl ₆ , Li ₂ IrCl ₆ , Na ₂
IrCl ₆ ]) or the like in the form of an aqueous solution. It may be added in the form of the same aqueous solution as the halide for forming the grains, or may be added as a separate additive liquid. The addition may be performed at any time before the formation of the grains, during the formation of the grains, or after the formation of the grains and before the chemical sensitization. Particularly preferred is the addition during the formation of the grains.

In the present invention, the preferred amount of iridium ion varies depending on the method of chemical sensitization. That is, when no gold sensitizer is used, 10 ^-8 to
Preferably used 10 ^-5 mol, more preferably it is used 10 ^-7 to 10 ^-5 mole.

On the other hand, when a gold sensitizer is used, it is preferably 0 to 10 ^-5 mol, more preferably 0 to 10 ^-6 mol, per mol of silver halide.

At the time of forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,628)
No. 3,704,130, No. 4,297,439, No. 4,276,37
No. 4) thione compounds (for example, JP-A-53-144319,
Nos. 53-82408 and 55-77737) and amine compounds (for example, JP-A-54-100717) can be used. In addition to the silver halide solvent, compounds that control the crystal habit by adsorbing on the grain surface, such as cyanine sensitizing dyes, tetrazaindene compounds, and mercapto compounds can be used.

In the present invention, as another method for preparing a photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below, and a part of the organic silver salt may form a photosensitive silver halide. .

These light-sensitive silver halide and a photosensitive silver salt forming component may be used in combination with various aspects, the amount, based on per support 1 m ² more, is preferably 0.001G～50g, more preferably Is 0.1 to 10 g.

The photosensitive silver halide emulsion may be chemically sensitized by any method in the photographic art.

The photosensitive silver halide emulsion to be used can be subjected to spectral sensitization for imparting sensitivity to blue, green, red, near-infrared light and the like with a known spectral sensitizing dye.

Representative spectral sensitizing dyes that can be used include:
Examples include cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like.

The preferred addition amount of these sensitizing dyes is 1 × 10 ^-6 per mol of the photosensitive silver halide or silver halide forming component.
Mol to 1 mol. More preferably, 1 × 10 ⁻⁵ to 1 ×
10 ^-1 mole.

The sensitizing dye may be added at any stage during the preparation of the silver halide emulsion. That is, it may be at any time such as at the time of forming silver halide grains, at the time of removing soluble salts, at the start of chemical sensitization, at the time of chemical sensitization, or after the end of chemical sensitization.

Since the heat-developable color light-sensitive material contains a reducing agent and other substances not contained in the conventional color light-sensitive material, the sensitizing dye is easily decomposed and desorbed during storage. Therefore, the types of sensitizing dyes that can be used are limited.

The sensitizing dye preferably used is a cyanine dye, particularly a cyanine dye having a thiazole nucleus and / or an oxazole nucleus and / or a selenazole nucleus. More preferably, two nuclei selected from a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, and a naphthoselenazole nucleus (which may be different or identical to each other) are bonded by a methine bond. It is a cyanine dye that has been used.

The photothermographic material of the present invention can be embodied as a black-and-white photographic material or a color photographic material. In the case of a color light-sensitive material, a dye-providing substance is used.

Dye-donating substances which can be used when the present invention is applied to color light-sensitive materials include, for example, JP-A-64-2473.
Nos. 7, 62-129852, 62-169158, non-diffusible dye-forming couplers, e.g. U.S. Pat.
The leuco dye described in 475,441, or the azo dye used in the thermal developing dye bleaching method described in, for example, U.S. Pat.No.4,235,957 can also be used as the dye-providing substance, but it is more preferable to form a diffusible dye or It is preferable to use a diffusible dye-donating substance that emits, and it is particularly preferable to use a compound that forms a diffusible dye by a coupling reaction.

Hereinafter, the diffusion type dye-providing substance that can be used in the present invention will be described. Diffusion-type dye-providing substances are those which correspond to the reduction reaction of photosensitive silver halide and / or the organic silver salt used as required, and can form or release a diffusible dye as a function of the reaction. Often,
Depending on the reaction mode, it can be classified into a negative dye-donating substance and a positive dye-donating substance.

As negative dye-donating substances, for example, U.S. Pat.
Nos. 3,079 and 4,439,513, JP-A-59-60434, and 59-6
No. 5839, No. 59-71046, No. 59-87450, No. 59-88730
Nos. 59-123837, 59-124329, 59-165054
And reducing dye-releasing compounds described in the specifications such as JP-A Nos.

As another negative type dye-providing substance, for example, U.S. Pat.
4,474,867, JP-A-59-12431, JP-A-59-48765, and
9-174834, 59-776642, 59-159159, 59
Coupling dye-releasing compounds described in the specification such as -231040.

Still another particularly preferred negative dye-donor substance of the coupling dye-forming compound is represented by the following general formula (A).

Formula (A) CpJB) In the formula, Cp represents an organic group (a coupler residue) capable of forming a diffusible dye by reacting (coupling reaction) with an oxidized form of a reducing agent, and J represents a reducing agent. Represents a divalent linking group bonded to an active site that reacts with the oxidized form of B, and B represents a ballast group. Here, the ballast group means that during thermal development processing,
It is a substance that does not substantially diffuse the dye-donating substance. A group that exhibits its action (such as a sulfo group) depending on the nature of the molecule, a group that exhibits its action according to its size (such as a group having a large number of carbon atoms), etc. Say. The coupler residue represented by Cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in order to improve the diffusibility of the formed dye.

As the ballast group, a group having preferably 8 or more, more preferably 12 or more carbon atoms is preferable, and a group that is a polymer chain is more preferable.

As the coupling dye-forming compound having a group that is a polymer chain, a compound having a polymer chain having a repeating unit derived from a monomer represented by the general formula (b) as the above group is preferable.

Formula (b) CpJY ₁ ZL) In the formula, Cp and J have the same meanings as those defined in Formula (A), Y represents an alkylene group, an arylene group or an aralkylene group, and 1 represents 0 or 1. And Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compounds represented by formulas (a) and (b) are described in JP-A-59-124339,
59-181345, 60-2950, 61-57943, 61-5
Publications such as 9336, U.S. Pat.Nos. 4,631,251 and 4,650,748
No. 4,656,124, and in particular, U.S. Pat.No. 4,656,124 and U.S. Pat.
Polymer type dye-providing substances described in the specifications of JP-A Nos. 51 and 4,650,748 are preferred.

Examples of the positive dye-donating substance include, for example, JP-A-59-1984.
No. 55430, No. 59-165054, No. 59-154445, No. 59-766
No. 954, No. 59-116655, No. 59-124327, No. 59-15244
There are compounds described in publications such as No. 0 and the like.

These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, and the type of the dye-providing substance, single use or a combination of two or more kinds, or the photographic constituent layer of the photographic material of the present invention may be a single layer or two or more.
The amount may be determined according to the above-mentioned multi-layer, etc., for example, the amount of use can be 0.005 to 50 g, preferably 0.1 to 10 g per 1 m ² .

The method of incorporating the dye-providing substance used in the present invention into the photographic component layer of the photothermographic material is arbitrary, and examples thereof include low-boiling solvents (methanol, ethanol, ethyl acetate, etc.) and / or
Alternatively, after dissolving in a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.), emulsifying and dispersing, or dissolving in an alkaline aqueous solution (eg, a 10% aqueous sodium hydroxide solution), an acid (eg, Neutralized with citric acid or nitric acid, etc.) or an aqueous solution of a suitable polymer (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.)
Can be used after solid dispersion.

In the photothermographic material of the present invention, it is preferable to use various organic silver salts for the purpose of increasing sensitivity and improving developability as necessary.

Organic silver salts that can be used in the photothermographic material of the present invention include JP-A-53-4921, JP-A-49-52626, and JP-A-52-52626.
-141222, 53-36224 and 53-37626, 53-
It has a silver salt or a heterocyclic ring of a long-chain aliphatic carboxylic acid as described in each publication such as 37610 and U.S. Pat.Nos. 3,330,633, 3,794,496, and 4,105,451. Silver salts of carboxylic acids, such as silver behenate, α
Silver (-(1-phenyltetrazolethio) acetate), JP-B-44-26582, JP-B-45-12700, JP-B-45-18416, and 4-
5-22185, JP-A-52-137321, JP-A-58-118638,
There is a silver salt of an imino group described in US Pat. No. 5,118,639 and US Pat. No. 4,123,274.

Among the above organic silver salts, a silver salt of an imino group is preferable, and particularly a silver salt of a benzotriazole derivative, more preferably benzotriazole and its derivative, 5-methylbenzotriazole and its derivative, sulfobenzotriazole and its derivative, N -Alkylsulfamoylbenzotriazoles and derivatives thereof are preferred.

The organic silver salts used in the present invention may be used alone or in combination of two or more. Further, a silver salt may be prepared in an appropriate binder and used as it is without isolation, or the isolated one may be used after being dispersed in a binder by an appropriate means. Examples of the dispersing means include, but are not limited to, those using a ball mill, a sand mill, a colloid mill, and a vibration mill.

The amount of the organic silver salt to be used is generally preferably 0.01 mol to 500 mol, more preferably 0.1 mol to 1 mol of the photosensitive silver halide.
~ 100 moles. More preferably, it is 0.3 to 30 mol.

As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used.

Examples of the reducing agent that can be used in the present invention include, for example, U.S. Patent Nos. 3,531,286, 3,761,270, and 3,764,
Nos. 328, RD (Research Disclosure) Nos. 12146, 15108, 15127 and JP-A-56-127
No. 27132, U.S. Pat.Nos. 3,342,599 and 3,719,492
P-phenylenediamine-based and p-aminophenol-based developing agents described in JP-A-53-135628, JP-A-57-79035, etc., phosphoramidophenol-based, sulfonamidoaniline-based development A main agent, a hydrazone-based color developing agent and a precursor thereof, or phenols, sulfonamidophenols, or polyhydroxybenzenes, naphthols, hydroxybinaphthyls and methylenebisnaphthols, methylenebisphenols, ascorbic acid, Pyrazolidones and pyrazolones can be used.

 The dye-providing substance may also serve as a reducing agent.

Particularly preferred reducing agents include N- (pN, N-dialkylamino) phenyl sulfamate described in JP-A-56-146133 and JP-A-62-727141.

 Two or more reducing agents may be used simultaneously.

The amount of the reducing agent used in the photothermographic material of the present invention is not necessarily constant depending on the type of photosensitive silver halide used, the type of organic silver salt and the type of other additives, but is not always constant. Usually, it is preferably in the range of 0.01 to 1500 mol, more preferably 0.1 to 200 mol, per 1 mol of the photosensitive silver halide.

As the binder that can be used in the photothermographic material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, There are synthetic or natural high-molecular substances such as cellulose derivatives, proteins, starch and gum arabic, and these can be used alone or in combination of two or more. In particular, it is preferable to use a combination of gelatin or a derivative thereof and a hydrophilic polymer such as polyvinylpyrrolidone and polyvinyl alcohol, and more preferably use a mixed binder of gelatin described in JP-A-59-229556 and polyvinylpyrrolidone. That is.

The preferred amount of the binder to be used is generally 0.05 g to 50 g, more preferably 0.2 g to ²⁰ g, per m ^{2 of the} support.

The binder is used in an amount of 0.1 to 1 with respect to 1 g of the dye-providing substance.
It is preferable to use 0 g, and more preferably 0.2 to 5 g.

The photothermographic material of the present invention can be obtained by forming a photographic component layer on a support. Examples of the support that can be used here include a polyethylene film, a cellulose acetate film, a polyethylene terephthalate film, and a polyethylene terephthalate film. Paper supports such as synthetic plastic films such as vinyl chloride, photographic base paper, printing paper, art paper, cast coated paper, baryta paper and resin coated paper, and electron beam curable resin compositions on these supports Is applied and cured.

When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, it is preferable that various thermal solvents be added to the photothermographic material and / or the image receiving member. The thermal solvent is a compound which is liquid during thermal development and promotes thermal development and / or thermal transfer. These compounds include, for example, U.S. Patent Nos. 3,347,675 and 3,667,959
No., (RD Research Disclosure) No.17643 (XI
I), JP-A-59-229556, JP-A-59-68730, JP-A-59-8423.
No. 6, No. 60-191251, No. 60-232547, No. 60-14241
No. 61-52643, No. 62-78554, No. 62-42153,
Nos. 62-44737 and U.S. Pat.
Nos. 666,477 and 3,667,959, JP-A-51-19525
No. 53-24829, No. 53-60223, No. 58-118640,
Organic compounds having polarity as described in JP-A-58-198038 can be mentioned, and particularly useful compounds for practicing the present invention include urea derivatives (eg, dimethylurea, diethylurea, phenyl). Urea), amide derivatives (eg, acetamido, benzamide, p
-Toluamide, etc.), sulfonamide derivatives (eg, benzenesulfonamide, α-toluenesulfonamide, etc.), polyhydric alcohols (eg, 1,6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, etc.), or polyethylene Glycols.

Among the above thermal solvents, a water-insoluble solid thermal solvent is particularly preferably used.

Specific examples of the water-insoluble thermal solvent include, for example,
There are those described in JP-A-62-136645, JP-A-62-139549 and JP-A-63-53548, and Japanese Patent Application Nos. 63-205228 and 63-54113.

Examples of the layer to which the thermal solvent is added include a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member, and the like.

The preferable addition amount of the hot solvent is usually 10% by weight to 500% by weight, more preferably 30% by weight to 200% by weight of the binder amount.

The organic silver salt and the thermal solvent may be dispersed in the same dispersion. The same binder, dispersion medium, and dispersion apparatus as those used for preparing the respective dispersions can be used.

In the photothermographic material of the present invention, in addition to the above components, various additives as necessary, for example, a development accelerator, an antifoggant,
It may contain a base precursor or the like.

As development accelerators, JP-A-59-177550 and JP-A-59-11
No. 1636, compounds described in JP-A-59-124333, or compounds disclosed in JP-A-61-159642 and development accelerator releasing compounds described in Japanese Patent Application No. 62-203908, or Japanese Patent Application No. 63-104645. Metal ions having an electronegativity of 4 or more described in (1) can also be used.

Antifoggants include, for example, U.S. Patent No. 3,645,739
Higher fatty acids described in Japanese Patent Publication No. 47-1111
No. 3 mercury salt, N-halogen compound described in JP-A-51-47419, and mercapto compound release described in U.S. Pat. No. 3,700,457 and JP-A-51-50725. Compound, arylsulfonic acid described in JP-A-49-125016, lithium carboxylate described in JP-A-51-47419, British Patent No. 1,455,271, JP-A-50-1
Oxidizing agents described in JP-A-01019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825, 51-32
2-thiouracils described in No. 23, sulfur alone described in 51-26019, 51-42529, 51-81124, 55
-93149, disulfide and polysulfide compounds described in JP-A-51-57435, rosin or diterpenes described in JP-A-51-57435, polymer acid having a free carboxyl group or sulfonic acid group described in JP-A-51-104338, U.S. Pat. No. 4,138,265, thiazolinethione described in JP-A-54-51821, U.S. Pat.No.4,137,079, 1,2,4-triazole or 5-mercapto-1,2,4-triazole, Thiosulfinic acid esters described in JP-A-55-140883, 1,2,3,4-thiatriazoles described in JP-A-55-142331, and 59-46641
No. 59-57233, dihalogen compounds or trihalogen compounds described in JP-A-59-57234,
Examples thereof include a thiol compound described in JP-A-111636, a hydroquinone derivative described in JP-A-60-198540, and a combination of a hydroquinone derivative and a benzotriazole derivative described in JP-A-60-227255.

Still another particularly preferred antifoggant is disclosed in
Inhibitors having a hydrophilic group described in JP-A-62-78554, polymer inhibitors described in JP-A-62-121452, and inhibitors having a ballast group described in JP-A-62-123456 are No.

Further, the colorless couplers described in Japanese Patent Application No. 62-320599 are also preferably used.

Examples of the base precursor include a compound that decarboxylates by heating to release a basic substance (eg, guanidinium trichloroacetate), and a compound that decomposes by a reaction such as an intramolecular nucleophilic substitution reaction to release amines, and the like. For example, JP-A-56-130745, JP-A-56-132332, British Patent 2,
No. 079,480, U.S. Pat.No. 4,060,420, JP-A-59-480
157637, 59-166943, 59-180537, 59-17
No. 4830, No. 59-195237, No. 62-108249, No. 62-1747
Base release agents described in No. 45, etc. can be exemplified.

In addition, various additives used in the photothermographic material as needed, such as an antihalation agent, an optical brightener, a hardener, an antistatic agent, a plasticizer, a spreading agent, a matting agent,
Surfactants, anti-fading agents and the like can be contained, and these are specifically described in RD (Research Disclosure), Vol. 170, June 1978, No. 17029,
-135825.

These various additives may be added not only to the photosensitive layer but also to a non-photosensitive layer such as an intermediate layer, a protective layer or a backing layer.

The photothermographic material of the present invention contains (a) a photosensitive silver halide, (b) a reducing agent, and (c) a binder. When a color photographic material is used, it contains (d) a dye-providing substance.
Further, it is preferable to contain (e) organic silver as required. These may be basically contained in one heat-developable photosensitive layer, but need not necessarily be contained in a single photographic component layer. For example, the heat-developable photosensitive layer is divided into two layers, a), (b), (c), and (e) are contained in one heat-developable photosensitive layer, and the other layer adjacent to the photosensitive layer contains a dye-donating substance (d). It may have a structure, and may be contained in two or more constituent layers as long as they can react with each other.

Further, the photothermographic layer may be provided in two or more layers of a low-sensitivity layer and a high-sensitivity layer, and a high-density layer and a low-density layer.

The photothermographic material of the invention has one or more photothermographic layers. When a full-color photosensitive material is used, generally, three heat-developable photosensitive layers having different color sensitivities are provided. In each photosensitive layer, dyes having different hues are formed or released by thermal development.

Usually, a yellow dye is combined with a blue photosensitive layer, a magenta dye is combined with a green photosensitive layer, and a cyan dye is combined with a red photosensitive layer. However, the present invention is not limited to this. It is also possible to combine near-infrared photosensitive layers.

The configuration of each layer can be arbitrarily selected according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on a support, and a blue-sensitive layer is sequentially formed on a support. , A green photosensitive layer and a red photosensitive layer, or a green photosensitive layer, a red photosensitive layer and a blue photosensitive layer on a support in this order.

In the photothermographic material of the invention, in addition to the photothermographic layer, a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer can be optionally provided. . To apply the heat-developable photosensitive layer and the non-photosensitive layer on a support, the same method as that used for coating and preparing a general silver halide photosensitive material can be applied.

Light sources used for exposure include a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, a cathode ray tube flying spot, a light emitting diode, a laser (eg, a gas laser, a YAG laser, a dye laser, a semiconductor laser, etc.), a CRT light source, and a FOT. Various types can be used alone or in combination. A semiconductor laser and a second harmonic generation element (SHG element) can also be used. In addition, exposure may be performed using light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like.

If necessary, the spectral composition of light used for exposure can be adjusted by a color filter.

Exposure time is preferably 1/100 second or less, 1/100
More preferably, it is 0 second or less.

In particular, it is preferably used for high-speed scanner exposure in which the exposure time per pixel is 10 microseconds or less.

 In the present invention, it is preferable to use a laser as a light source.

The photothermographic material of the present invention is usually preferably used after imagewise exposure.
The development can be carried out simply by heating in a temperature range of 80 ° C to 200 ° C, more preferably 100 ° C to 170 ° C, preferably for 1 second to 180 seconds, more preferably for 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image receiving layer may be performed simultaneously with the thermal development by bringing the image receiving member into close contact with the photosensitive surface of the photosensitive material and the image receiving layer during thermal development, or may be brought into close contact with the image receiving member after thermal development. Alternatively, the transfer may be performed by closely adhering after supplying water and further heating if necessary. Also,
Prior to exposure, preheating may be performed in a temperature range of 70 ° C to 180 ° C. Also, as described in JP-A-60-143338 and JP-A-61-162041, in order to enhance mutual adhesion, the photosensitive material and the image receiving member are heated to 80 ° C. to 250 ° C. immediately before thermal development transfer.
May be preheated.

Various heating means can be used for the photothermographic material of the present invention.

As the heating means, all methods applicable to ordinary photothermographic materials can be used.For example, the heating means can be brought into contact with a heated block or plate, or a heat roller or a heat drum, or can be passed through a high-temperature atmosphere. Or using high-frequency heating, and further providing a conductive layer containing a conductive substance such as carbon black on the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer, and utilizing Joule heat generated by energization. You can also. The heating pattern is not particularly limited. For example, a method of preheating (preheating) and then heating again, and even when heating at a high temperature for a short time or at a low temperature for a long time, the temperature is continuously increased and continuously. Alternatively, the heating may be repeated or the heating may be repeated, and discontinuous heating is also possible, but a simple pattern is preferable. Further, a system in which exposure and heating proceed simultaneously may be used.

When the present invention is a transfer type photothermographic material, an image receiving member is used as described above. In this case, the image-receiving layer effectively used in the image-receiving member may be any layer having a function of receiving the dye in the heat-developable photosensitive layer released or formed by thermal development, such as a tertiary amine or quaternary amine. As the polymer containing an ammonium salt, those described in US Pat. No. 3,709,690 are preferably used. Typical image receiving layers for diffusion transfer include ammonium salts, 3
Some are obtained by mixing a polymer containing a secondary amine or the like with gelatin or polyvinyl alcohol and coating the mixture on a support. Another useful dye-receiving substance has a glass transition temperature of 40 described in JP-A-47-207250.
One formed of a heat-resistant organic high-molecular substance having a temperature of not lower than 250 ° C. and higher.

These polymers may be supported on a support as an image receiving layer, or may be themselves used as a support.

As a polymer, "Polymer Handbook, Second Edition" (Joy Brand Wrap, EH Inmargat ed.) John Willi and Sons Publishing @ Polymer Handbook 2nd ed. (J. Brandrup, E.
H. Immergut) Synthetic polymers having a glass transition temperature of 40 ° C. or higher described in John Wiley & Sons II are also useful.
Generally, the molecular weight of the polymer substance is 2000 to 2000.
00 is useful. These polymer substances may be used alone or as a blend of two or more kinds, or two or more kinds may be used in combination as a copolymer.

Particularly preferred image receiving layers include a layer composed of polyvinyl chloride described in JP-A-59-223425 and a layer composed of polyvinyl chloride described in JP-A-60-19223.
No. 138, a layer composed of a polycarbonate and a plasticizer.

These polymers can be used as a support and image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or may be formed from multiple layers. Good.

As the support for the image receiving member, any material such as a transparent support and an opaque support may be used. For example, films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, and polypropylene, and these supports Supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, talc, etc., baryta paper, resin-coated paper in which a thermoplastic resin containing pigment is laminated on paper, cloth, glass, aluminum Metals such as, etc., and an electron beam-curable resin composition containing a pigment was coated on these supports, and the cured supports were provided, and a coating layer containing the pigment was provided on these supports. And a support. Further, various coated papers such as cast coated paper described in JP-A-62-283333 are also useful as a support.

Further, an electron beam-curable resin composition containing a pigment is applied on paper, and the support is cured, or the pigment-coated layer is provided on paper, and the electron beam-curable resin composition is provided on the pigment applied layer. Can be used as an image receiving member because the resin layer itself can be used as an image receiving layer.

The photothermographic material of the present invention is described in RD (Research Disclosure Magazine) 15108, JP-A-57-198458, and JP-A-57-198458.
No. 07250, as described in JP 61-80148,
It can be a so-called mono-sheet type photothermographic material in which a photosensitive layer and an image receiving layer are provided on the same support.

EXAMPLES Hereinafter, specific examples of the present invention will be described. However, needless to say, the present invention is not limited by the embodiments described below.

Example 1 Preparation of Silver Iodobromide Emulsion (Em-1) A silver iodobromide emulsion (Em-1) was prepared using the following five types of solutions.
-1) was adjusted. As the seed emulsion, a silver iodobromide emulsion (SE-1) having a silver iodide content of 2 mol% and an average grain size (length of one side of a cube having the same volume; the same applies to the following description) was used. .

(Solution A-1) Ossein gelatin 1.45 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% methanol solution 5.0 ml 28% ammonia water 29 ml Seed emulsion (SE-1) 0.071 mol equivalent ion-exchanged water 1750 ml ( Solution B-1) Ossein gelatin 5.0 g KBr 200.0 g KI 5.8 g Finish to 500 ml with ion-exchanged water (Solution C-1) AgNO ₃ 246.3 g 28% ammonia water 200.9 ml Finish to 414 ml with ion-exchanged water (Solution D- 1) Required amount of pAg adjustment for 50% aqueous KBr solution (Solution E-1) Required amount of pH adjustment for 56% acetic acid aqueous solution At 40 ° C., a mixing stirrer disclosed in JP-A-57-92523 and JP-A-57-92524 was used. (Solution B-1) and (Solution C-1) were added to (Solution A-1) at the same flow rate by the simultaneous mixing method.

During the simultaneous mixing, the pH was kept constant at 8.0, and the control was performed while changing the flow rate of (Solution E-1) by using a roller tube pump having a variable flow rate.

The pAg was adjusted to 8.8 at the start of the addition of (Solution B-1) and (Solution C-1), and then continuously changed in proportion to the amount of (Solution B-1). -1) and (Solution C-1) were controlled to 9.3 at the end of addition. The pAg was controlled by changing the flow rate of (Solution D-1) using a roller tube pump having a variable flow rate.

(Solution B-1) and (Solution C-1) are added at an allowable maximum speed (critical speed) at which no small particles are generated.
-1) was completed when all were added. Subsequently, the pAg was adjusted to 10.4 and the pH was adjusted to 6.0 using (Solution D-1) (Solution E-1).

Thereafter, after dispersing in an aqueous solution containing 45.65 g of ossein gelatin, the total amount was adjusted to 1200 ml with distilled water, and pAg was further reduced at 40 ° C. using (solution D-1) (solution E-1).
8.5 and pH were adjusted to 5.8.

The emulsion (Em-1) thus obtained was a silver iodobromide emulsion having a silver iodide content of 2 mol%. As a result of observation with an electron microscope, the average particle size was 0.25 μm, and the variation coefficient of the particle size distribution was observed. The emulsion was found to be a 12% monodisperse emulsion.

The shape of the obtained silver iodobromide grains is almost cubic,
The corners and sides were slightly rounded.

Preparation of silver iodobromide emulsion (Em-2 to 5) In the preparation of silver iodobromide emulsion (Em-1),
1) When 296 ml was added, a silver iodobromide emulsion was prepared in exactly the same manner as Em-1, except that the amount of potassium hexachloroiridate (IV) (K ₂ IrCl ₆ ) shown in Table 1 was added as an aqueous solution. Em-2 to 5 were prepared.

Emulsions Em-2 to 5 thus obtained are silver iodobromide emulsions having a silver iodide content of 2 mol%, as in Em-1, and as a result of observation with an electron microscope, a single emulsion having an average grain size of 0.25 μm was obtained. It was found to be a dispersed emulsion. The particle shape is the same as Em-1, and the variation coefficient of the particle size distribution is shown in Table-2. Each emulsion contains the iridium ions in the amounts shown in Table 2.

Preparation of Red-Sensitive Emulsion-1 (R-1 to 5) 300 ml of each of the silver iodobromide emulsions Em-1 to 5 prepared as described above was stirred at 55 ° C. while stirring at 55 ° C. to obtain the following sensitizing dye (a) 150 mg was added as a 1% methanol solution.
After 0 minute, 30 μmol of sodium thiosulfate was added as a 0.1% aqueous solution. Keep the temperature at 55 ° C and stir for 150
After aging for a minute, the temperature was lowered to 40 ° C, and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 45 was added.
The emulsion was stabilized by adding 0 mg and the following antifoggant ST-1 250 mg, and the total amount was adjusted to 540 ml with ion-exchanged water. Thus, red-sensitive emulsions R-1 to R-5 were obtained.

Preparation of Red-Sensitive Emulsion-2 (R-11 to 15) 300 ml of each of silver iodobromide emulsions Em-1 to 5 was kept at 52 ° C. and stirred, and 150 mg of the above sensitizing dye (a) was converted into a 1% methanol solution. 10 minutes later, 15 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and 60 minutes later, 10 μmol of chloroauric acid (as a 0.05% aqueous solution) and 20 μmol of ammonium thiocyanate (a 0.1% aqueous solution) were added. Optimum time (30-80 minutes) with stirring at 52 ° C
After aging, the temperature was lowered to 40 ° C.
The emulsion was stabilized by adding 450 mg of 6-methyl-1,3,3a, 7-tetraazaindene and 250 mg of the above-mentioned antifoggant ST-1, and the total amount was adjusted to 540 ml with ion-exchanged water. Thus, red-sensitive emulsions R-11 to R-15 were obtained.

Preparation of Red-Sensitive Emulsion-3 (R-16 to 20) In the preparation of R-11, the amounts of chloroauric acid and ammonium thiocyanate added were changed as shown in Table 3, and the ripening time after the addition of chloroauric acid was 30. R-16 to R-20 were prepared in exactly the same manner as for R-11 except that the optimization was carried out in the range of 120120 minutes.

Preparation of Red-Sensitive Emulsion-4 (R-21) R-11 was prepared in the same manner as R-11 except that an aqueous solution of chloroauric acid and an aqueous solution of ammonium thiocyanate were separately added to the emulsion without prior mixing. R-21 was prepared in the same manner.

Preparation of Red-Sensitive Emulsion-5 (R-31) R-2 was prepared in the same manner as R-2 except that 15 mg of the following sensitizing dye (b) was added as a 1% methanol solution simultaneously with the sensitizing dye (a). R-31 was prepared in the same manner.

Preparation of organic silver salt dispersion 28.8 g of benzotriazole silver obtained by reacting benzotriazole and silver nitrate in a water-alcohol mixed solvent
And 16.0 g of poly (N-vinylpyrrolidone) and 1.33 g of sodium 5-methylbeenzotriazole were dispersed in an alumina ball mill to adjust the pH to 5.5 to 200 ml.

Preparation of Dye Donor Dispersion-1 35.5 g of the following polymer dye donor (1) and 5.0 g of the following hydroquinone compound were dissolved in 140 ml of ethyl acetate, and 124 ml of a 5% by weight aqueous solution of alkanol XC (manufactured by DuPont) and 14.4 g of gelatin were prepared. After mixing with 195 ml of an aqueous gelatin solution containing and dispersing with an ultrasonic homogenizer, and distilling off ethyl acetate, the pH was lowered.
The mixture was adjusted to 5.5 to 475 ml to obtain Dye Donor Dispersion-1.

Preparation of Reducing Agent Solution 20.0 g of a reducing agent (the following compound RE-1), 13.3 g of a reducing agent (the following compound RE-2), and poly (N-vinylpyrrolidone) 14.
6 g, the following fluorine-based surfactant 0.50 g dissolved in water, pH 5.5
To obtain a 250 ml reducing agent solution.

Preparation of Thermal Solvent Dispersion A 25% aqueous polyvinylpyrrolidone solution containing 25 g of the following thermal solvent-1 and 0.04 g of the following surfactant [1]
The mixture was dispersed in alumina with an alumina ball to make 120 ml.

Preparation of photosensitive material The red-sensitive silver iodobromide emulsion prepared above (R-1 to 5, R
-11 to 21, R-31), using an organic silver salt dispersion, a dye-donor dispersion, a reducing agent dispersion and a hot solvent dispersion, corresponding to the silver iodobromide emulsion No. Photosensitive materials Nos. 1 to 5, 11 to 21, and 31 having such a two-layer structure were prepared.

Preparation of Image Receiving Member-1 Polyvinyl chloride (n = 1,100, manufactured by Wako Pure Chemical Industries, Ltd.) in tetrahydrofuran was coated on 150 g / m ² photographic baryta paper, and the image was received at 12 g / m ^{2 of} polyvinyl chloride. Member-1 was created.

Low illuminance long exposure For the photothermographic materials No. 1 to 5, 11 to 21, and 31,
Using a tungsten lamp as a light source, pseudo-monochromatic light was produced by passing through a Toshiba color glass filter R-60 and a Toshiba interference filter KL-63, and exposure was performed for 30 seconds through a step wedge. The irradiation energy at the exposure position can be measured with an optical power meter (Ando Electric AQ-
2101, sensor: AQ-2702), 633n
It was 1180 erg / cm ² in terms of m monochromatic light.

High-intensity short-time exposure (scanner exposure) For the photothermographic materials Nos. 1 to 5, 11 to 21, and 31,
Scanning exposure using a scanning exposure device equipped with a He-Ne laser (oscillation wavelength 633 nm) as a red light source, a He-Ne laser (oscillation wavelength 544 nm) as a green light source, and an AlGaAs semiconductor laser (oscillation wavelength 780 nm) as an infrared light source. Was performed.

 The attached drawing is a block diagram of the scanning exposure apparatus.

The signal IR is input to the semiconductor laser modulation circuit 27, the semiconductor laser 1 is modulated by the output signal 31, and the modulated output light 34 is converged by the lens 2, and the filter 4,
After passing through the lens 5, only the infrared light component is reflected by the dichroic mirror 6 in a certain direction of the polygon mirror 19.

The green component laser light 35 output from the He-Ne laser 7 passes through the lens 8 and is input to the optical modulator 9, and outputs a light 38 modulated according to the signal G. Through the path 11, only the green component light is reflected by the dichroic mirror 12, becomes a light 44 mixed with the infrared component light 43 reflected by the dichroic mirror 6, and enters the dichroic mirror 18. Further, in the same manner as above, the He-Ne laser 13
The outputted red component laser light 36 passes through the lens 14 and is input to the optical modulator 15 and outputs light 39 modulated according to the signal R. The light 39 passes through the path of the filter 16 and the lens 17. , Only red component light is dichroic mirror 18
Is reflected by the polygon mirror, and becomes a light 45 mixed with the light 44 already mixed with the infrared light component and the green light component.
Guided to 19. The light scanned by the polygon mirror 19 is subjected to fθ conversion by the fθ lens 20, and is imaged on the photosensitive material 23 via the mirror 21 and the cylindrical lens 22. As described above, the light whose intensity is modulated corresponding to the signals R, G, and IR is exposed on the photosensitive material.

The stage 24 supporting the photosensitive material 23, due to the mutual movement of the spur gear 30 provided on the side surface and the gear 25 provided on the motor 26,
The rotational movement of the motor 26 is transmitted so that the motor 26 can be translated.

The polygon mirror 19 is installed so as to be driven by a polygon mirror driving unit 47. Therefore, the signal R,
The control signal generator 48 is synchronized with G and IR by the input SYNC signal.
The motor drive circuit 46 is operated by the signal output from the, the motor 26 is driven, and the stage 24 is transported. The rotation of the polygon mirror 19 is also controlled. By the above, photosensitive material
At 23, a two-dimensional image is exposed.

Using this exposure apparatus, the photothermographic materials Nos. 1 to 5, 11 to 21, and 31 were exposed while changing the exposure amount stepwise.

The exposure time per pixel is 0.3 microsecond.

After each of the above exposure to the photothermographic material,
The sheet was superposed on the image receiving member-1, and each was subjected to thermal development at 145 ° C. for 70 seconds. Next, when the photosensitive material and the image receiving member were immediately peeled off, a negative magenta image was obtained on the polyvinyl chloride of the image receiving member.

Using a densitometer (PDA-65,
(Konica Corporation)), the sensitometry of green light was measured. The reciprocal of the exposure amount (erg / cm ² ) giving a reflection density of minimum density + 0.3 was defined as sensitivity. The sensitivity at the time of exposure for 0.3 microsecond is S _H , and the sensitivity at the time of exposure for 30 seconds is S _L. The resulting S _H, shown in Table 5 and S _L and S _H / S _L.

The results in Table -5, S _H / S _L can be increased by adding a gold sensitizer and iridium ions as described above, a low-sensitive material is obtained with high and low light sensitivity is high light sensitivity It is understood that it is possible.

Example-2 Infrared-sensitive silver iodobromide emulsions, green-sensitive silver iodobromide emulsions, and dye-donor dispersions-2 and 3 were prepared as follows.

Preparation of Infrared Photosensitive Emulsion-1 (IR-1) 300 ml of silver iodobromide emulsion Em-2 was kept at 55 ° C. and stirred, and the following sensitizing dye (c) 50 mg and the following sensitizing dye (d )
30 mg of each was added as a 0.1% methanol solution, and 10 minutes later, 50 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and the mixture was kept at 55 ° C. for 180 minutes with stirring, and then kept at 40 ° C. To 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene
The emulsion was stabilized by adding 450 mg and the above-mentioned antifoggant ST-1 250 mg, and the total amount was adjusted to 540 ml with ion-exchanged water. Thus, an infrared-sensitive emulsion IR-1 was obtained.

Preparation of infrared-sensitive emulsion-2 (IR-2) 300 ml of silver iodobromide emulsion Em-2 was kept at 52 ° C and stirred to obtain 50 mg of the sensitizing dye (c) and the sensitizing dye (d )
30 mg each was added as a 0.1% methanol solution, 10 minutes later, 15 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and 60 minutes later, 5 μmol of chloroauric acid (as a 0.05% aqueous solution) and ammonium thiocyanate (a 0.1% aqueous solution) were added. ) 10 μmol was added. Keep it warm at 52 ° C,
After aging for 55 minutes with stirring, the temperature was lowered to 40 ° C., and 450 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 250 mg of the antifoggant ST-1 were added. The emulsion was stabilized with ion-exchanged water to adjust the total volume to 540 ml. Thus, an infrared-sensitive emulsion IR-2 was obtained.

Preparation of Green-Sensitive Emulsion-1 (G-1) 300 ml of silver iodobromide emulsion Em-2 was stirred while keeping it at 55 ° C., and 250 mg of the following sensitizing dye (e) was added as a 1% methanol solution. Ten minutes later, 50 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and the mixture was kept at 55 ° C. and aged for 150 minutes with stirring.
℃, 4-hydroxy-6-methyl-1,3,3a, 7-
450 mg of tetraazaindene and the antifoggant ST-1250
Stabilize the emulsion by adding
It was adjusted to 0 ml. Thus, a green-sensitive emulsion G-1 was obtained.

Preparation of Green-Sensitive Emulsion-2 (G-2) 300 ml of silver iodobromide emulsion Em-2 was stirred while being kept at 52 ° C., and 150 mg of the sensitizing dye (e) was added as a 1% methanol solution, respectively. Ten minutes later, 15 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and 60 minutes later, 5 μmol of chloroauric acid (as a 0.05% aqueous solution) and 10 μmol of ammonium thiocyanate (a 0.1% aqueous solution) were added.
The temperature was kept at 52 ° C as it was, and aging was continued for 75 minutes with stirring, then the temperature was lowered to 40 ° C, and 450 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and the above-mentioned antifogging were prevented. The emulsion was stabilized by adding 250 mg of the agent ST-1, and the total volume was adjusted to 540 ml with ion-exchanged water. Thus, a green sensitive emulsion G-2 was obtained.

Preparation of Dye Donor Dispersion-2 In the preparation of Dye Donor Dispersion-1, except that the dye donor was changed to the following polymer dye donor (2),
Dye-donating substance dispersion liquid-2 was prepared in the same manner as described above.

Preparation of Dye Donor Dispersion-3 Dye Donor Dispersion-3 was obtained in the same manner as Dye Donor Dispersion-1 except that the dye donor was changed to the following polymer dye donor (3).

Preparation of photosensitive material Using the organic silver salt dispersion, the red-sensitive silver iodobromide emulsion, the dye-donor dispersion, the reducing agent dispersion and the hot solvent dispersion prepared in the above-and Example 1, Photosensitive materials Nos. 101 to 104 having a multilayer structure as shown in Table 7 were prepared. The color-sensitive silver iodobromide emulsions were used in combination as shown in Table 6 below.

Low-illumination long-time exposure In the low-illumination long-time exposure of Example 1, in addition to Y-51 and KL-54, a combination of filters (combination of a Toshiba color glass filter and a Toshiba interference filter) is used.
(Green light) and a combination of R-68 and KL-78 (infrared light) in the same manner as in Example 1, except that the photothermographic materials Nos. Illumination Long exposure was performed. Maximum irradiation energy in the exposure position, the green light is 730erg / cm ² in terms of 545 nm, the infrared light was 1520erg / cm ² in terms of 780 nm.

High-illuminance short-time exposure Scanning exposure was performed using the scanning exposure apparatus used for high-illuminance short-time exposure in Example-1.

Each of the photothermographic materials Nos. 101 to 104 was subjected to the above-described exposure, and then superposed on the image receiving member-1, and each was subjected to thermal development at 145 ° C for 80 seconds. Next, when the photosensitive material and the image receiving member were quickly peeled off, negative cyan, magenta and yellow images were obtained on the polyvinyl chloride of the image receiving member.

The reflection density of the obtained transfer negative image was measured by sensitometry for red light, green light and blue light with a densitometer (PDA-65, manufactured by Konica Corporation). The reciprocal of the exposure amount (erg / cm ² ) giving a reflection density of minimum density + 0.3 was defined as sensitivity. The sensitivity at the time of exposure for 0.3 microsecond is S _H , and the sensitivity at the time of exposure for 30 seconds is S _L. The obtained S _H , S _L and S _H /
The S _L is shown in Table 8.

From Table 8, in the green-sensitive emulsion and an infrared-sensitive emulsion, also if these were multilayer coating, by adding a gold sensitizer and iridium as previously described, to increase the S _H / S _L be able to.

Example-3 The photothermographic materials Nos. 101 to 104 produced in Example-2 were subjected to the high-intensity short-time exposure of Example-2, and then placed on a desk in a dark room protected from light. Konica Safelight Glass No.9B (25.
4 × 30.5 cm, yellow-green).

Standing time and the minimum density Dmin (red, blue) and the relationship between S _H are shown in Table 9 and Table 10.

As is clear from Table-9, the photosensitive material of the present invention has a small fluctuation in minimum density and sensitivity in safelight irradiation. In contrast, a large variation in minimum density and sensitivity in the irradiation of S _H / S _L <2 remain S _H greatly photosensitive material No.104 in safelight. Therefore, the photosensitive material of the present invention is easy to handle under safelight.

Konica Safelight Glass No.9B transmits very little infrared light. As is clear from Table 10, the photosensitive material of the present invention has a small variation in Dmin and sensitivity even when irradiated with weak infrared light.

Therefore, it is considered that the device is stable against stray light in the device.

[Effects of the Invention] According to the present invention, the suitability for high-illuminance short-time exposure is excellent, that is, the suitability for scanner exposure is excellent, and handling under a safelight is easy. It was possible to obtain a stable photothermographic material, which hardly causes a problem.

[Brief description of the drawings]

The attached drawing is a block diagram showing an example of a scanning exposure apparatus. 1. Semiconductor laser (780nm) 2, 8, 14 ... Convergent lens 4, 10, 16 ... Filter 5, 11, 17 ... Lens 6, 12, 18 ... Dichroic mirror 7 ... He-Ne laser ( 544 nm) 13 He-Ne laser (633 nm) 9, 15 Optical modulator 19 Polygon mirror 20 f-θ lens 21 Mirror 22 Cylindrical lens 23 Photosensitive material 24 Stage 25 gear 26 motor 30 spur gear 27 semiconductor modulation circuit 46 motor drive circuit 47 polygon mirror drive 48 control signal generator

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-2249 (JP, A) JP-A-62-954 (JP, A) JP-A-2-40646 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 8/40 G03C 1/498

Claims (4)

(57) [Claims] 1. A heat-developable color light-sensitive material comprising at least a light-sensitive silver halide particle, a reducing agent, a dye-providing substance and a binder on a support, sensitized with gold and sulfur,
And a photosensitive layer containing a silver halide emulsion containing iridium ions.
And sensitivity the reciprocal of an exposure amount giving a high optical density, the sensitivity when exposed with 0.3 microseconds when the sensitivity S _L when exposed with S _H, 30 seconds, is S _H / S _L ≧ 2.0 A heat-developable color light-sensitive material, comprising: 2. The heat-developable color light-sensitive material according to claim 1, wherein S _H / S _L ≧ 4.0. 3. The heat-developable color light-sensitive material according to claim 1, wherein S _H / S _L ≧ 8.0. 4. The heat-developable color light-sensitive material according to claim 1, wherein the maximum wavelength of the spectral sensitivity is S _H / S _L ≧ 4.0 in the red light-sensitive layer having a wavelength shorter than 680 nm.