JPH095968A - Dye image receiving material - Google Patents

Abstract

PURPOSE: To decrease for during silver development in an unexposed part and to increase the rate of silver development in an exposed part by incorporating a hydrophilic binder, a dye mordant, a specified compd. and a nitrogen-contg. heterocyclic compd. on a supporting body to constitute a dye image receiving material. CONSTITUTION: This dye image receiving material is used in the process of heat development and dye transfer in the combination with a diffusion transfer- type heat developing color photosensitive material containing photosensitive silver halide and dye donating material which forms or releases diffusive dyes. The dye image receiving material contains a hydrophilic binder, a dye mordant, a compd. expressed by formula I and a nitrogen-contg. heterocyclic compd. expressed by formula II on a supporting body. In formula I, Y represents an atomic group necessary to form a five- or six-member ring, R1 is a hydrogen atom or alkyl group which may have substituents, and R2 is a hydrogen atom or alkyl group which may have substituents. In formula II, W is =N- or =C(R5 )-, R3 is a hydrogen atom or 1-4C alkyl group, and R4 and R5 are hydrogen atoms or amino groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye image receiving material used in combination with a diffusion transfer type heat developable color light-sensitive material, and more particularly to a dye image receiving material in which the maximum and minimum densities of a transferred dye image are improved.

[0002]

2. Description of the Related Art Conventionally, a method of obtaining a diffusion transfer image on an image receiving material by combining a silver halide photographic light-sensitive material containing a photosensitive silver halide and an image receiving material and performing development in the presence of a small amount of water or alkali. Are known, and a silver salt diffusion transfer system, a wet color diffusion transfer system, a heat development type color diffusion transfer system and the like are known.

Since such a diffusion transfer method does not require a bath treatment, it has advantages of downsizing of the apparatus and easy handling.

In particular, much research has been conducted in recent years on the heat development method in which the development step is performed by heating, and it is known to obtain a monochrome image and a color image. Also,
A so-called transfer type photothermographic material is also well known, which transfers an image obtained by heat development from the photographic material to the image receiving layer.

The present invention relates to a dye image receiving material which is used in combination with such a transfer type photothermographic material (hereinafter, also simply referred to as a photosensitive material), and has an improved maximum density and minimum density of a transferred image.

Conventionally, many various attempts have been made to improve the maximum density and the minimum density of a transferred image. Particularly important points are to reduce the fog during silver development of the silver halide emulsion and to achieve faster silver halide developability.

In particular, a dye which does not release a movable dye in a portion of a silver halide emulsion reduced to silver (hereinafter referred to as silver development) and which releases a mobile dye when silver development is not performed. In the heat development transfer method using a photothermographic material using a donor substance (hereinafter referred to as a positive dye donor substance), fogging of silver development is likely to be a problem.

The positive type dye-donating substance itself usually releases a dye under the condition of heat development, and the dye release is suppressed by the development of silver. Therefore, when the silver development speed in the exposed area is low, the fog of the transferred image increases, and when the fog in the silver development is high, the maximum density of the transferred image tends to decrease.

In particular, when the hardness of a photothermographic material containing a positive type dye-donating substance varies due to fluctuations in manufacturing conditions or so-called post-hardening during storage of the photosensitive material, the water absorption amount of the photosensitive material fluctuates and silver The developing speed easily fluctuates. As a result, a problem that the performance of the transferred image is likely to vary is likely to occur.

Conventionally, many techniques have been proposed to improve such points.

JP-A-62-40454 and JP-A-Hei-4
No. 3,555,752 discloses that a dye image-receiving material contains an antifoggant. However,
If the antifoggant is simply contained, the silver development rate in the exposed portion tends to be decreased easily when the amount for obtaining a sufficient antifoggant effect is added. When used, there is a problem that the minimum density of the transferred image tends to increase.

Japanese Unexamined Patent Publication No. 62-283335 discloses an image forming method in which heat development is carried out in the presence of a silver halide solvent. However, when a silver halide solvent as disclosed herein is used, a phenomenon generally referred to as dissolution physical development tends to occur, and fog in silver development tends to be high, but the acceleration effect of silver development itself is not so great. not big.

Japanese Unexamined Patent Publication No. 63-250646 describes an image forming method in which silver is developed preferentially for a certain period of time prior to the dye releasing reaction, and then heat development is carried out. Specifically, it is held at a temperature lower than the heat development temperature for a certain period of time, and then heat development is carried out. However, when such a system is adopted, the development time is extended and the temperature control becomes complicated. There is a point.

[0014]

The first object of the present invention is to develop silver in the unexposed area during thermal development using a diffusion transfer type photothermographic material (hereinafter also simply referred to as a photothermographic material). And to provide a dye image-receiving material having an improved silver developing speed in the exposed area.

A second object of the present invention is to provide a dye image receiving material capable of obtaining an excellent dye image at a low minimum density (Dmin) without lowering the maximum density (Dmax) by heat development transfer.

A third object of the present invention is to provide a dye image receiving material in which the photographic performance is less affected by the variation in the film hardness of the diffusion transfer type heat developable color light-sensitive material.

[0017]

The above object of the present invention is achieved by the following constitution.

1. On a support, a diffusion transfer type heat-developable color photosensitive material containing a photosensitive silver halide and a dye-donor substance that forms or releases a diffusible dye and a dye image-receiving material used in combination during heat development and dye transfer are provided. A dye image receiving material comprising a hydrophilic binder, a dye mordant, and a compound represented by the following general formula (1) and a nitrogen-containing heterocyclic compound represented by the following general formula (2).

[0019]

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In the formula, Y represents an atomic group necessary for forming a 5- or 6-membered ring and may form a condensed ring. R
₁ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group, R ₂ is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, and an aryl group, -SO ₃ H , -COOR ', -CONHR',-
_{NHCOR ', - SO 2 NR'R "} , - NHSO 2 R''. Represents the proviso R', or -SR and R" each represents a hydrogen atom, an alkyl group or an aryl group. However, at least one of R ₁ and R ₂ has at least one water-soluble group selected from a carboxyl group, a sulfo group or a sulfonamide group as a substituent.

[0021]

[Chemical 6]

In the formula, W represents = N- or = C (R ₅ )-, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄ and R ₅ are hydrogen atom, amino group, —COO
R _11, -NHCOR _12, represents a -CONH ₂ or an alkyl group having 1 to 4 carbon atoms. R ₁₁ represents a hydrogen atom or an alkyl group, and represents an R ₁₂ alkyl group. However, the total number of carbon atoms of R ₃ , R ₄ and R ₅ is 0 to 4.

2. 2. The dye image receiving material as described in 1 above, wherein the dye image receiving material further contains a compound represented by the following general formula (3a) or (3b).

[0024]

[Chemical 7]

In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and this nitrogen-containing heterocycle may have a substituent in addition to the --COOM group. M represents an alkali metal or a substituted or unsubstituted guanidinium ion, amidinium ion or quaternary ammonium ion.

[0026]

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In the formula, Ar represents a substituted or unsubstituted phenyl group or pyridyl group, and M is a general formula (3
It is the same as M of a).

3. The dye image-receiving material according to claim 2, wherein the heat development and the dye transfer are performed in the same step, and a small amount of water is supplied from the outside.

4. 4. The dye image receiving material according to any one of 1 to 3 above, wherein the dye image receiving material further contains a water-soluble bromide in an amount of 0.01 to 1 mmol per 1 m ² of the dye image receiving material.

The present invention will be described in detail below.

First, the compound represented by the general formula (1) will be described.

In the general formula (1), Y represents a group of atoms necessary for forming a 5- or 6-membered ring, and examples of the ring include heterocycles such as imidazole, triazole, tetrazole, thiazole, oxazole, pyrimidine, and the like. The ring may form a condensed ring. R ₁ is a hydrogen atom,
An alkyl group which may have a substituent (for example, a linear or branched alkyl group having 1 to 6 carbon atoms), an aryl group (for example, a phenyl group, a naphthyl group, etc.), R ₂ is a hydrogen atom, and each has a substituent. Alkyl groups (eg, linear or branched alkyl groups having 1 to 4 carbon atoms), alkenyl groups (eg, vinyl group, allyl group, etc.) and aryl groups (eg, phenyl group, naphthyl group, etc.) ), - SO ₃ H, -
COOR ', - CONHR', - NHCOR ', - SO 2 N
Represents R′R ″, —NHSO ₂ R ′, or —SR ′, wherein R ′ and R ″ are each a hydrogen atom, an alkyl group (for example, a linear or branched alkyl group having 1 to 4 carbon atoms) or an aryl group. (For example, a phenyl group, a naphthyl group, etc.) is represented. R above
Examples of the substituent of ₁ , R ₂ include an alkyl group, a sulfonamide group, a carboxyl group, a sulfo group, etc.
At least one of R ₁ and R ₂ has at least one water-soluble group selected from a carboxyl group, a sulfo group or a sulfonamide group as a substituent.

In the general formula (1), particularly preferable compounds are represented by the following general formulas (1a) to (1c).

[0034]

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[0035] In formula, R _1, R ₂ have the same meanings as R _1, R ₂ in the general formula (1).

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

[0037]

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[0038]

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Among the compounds represented by the general formulas (1a) to (1c), the compound represented by the general formula (1a) is particularly preferable.

Next, the compound represented by the general formula (2) will be described.

In the general formula (2), W represents = N- or = C (R ₅ )-, R ₃ is a hydrogen atom and has 1 carbon atom.
Represents an alkyl group of 4 to 4. R ₄ and R ₅ are a hydrogen atom, an amino _{group, -COOR 11, -NHCOR 12, -CONH} 2
Alternatively, it represents an alkyl group having 1 to 4 carbon atoms. R ₁₁ represents a hydrogen atom or an alkyl group, and represents an R ₁₂ alkyl group.
However, the total number of carbon atoms of R ₃ , R ₄ and R ₅ is 0 to 4
And is preferably 0-2. The alkyl group represented by R ₃ , R ₄ and R ₅ preferably has 2 or less carbon atoms. W is particularly preferably = N-.

Specific examples of the compound represented by the general formula (2) are shown below.

[0043]

[Chemical 12]

The compound represented by the general formula (1) is generally water-soluble and is added as an aqueous solution to the image receiving layer or other layers constituting the image receiving material (however, the image receiving layer side with respect to the support). The addition amount is 0.001 per 1 m ² of the image receiving material.
~ 1 mmol is preferable, and more preferably 0.01 ~.
It is 0.3 mmol. When the compound represented by the general formula (1) has a —COOH group or a —SO ₃ H group, it may be used as a salt of alkali, alkaline earth, amine or the like.

The compound represented by the general formula (2) is also generally water-soluble and is added as an aqueous solution to the image receiving layer or the layer constituting the other image receiving material (however, the image receiving layer side with respect to the support). The addition amount is 0.01 to 1 m ² of the image receiving material.
10 mmol is preferable, and 0.1 to 3 mmol is more preferable. When adding the compound represented by the general formula (2), it may be neutralized with sodium hydroxide or the like and added.

Two or more kinds of the compound represented by the general formula (1) and the compound represented by the general formula (2) may be used in combination. The ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is 0.005 in molar ratio.
-1 is preferable, and more preferably 0.01-0.5.

The dye image-receiving material of the present invention preferably further contains the compound represented by the general formula (3a) or (3b).

In the general formula (3a), Q represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle (eg, pyridine ring, pyrimidine ring, etc.), and this nitrogen-containing heterocycle is --COOM. It may have a substituent in addition to the group.
M represents an alkali metal or a substituted or unsubstituted guanidinium ion, amidinium ion or quaternary ammonium ion. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, etc.), a carboxyl group and the like.

In the general formula (3a), Ar represents a substituted or unsubstituted phenyl group or pyridyl group, and M is the same as M in the general formula (3a). Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, etc.), an alkoxy group (eg, methoxy group, etc.) and the like.

The compound represented by the above general formula (3a) or (3b) easily forms a complex with a metal such as zinc, calcium or aluminum, so that the photothermographic material can contain zinc hydroxide, calcium hydroxide or hydroxide. When aluminum is contained and the photothermographic material and the dye image-receiving material are superposed in the presence of a small amount of water, alkali can be rapidly released.

Regarding this technique, for example, US Pat.
260,598, JP-A-62-187847, and JP-A-6-187847.
2-187341, 62-129848, and Japanese Patent Application No. 6-221887.

Next, examples of the compound represented by formula (3a) or (3b) are shown below.

[0053]

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The dye image-receiving material of the present invention preferably further contains a water-soluble bromide in order to improve discrimination of silver development of the photothermographic material. As the water-soluble bromide, alkali metal salts such as sodium bromide and potassium bromide, and ammonium salts are preferable. The amount of the soluble bromide added is 0.01 to 1 mmol, preferably 0.02 to 0.5 mmol, per 1 m ² of the image receiving material.

The hydrophilic binder of each layer constituting the dye image-receiving material of the present invention is preferably composed mainly of gelatin.
The gelatin may be ordinary alkali-treated gelatin or acid-treated gelatin. Besides gelatin, gelatin derivatives such as phenylcarbamoyl gelatin and phthalated gelatin,
And other hydrophilic polymers. Examples of such hydrophilic polymers include polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, dextran, dextran sulfate, polystyrene sulfonic acid, carrageenan, polyacrylic acid-polyvinyl alcohol copolymer, styrene-maleic acid copolymer, Examples include carboxymethyl cellulose and hydroxymethyl cellulose. These hydrophilic polymers may be used not only as a binder but also as a thickener for giving the coating liquid a viscosity necessary for coating.

The dye image receiving material of the present invention (hereinafter, also simply referred to as image receiving material) contains a dye mordant (hereinafter also simply referred to as mordant).

As a preferable dye mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is used.
For example, JP-A-48-75237 and JP-A-50-612.
28, 50-80132, 50-73.
No. 440, No. 53-129034, No. 54-
No. 145529, No. 55-142339, No. 56-161410, No. 59-219745, No. 62-30249, and No. 62-3415.
Polymer mordants having a quaternary ammonium group described in, for example, US Pat.
Polyvinylpyridine mordants described in JP-A-60-23851, for example, US Pat. No. 4,115,12.
4, British Patents 2,056,101, 2,093,
041, JP-A-59-55436 and JP-A-60-2.
No. 3854, No. 60-39644, No. 60-
No. 60643, No. 60-118834, No. 6
No. 0-122941, JP-A No. 60-235124, and the like, polyvinyl imidazole-based mordants,
A mordant described in JP-A-47-3689, in which a group having a mordant ability is grafted, and JP-A-60-578.
Combined use of a tertiary amine-based mordant and a quaternary ammonium-based mordant described in JP-A-36-36, JP-A-63-1.
Examples thereof include mordants having an image stabilizing group described in JP-A-98051 and JP-A-2-32335.

Specific examples are the following compounds, but the present invention is not limited thereto.

[0059]

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[0060]

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A particularly preferred mordant is a mordant having a vinylimidazole group.

As a preferable image-receiving material, an image-receiving layer containing a dye mordant on a support and 1 provided thereon
Alternatively, there is an image receiving material composed of two or more protective layers. Further, as another preferable image receiving material, a support, an image receiving layer,
An image receiving material having an ultraviolet absorber-containing layer and a protective layer on a support in this order is mentioned. It is also possible to have an undercoat layer having a hydrophilic bander.

Further, the image receiving material of the present invention may have a back layer on the side opposite to the base precursor-containing layer.
The back layer may be either a hydrophilic binder or a hydrophobic binder, and may contain a matting agent.

The image-receiving material of the present invention may contain various compounds other than the above. Examples of such additives include stain inhibitors and ultraviolet absorbers (for example, benzophenone compounds and benzotriazole compounds described in JP-A-60-130735 and JP-A-61-153638). , Fluorescent whitening agents (e.g., diaminostilbene compounds described in JP-A-61-143752, compounds described in JP-A-63-147166), image stabilizers (e.g. 59-182785, 61-159644, development accelerators, organic fluorine compounds, silicone oils, surfactants, hardeners, polymer latices (for example, described in JP-A-61-156045), Examples thereof include matting agents, antifungal agents and various transition metal ions.

Next, the method for producing the image receiving material of the present invention will be described in more detail.

The compound represented by the general formula (1), (2) and (3a) or (3b) added to the image receiving material of the present invention constitutes the image receiving material as long as it is on the side where the light sensitive material is superposed. Can be added to the coating liquid for forming any layer, and can be added to all or a part of the coating liquid for forming the hydrophilic binder-containing layer.
The general formula (1), (2) and (3a) or (3) of the present invention
Since the compound represented by b) is generally highly water-soluble, even if it is added to any layer of the hydrophilic binder-containing layer, it rapidly diffuses between the layers after coating and becomes in an equilibrium state.

The base precursor may be added to the coating solution in advance, and the coating solution may be stagnant for continuous coating, or may be added inline immediately before coating (for example, within about 10 seconds). Good.

In the image-receiving material of the present invention, when the compound represented by the general formula (3a) or (3b) is added, sodium hydroxide or alkali hydroxide salt is added to the corresponding carboxylic acid to neutralize it. Maybe, Japanese Patent Application No. 6-22
As described in No. 9773, equivalent amounts of sodium carbonate and potassium carbonate may be added, and carbon dioxide may be volatilized after coating and drying.

The pH of the coating solution forming the image receiving material is
About 6-8.5 is preferred. The film surface pH of the image receiving layer surface after coating and drying is preferably about 9 or more, and more preferably 9.5 or more.

Here, the membrane surface pH of 30 μl was dropped onto the hydrophilic binder layer surface with a microsyringe, and immediately the surface p
It refers to the pH measured at 20 to 25 ° C. using the H electrode.

The hydrophilic binder of the image receiving material needs to be hardened by a hardener. As the hardener, conventionally known hardeners for organic and inorganic photography can be used. Specifically, aldehyde hardeners, epoxy hardeners, vinyl sulfone hardeners, Acryloyl type hardeners, dichloro-s-triazine type hardeners, carboxy activated type hardeners and the like are used, but the film of the image receiving material of the present invention has a high pH of 9 or more during the drying process and the subsequent storage process. Hardeners that themselves are susceptible to hydrolysis are less preferred, for example dichloro-
The s-triazine type hardener and the ethyleneimino type hardener are less preferable when they are used alone.

Particularly preferred hardeners are vinyl sulfone hardeners, epoxy hardeners and acryloyl hardeners.

The above-mentioned hardener is generally preferably added to a coating solution containing no base precursor or mordant. Most preferably, a hardener is added to the coating liquid that forms the protective layer.

The above various coating liquids for forming the image receiving material can be coated on the support at the same time or layer by layer, but it is preferable to coat all the hydrophilic binder layers at the same time.

When the image-receiving material is applied continuously, the above-mentioned various coating solutions are generally stagnant at 25 to 40 ° C. The coating method may be any conventional method for photographic use.

When the pH of the film surface after drying is less than 9, the rapid rate of pH increase which is the effect of the present invention cannot be obtained.

In order to bring the pH of the film surface to 9 or more after drying, it is necessary to evaporate carbon dioxide gas sufficiently during the drying process. For that purpose, the film temperature is 3 at least in a part of the drying.
From the viewpoint of rapid production, it is preferable to temporarily raise the temperature to 5 ° C or higher. Particularly, it is preferable to temporarily set the temperature to 40 ° C. or higher.

The dried image receiving material is temporarily conditioned under a greenhouse condition of 20 to 30 ° C. and a relative humidity of 40 to 60%, and then wound in a roll state.

The coated image-receiving material is generally heated and stored at 30 to 40 ° C. for a certain period of time for hardening reaction, but since the image-receiving material of the present invention has a high film surface pH. However, such heating is not always necessary.

As the support used in the dye image-receiving material of the present invention, a support known as a support for conventional photography can be used. The reflective support is preferably a paper support whose both surfaces are coated with polyethylene or the like, but a polyethylene phthalate support containing or coated with a white pigment such as barium sulfate or titanium dioxide is preferably used. Also, OH
As the transparent support for P or the like, a polyethylene terephthalate support is preferably used.

Next, the diffusion transfer type photothermographic material which is used in combination with the dye image-receiving material of the present invention (hereinafter also simply referred to as photothermographic material) will be described.

The photothermographic material contains at least a photosensitive silver halide and a dye-donor which forms or releases a diffusible dye.

As the photosensitive silver halide, a conventionally known one can be used, and for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide can be used. .

These silver halides have a uniform composition from the inside to the surface of the grain, a so-called core / shell type in which the composition is different between the inside and the surface, or a multi-layer structure in which the composition changes stepwise or continuously. It may be silver halide. Further, silver halide in which a component having a specific composition is localized inside the grain (for example, silver iodobromide in which silver iodide is localized inside the grain) can also be used.

Further, the silver halide may be either monodisperse with a relatively uniform grain size or polydisperse with a broad grain size distribution.

The shape of silver halide may be cubic, spherical, octahedron, dodecahedron, tetrahedron or the like having a clear crystal habit or not. Further, for example, JP-A-58-111933 and JP-A-58-11193.
No. 4, Research Disclosure 22534, which has two parallel crystal planes, each of which has a larger area than the other crystal planes. Tabular silver halide having a thickness ratio of about 5: 1 or greater can also be used.

Further, for example, US Pat. No. 2,592,25
No. 0, 3,220,613, 3,271,257
No. 3,317,322 and 3,511,622
Nos. 3,531,291 and 3,447,927
Nos. 3,761,266 and 3,703,584
Nos. 3,736,140 and 3,761,276
No., JP-A-50-8524, JP-A-50-38525,
The internal latent image type silver halide emulsions described in JP-A No. 52-15661, JP-A No. 55-127549, etc., whose grain surfaces are not fogged in advance, can also be used.

The photosensitive silver halide can be formed at any stage of the grain formation by using iridium, gold, rhodium, iron,
Metal ion species such as lead can be added in the form of a suitable salt.

In this case, it is general to add these metal ions in the range of 10 ^-7 to 10 ^-5 mol per mol of silver.

The photosensitive silver halide emulsion preferably has a grain size of about 0.05 to 2 μm, more preferably about 0.1.
Is about 1.0 μm. Further, for the purpose of gradation adjustment, it is possible to use silver halides having different average grain sizes in the same photosensitive layer in combination.

The photosensitive silver halide emulsion is obtained by chemically sensitizing the surface of the silver halide grain with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate). You can

The chemical sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing nitrogen-containing heterocyclic compound.

Further, the photosensitive silver halide can be spectrally sensitized to blue, green, red and infrared light by a known spectral sensitizing dye. A typical sensitizing dye is, for example, JP-A-59-59.
-180553, 60-140335,
No. 60-263937, No. 61-65232, No. 61-153635, No. 61-15363.
1, gazette 62-32446 gazette, gazette 63-612.
42, 63-138343, and JP-A-3-
No. 163440, No. 4-31854, No. 4-
No. 34547, No. 5-45833, etc. are described. Furthermore, for example, JP-A-62-39846, JP-A-62-86360, JP-A-62-89037, JP-A-62-147450, and JP-A-62-1474.
As described in JP-A-51, the sensitizing dyes may be used in combination of two or more kinds in a single silver halide.

The amount of these sensitizing dyes used is preferably 10 ^-5 to 10 ^-2 mol per mol of silver halide. The sensitizing dye may be added at any stage of the silver halide emulsion, and any of during the formation of silver halide grains, the removal of soluble salts, the start of chemical sensitization, the time of chemical sensitization, or the end of chemical sensitization. May be

These photosensitive silver halide and photosensitive silver salt-forming components are preferably used in an amount of about 0.01 to 10 g, and more preferably 0.05 to 1 g (per each photosensitive layer) per 1 m ² of the photosensitive material. Used.

As the dye-providing substance, a diffusion-resistant dye-providing substance capable of forming or releasing a diffusible dye during heat development is preferably used. Such dye-donor substances are
Conventionally known dye-donor substances are used in the diffusion transfer system.

First to release diffusible dye upon thermal development
Is a dye-donor substance that releases a diffusible dye by being oxidized during heat development.
No. 48-33826, No. 53-50736,
No. 51-113624, No. 56-12642, No. 57-650, No. 51-104343, No. 53-46730, and No. 54-130122.
No. 57-85055 and No. 59-1650.
54, 61-193149 and 61-2.
No. 28443 (Negative dye-providing substance).

Another example of this type is that it releases a diffusible dye upon hydrolysis in the presence of an alkali, but does not release a diffusible dye by reacting with an oxidized product of a developing agent. Such dye-providing substances include, for example, JP-A-51-63618, JP-A-53-69033, JP-A-54-130927, and JP-A-49-11162.
8, gazette 52-4819 gazette, gazette 59-1243.
No. 27, No. 59-152440 and the like (positive dye-providing substance).

Another example of this type of dye-donor element is that which does not itself release a dye, but which reacts with the remaining reducing agent not used in development to release a diffusible dye. For example, JP-A-53-35533, JP-A-53-
110827, U.S. Pat. No. 4,358,525, JP-A-54-130927, and JP-A-56-164.
No. 342, No. 62-215270, and JP-A-1
-120553, Japanese Patent Publication No. 4-11017,
No. 3-65535, etc. (positive dye-providing substance).

As another type of dye-providing substance, diffusibility in the presence of a silver ion or a soluble silver ion complex constituting silver halide or organic silver which is not used for development during thermal development and remains. There are those that release the dye of
JP-A-59-180548, US Pat. No. 43628
06, 3719489, and 4375507.
No. (positive dye-donor).

Further, Japanese Patent Publication No. 48-39165, US Pat. No. 3,227,550, and Japanese Patent Laid-Open No. 57-18674.
4, gazette 58-79247 gazette, gazette 59-176.
A coupler in which a diffusible image-forming dye is previously bound to a leaving group of an active site described in Japanese Patent No. 744, etc. can also be used in the present invention (negative dye-providing substance).

Further, US Pat. Nos. 3,134,764, 3,597,200, 3,544,546, 3,482,972, and JP-A-59-165054 and 61- 193149 gazette, the same 61-22844.
As described in JP-A-3, etc., it itself has a reducing property with respect to silver halide and a diffusibility under alkaline conditions, but it is oxidized in correspondence with the development of silver halide. A dye-providing substance which reduces diffusivity by being added can also be used in the present invention (positive dye-providing substance).

On the other hand, as the dye-donating substance used in the method of forming a diffusible image-forming dye at the time of thermal development, an oxidized product of a developer and a cup produced at the reduction of silver halide and / or organic silver are used. There are dye-donor substances that undergo a ring reaction to form a diffusible dye, examples of which include, for example,
U.S. Pat. No. 3,531,286, Japanese Patent Publication No. 3-60419
JP-A Nos. 1-46054, 1-40973, 1-335334, 3-74818, and JP-A-62-123456, 63-118.
No. 155, No. 63-144350, etc. (negative dye-providing substance).

These dye-donor substances may be used alone or
Two or more kinds may be used in combination, and the amount thereof used may vary widely depending on the kind of the dye-donor substance and the use of the photothermographic material. Approximately 0.05 per 1 m ^{2 of} photothermographic material
It is preferably from 10 to 10 g, more preferably from 0.1 to 5 g.

As a method of incorporating the above dye-donor substance into the photographic constituent layer of the photothermographic material, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate,
A method of emulsifying and dispersing in a hydrophilic colloid solution using a known high-boiling-point organic solvent such as tricresyl phosphate or poly (N-butylacrylamide), an acid after being dissolved in an alkaline hydrophilic colloid aqueous solution. It can be appropriately selected and used from known methods such as a method of neutralizing and dispersing with a hydrophilic colloid, or a method of mechanically wet pulverizing into a fine particle solid state in a hydrophilic colloid aqueous solution and dispersing. When the fine particles are dispersed and used, the average particle diameter thereof is generally preferably 0.05 to 10 μm, and more preferably 0.1.
２2 μm.

The general formula (3) contained in the image receiving material of the present invention is
When the photothermographic material contains a sparingly water-soluble metal compound that releases an alkali through a complex-forming reaction with the compound represented by a) or (3b), alkali is generated by simply supplying water from the outside during thermal development. You can

Such a water-insoluble metal compound is 20
Metal oxides, hydroxides, carbonates, phosphates, silicates, borates, aluminates, etc., whose solubility in water at 0 ° C (the number of grams of solute dissolved in 100 g of water) is 0.5 or less Is more preferable, and more preferably represented by the following general formula (4).

General Formula (4) ZmXn In the general formula (4), Z represents a metal other than an alkali metal, X represents an oxide ion, a hydroxide ion, a carbonate ion, a phosphate ion, a silicate ion, boric acid. Represents an ion or an aluminate ion. m and n each represent an integer such that the valences of Z and X are balanced. The metal compound represented by the general formula (2) may have water of crystallization and may form a double salt.

Preferred examples of Z include Zn ²⁺ and C
o ²⁺ , Ni ²⁺ , Fe ²⁺ , Mn ²⁺ , Cu ²⁺ , Hg ²⁺ , Zr
^Examples thereof include transition metal ions such as ²⁺ and alkaline earth metal ions such as Ba ²⁺ , Sr ²⁺ and Ca ²⁺ . Particularly preferred is Zn ²⁺ ion.

Preferred examples of X are oxide ions,
Examples thereof include hydroxide ion, phosphate ion and carbonate ion, with hydroxide ion being particularly preferred.

Next, specific examples of the water-insoluble metal compound represented by the general formula (4) will be given below.

Zn (OH) ₂ , ZnO, Co (OH) ₂ ,
CoO, Ni (OH) ₂ , Cu (OH) ₂ , Fe (OH)
₂ , Mn (OH) ₂ , BaCO ₃ , SrCO ₃ , CaC
O ₃ , basic zinc carbonate, basic cobalt carbonate, basic nickel carbonate, basic bismuth carbonate Among these complex-forming compounds, especially, when dispersed in a dispersion medium containing water, the dispersion liquid is not colored. preferable.
Most preferred is Zn (OH) ₂ .

The combination of the compound represented by the general formula (4) and the compound represented by the general formula (3a) or (3b) is arbitrary, and each compound may be used alone or in combination of two kinds. You may use together the above.

The preferred amount of use varies depending on the state of the system and the amount of alkali necessary for the system, but a preferred use ratio is represented by the compound represented by the general formula (4): the general formula (3a) or (3b). The compound is 5: 1 to 5: 1 by molar ratio.
It is in the range of 1: 5, and particularly preferably used in the molar ratio range of 3: 1 to 1: 2.

A known organic silver salt can be used in the light-sensitive material used in the above-mentioned image forming method, if necessary, for the purpose of increasing sensitivity and improving developability.

The organic silver salt that can be used in the present invention can be any organic silver salt known in the field of photothermographic materials, and the main organic silver salt is, for example, silver of a long-chain aliphatic carboxylic acid. Examples thereof include salts and silver salts of carboxylic acids having a heterocycle (for example, silver behenate, α- (1-phenyltetrazolethio) acetic acid silver) and silver salts of compounds having an imino group. Further, acetylene silver described in JP-A-61-249044 and the like can be used, but among them, silver salts of compounds having an imino group are preferable, and silver salts of benzotriazole and its derivatives are particularly preferable. The amount of the organic silver salt used is preferably 0.005 g to 10 g, and more preferably 0.01 to 5 g per 1 m ² of the light-sensitive material.

The photothermographic material may contain a reducing agent as its constituent component. As the reducing agent used here, an appropriate one can be selected and used from conventionally known ones according to the developing mechanism and the dye forming or releasing mechanism. The reducing agent referred to herein includes a reducing agent precursor that releases the reducing agent during development.

Examples of the reducing agent that can be used in the present invention include Research Disclosure 1214.
6, 15108, 15127 and JP-A-56.
-27132, 53-135628, 57-7
P-phenylenediamine system described in No. 9035, and p
-Aminophenol type developing agent, phosphoric amide phenol type developing agent, sulfonamide aniline type developing agent,
And hydrazone-based developing agents, phenols, sulfonamide phenols, polyhydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and the above various There are reducing agent precursors.

Further, the dye-providing substance can also serve as the reducing agent.

Two or more reducing agents may be used in combination, especially 1
A combination of -aryl-3-pyrazolidone and a diffusion-resistant hydroquinone derivative is preferred. The total amount of the reducing agent is preferably in the range of 0.2 to 10 mol based on the total amount of the photosensitive silver halide.

A hydrophilic binder is preferably used in the photothermographic material. As the hydrophilic binder, the same binder as that used in the dye image-receiving material can be used.

The amount of the hydrophilic binder used is usually Support 1
The total amount per m ² is preferably 0.5 to 20 g, more preferably ² to 8 g. The amount of the photosensitive layer and the non-photosensitive layer used per layer is generally 0.2 to ² per 1 m ^{2 of the} support.
It is preferably g.

The binder is preferably hardened with a known photographic hardener. Examples of the hardener include a vinyl sulfone hardener, an aldehyde hardener, an epoxy hardener, an N-methylol hardener, and a halogen-substituted -S- hardener.
And triazine-based hardeners. Further, the hardener may be a polymer hardener.

In addition to the above, various additives as shown below can be used in the above-mentioned photothermographic material, if necessary.

[Thermal Solvent] The thermal solvent used for the purpose of accelerating the transfer of the dye in the photothermographic material and / or the image receiving material is a compound which is liquefied during the heat development and has the action of accelerating the heat development and the thermal transfer of the dye. However, it is preferably in a solid state at room temperature.

Examples of the thermal solvent that can be used in the present invention include US Pat. Nos. 3,347,675 and 3,66.
7,959, 3,438,766, 3,66
No. 6,477, Research Disclosure (No. 1)
7643), Japanese Patent Laid-Open Nos. 19-19525 and 53-53.
No. 24829, No. 53-60223, No. 58-118.
640, 58-198038, 59-2295.
56, 59-68730, 59-84236.
No. 60, No. 60-191251, No. 60-232547.
No. 60, No. 60-14241, No. 61-52643, No. 62-78554, No. 62-42153, No. 62-.
44737, 63-53548, 63-161.
Examples thereof include compounds described in JP-A No. 446, JP-A Nos. 1-224751 and 2-863.

[Development accelerator] For example, JP-A-59-177.
No. 550, No. 59-111636, No. 59-1243
No. 33, No. 61-72233, No. 61-236548
And JP-A-1-152454 are useful, and compounds disclosed in JP-A-61-159542 and JP-A-1-159454 are useful.
No. 04645 and JP-A-1-110767 can also be used.

[Antifoggant] For example, US Pat.
No. 00,457, mercapto compound-releasing compounds described in JP-A Nos. 51-50725, 2-297548 and 2-282241, and sulfinic acids and thiosulfonic acids described in 53-19825. Two
Sulfur No. 6019, No. 51-42529, No. 51-
No. 81124 and No. 55-93149, disulfides and polysulfides, US Pat. No. 4,138,
No. 265, thiazolithion, JP-A-54-5182
No. 1, 55-142331, U.S. Pat. No. 4,13.
Triazoles described in 7,079, JP-A-55-14
Thiosulfinic acid esters described in 0883, thiol compounds described in JP-A-59-111636, and 60-
The hydroquinone derivative etc. of 198540 and 60-227255 are mentioned.

Other preferable antifoggants include an antifoggant having a hydrophilic group described in JP-A-62-78554, a polymer anti-foggant described in JP-A-62-121452, and JP-A-62-1825. The antifoggant having a ballast group described in No. 123456 can be mentioned.

Water-soluble halides (potassium bromide, potassium iodide, sodium chloride, etc.) can also be used for the purpose of preventing fog and other purposes.

[Silver ion scavenger] JP-A-63-1633
No. 45, a physical development nucleus, a diffusion resistant compound that forms a stable complex against silver ions, and a compound that forms a sparingly soluble silver salt, described in JP-A-63-501745, page 6. A compound etc. are mentioned.

Various known photographic additives other than those mentioned above can be used in the photothermographic material. Examples thereof include water-soluble or hydrophobic filter dyes, colloidal silver, optical brighteners, antistatic agents, Can contain surfactants (anionic, cationic, nonionic, fluorine-containing anion, etc.), inorganic and organic matting agents, anti-fading agents, ultraviolet absorbers, white background color tone adjusting agents, anti-vibration agents, etc. . These are specifically described in RD (Research Disclosure) No. No. 17029, the same No. No. 29963, JP-A Nos. 62-135825 and 64-13546.

These various additives are used in the photosensitive layer, the intermediate layer,
It can be appropriately added to any constituent layer such as a mordant layer, an undercoat layer, a protective layer or a backing layer.

When the photothermographic material comprises two or more photosensitive layers, an intermediate layer is preferably used between the two photosensitive layers for the purpose of preventing color mixture. In the intermediate layer, for the purpose of effectively preventing color mixing, a reducing agent such as a diffusion-resistant hydroquinone derivative for preventing interlayer migration of the oxidized form of the reducing agent, and silver ion for preventing the diffusion of silver ion. A scavenger can be added.

The support used in the photothermographic material is preferably a transparent or opaque synthetic plastic film such as a polyethylene terephthalate film or a polyethylene naphthalate film, a polyethylene resin coated paper, and electron beam curing on these various supports. Examples thereof include a support coated with and cured with a functional resin composition.

When the photothermographic material used in the image forming method using the image receiving material of the present invention is used as a full-color recording material, it usually has three photosensitive layers having different color sensitivities, and each photosensitive layer has The heat development forms or releases dyes having different hues. In this case, generally, the yellow dye (Y) is in the blue photosensitive layer (B), the magenta dye (M) is in the green photosensitive layer (G), and the cyan dye is in the red photosensitive layer (R). Although the dye (C) is combined, the present invention is not limited to this, and any combination is possible.
Specifically, (BC)-(GM)-(RY),
A combination of (infrared photosensitivity-C)-(G-Y)-(RM) is also possible. Further, as described in JP-A-4-329541 and the like, the present invention can be applied to a light-sensitive material having two different color sensitivities in the infrared region and the third color sensitivities in the red region.

Further, as described in JP-A-60-162251, the present invention can be applied to a system in which a black image is formed by using a diffusible dye.

The light-sensitive material used in the image forming method using the image-receiving material of the present invention includes non-photosensitive materials such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a peeling layer in addition to the photosensitive layer. A conductive layer can be optionally provided.

When a paper support is used as a support for the photothermographic material and the image receiving material of the present invention, a support in which both sides of the paper support are coated with polyethylene is particularly preferable. In this case, at least one side is covered. It is preferable that the polyethylene contains titanium oxide.

It is preferable that the paper support coated with such polyethylene has excellent smoothness, and the surface on the side on which the dye image-receiving layer or the photosensitive layer is coated is JIS-P-
The Beck's smoothness specified in 8119 is preferably 50 seconds or more, more preferably 100 seconds or more, and the surface of the support has a cutoff value of 0 from the cross-sectional curve measured according to the standard of JIS-B-0610. When measuring the maximum undulation of a filter with a reference length of 2.5 mm for a filtered undulation curve guided under the condition of 0.8 mm, the maximum undulation may be within 4 μm or more at 100 arbitrary measurement points. The center line average roughness Ra in that case is preferably 3 μm or less.

Further, the base paper of the polyethylene-coated paper is described in JP-A-4-321043, page 4, column 6, line 32 to line 5.
It preferably has the structure and characteristics described in page 8, column 28.

The photothermographic material and the image receiving material may have a so-called back layer in order to balance curl and improve slipperiness. For the back layer, either a hydrophilic binder or a hydrophobic binder can be used, but it can be appropriately selected according to the application and the constitution.

The light-sensitive material used in the image forming method can be exposed by known exposure means suitable for the color sensitivity of the light-sensitive material.

As exposure light sources that can be used, tungsten lamps, halogen lamps, xenon lamps,
A mercury lamp, a CRT light source, a FO-CRT light source, a light emitting diode, a laser light source (for example, a gas laser, a dye laser, a YAG laser, a semiconductor laser, etc.) can be used alone or in combination. Further, a light source in which a semiconductor laser and an SHG element (second harmonic generation element) are combined can also be used.

The exposure time varies depending on whether one screen is exposed once or digitally on a pixel-by-pixel basis. In the former case, it is usually 0.001 to 10 seconds, and In the latter, it is 10 ^-8 to 10 per pixel
^-It is performed in the range of ² seconds. In the case of digital exposure, one exposure may be performed per pixel, or multiple exposure may be performed in which multiple exposures are performed. In the case of performing multiple exposure, it is possible to shift the image area little by little each time.

An image forming method using the dye image-receiving material and the photothermographic material of the present invention is preferably carried out after or at the same time as imagewise exposure of the photothermographic material, preferably 60 to 120.
° C, more preferably 70 to 100 ° C, preferably 1
It is heat-developed for -100 seconds, more preferably 2-60 seconds to form a dye image. It is preferable that the transfer of the diffusible dye to the image receiving material is performed at the same time as the thermal development by bringing the image receiving layer surface of the image receiving material into close contact with the photosensitive layer side of the photosensitive material during the thermal development.

In the above-mentioned photothermographic material, it is preferable that a small amount of water is supplied to the photothermographic material immediately before the heat development, and then both of them are bonded together for the heat development. In this case, the water may be mere water, or may be water containing a surfactant, an antifoggant, a development accelerator, a fluorescent whitening agent or an antifungal agent, and may also have the general formula of the present invention ( It may be water containing the compound represented by 1). The amount of water supplied is preferably within the range of the maximum swollen film thickness of the supplied photothermographic material.

When the heat-developable light-sensitive material is superposed on the image-receiving material and subjected to heat-development, known heating means can be applied. For example, it is brought into contact with a heated heat block or a surface heater, or a heat roller is used. A method of conveying while contacting,
A well-known heat development method such as a method of performing heat development while holding and conveying both between the heat drum and the belt, and a method of passing through an atmosphere maintained at a high temperature can be applied.

The heating pattern at the time of heat development is not particularly limited, and it may be carried out at a constant temperature, at a high temperature in the early stage of development and at a low temperature in the latter half of the development, or vice versa. Any method such as a method of changing the area or a method of continuously changing the temperature can be used. In particular, as described in JP-A-63-250646, it is also possible to develop at a low temperature in advance so that silver development takes place preferentially prior to the dye-releasing reaction, and after performing silver development to some extent, heat development. I can.

[0150]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Dioxide of a reflective support in which 100 g / m ² of a paper support was coated with polyethylene on both sides (however, the polyethylene layer on the dye image receiving layer side contained 12% by weight of titanium dioxide based on polyethylene). A 0.1 μm-thick gelatin subbing layer is applied to the titanium-containing layer side, and the following structure is applied on top of it: 3
Seed coating solution was applied to prepare a dye image receiving material-1.

The addition amount is shown in 1 m ² of the image receiving material.

First layer: acid-treated gelatin (Ca content: 80 μg / 1 g gelatin) 2.4 g mordant 2.0 g surfactant-1 0.15 g surfactant-2 0.03 g image stabilizer-1 0.12 g image stabilizer- 2 0.2 g High-boiling organic solvent-1 0.20 g Water-soluble polymer 1 0.14 g Base precursor (Exemplified compound 3-5) 2.8 g Second layer: Alkali-treated gelatin (Ca content: 80 μg / 1 g gelatin) Ca content 0.6 g Surfactant-2 0.056 g UV absorber-1 0.18 g UV absorber-2 0.12 g High boiling point organic solvent-1 0.18 g Water-soluble polymer 1 0.03 g Base precursor (Exemplified compound 3-5) 0.8 g Third layer: Alkali-treated gelatin (Ca content: 80 μg / 1 g gelatin) Ca content 0.5 g Surfactant-2 0.04 g Silicon oil 0.024 g Optical brightener 0.006 g Water-soluble polymer 2 0.07 g Water-soluble polymer 1 0.022 g A group precursor (Exemplified Compound 3-5) Structure of 0.4g hardener -1 0.1 g additives below.

[0154]

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[0155]

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Next, in the dye image receiving material-1, the dye image receiving material obtained by adding the compound represented by the general formula (1) and the compound represented by the general formula (2) to the third layer in the amounts shown in Table 1 is used. -2
To 14 were prepared in the same manner as the dye image receiving material-1.

The obtained dye image-receiving materials-1 to 14 were wound at 23 ° C. (humidity is about 30 to 60%) in a state of being wound into a roll, and then 2
After being stored for a day, it was stored at 30 ° C. (humidity was between 30 and 60%) for 3 days to harden it.

On the other hand, Photothermographic Material-1 was prepared as follows.

A reflective support (thickness: about 155 μm) in which both sides of a 100 g / m ² paper support are coated with polyethylene (however, the polyethylene layer on the dye image receiving layer side contains 12% by weight of titanium dioxide based on polyethylene). A 0.1 μm-thick gelatin subbing layer was applied to the titanium dioxide-containing layer side, and six types of coating solutions having the following constitutions were applied thereon to prepare a photothermographic material-1. The addition amount of each is shown as an amount per 1 m ^{2 of the} photothermographic material, and the photosensitive silver halide emulsion shows a value converted into silver.

First layer (first infrared-sensitive layer) Alkali-treated gelatin 0.18 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0.55 g (Ca content: 50 μg / 1 g gelatin) First infrared Photosensitive silver halide emulsion (Em-1) 0.075 g Cyan dye-donor (CM-1) 0.57 g Reducing agent-1 0.33 g High boiling point organic solvent-2 0.59 g Surfactant-2 0.082 g Antifoggant-1 0.43 mg Potassium bromide 0.13 mg Water-soluble polymer 3 0.041 g Second layer (first intermediate layer) Alkali-treated gelatin 0.24 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0 0.51 g (Ca content: 50 μg / 1 g gelatin) Water-soluble polymer 3 0.09 g Zinc hydroxide (average particle size: about 0.5 μm) 0.62 g Reducing agent-1 0.08 g Reducing agent-2 0.11 g Surfactant-2 0.07 g High boiling point organic solvent-1 0.33 g Infrared dye 0.06 g Polyethyleneimine 0.1 g Compound-1 0.12 g Antifoggant-2 0.25 mg Sodium sulfite 0.0021 g Third layer (red photosensitive layer) Alkali-processed gelatin 0.22 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0.58 g (Ca content : 50 μg / 1 g gelatin) Water-soluble polymer 3 0.021 g Red photosensitive silver halide emulsion (Em-2) 0.099 g Yellow dye-donor (YM-1) 0.78 g Reducing agent-1 0.40 g High boiling organic Solvent-2 0.52 g Surfactant-2 0.071 g Antifoggant-1 0.46 mg Potassium bromide 0.11 mg Layer (second intermediate layer) Alkali-treated gelatin 0.24 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0.51 g (Ca content: 50 μg / 1 g gelatin) Water-soluble polymer 3 0.082 g Zinc hydroxide ( Average particle size: about 0.2 μm) 0.38 g Reducing agent-1 0.06 g Reducing agent-2 0.08 g Surfactant-2 0.07 g High boiling point organic solvent-1 0.30 g Polyethyleneimine 0.11 g Compound- 1 0.10 g Antifoggant-2 0.25 mg Sodium sulfite 0.0024 g Fifth layer (second infrared photosensitive layer) Alkali-treated gelatin 0.08 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0.31 g (Ca content: 50 μg / 1 g gelatin) Water-soluble polymer 3 0.021 g Second infrared photosensitive resin Silver Genide Emulsion (Em-3) 0.042 g Magenta Dye Donor (MM-1) 0.32 g Reducing Agent-1 0.11 g High Boiling Organic Solvent-2 0.21 g Surfactant-2 0.023 g Antifoggant Agent-1 0.22 mg Potassium bromide 0.024 mg Sixth layer (protective layer) Alkali-treated gelatin 0.29 g (Ca content: 90 μg / 1 g gelatin) Phenylcarbamoyl gelatin 0.21 g (Ca content: 50 μg / 1 g gelatin) Water-soluble polymer 3 0.022 g Reducing agent-1 0.06 g Surfactant-2 0.06 g High boiling point organic solvent-1 0.30 g Polyethyleneimine 0.08 g Matting agent (silica; average particle size about 3 μm) 01g Hardener 0.15g In the first layer, the third layer and the fifth layer, reducing agent-1,
The dye-providing substances were each added together with the high-boiling organic solvent-2 by emulsifying and dispersing in an aqueous gelatin solution in the presence of Surfactant-2.

In addition, in the second layer, the infrared dye, the compound-1 and the reducing agent-1 were added together with the high boiling point organic solvent-1 by emulsifying and dispersing in an aqueous gelatin solution in the presence of the surfactant-2.

In the fourth layer, compound-1 and reducing agent-1
Was added by emulsifying and dispersing in an aqueous gelatin solution in the presence of surfactant-2 together with high boiling point organic solvent-1.

After dispersing the above-mentioned three types of emulsion dispersions, ethyl acetate used as a dispersion aid was removed under reduced pressure.

Further, zinc hydroxide and reducing agent-2 were separately added separately in an aqueous gelatin solution in the presence of surfactant-2 by wet pulverization and fine dispersion using a sand mill disperser.
Zinc hydroxide had an average particle size of about 0.2 μm, and reducing agent-2 had an average particle size of about 0.25 μm.

In each coating solution, the total content of methanol used for dissolving ethyl acetate and various additives was 2% or less in all coating solutions.

Next, each photosensitive silver halide emulsion used is shown below.

Each silver halide emulsion has an average grain size of 0.18 μm.
m silver iodobromide seed emulsion (silver iodide content: 2 mol%) was simultaneously mixed with a silver nitrate aqueous solution and a potassium bromide aqueous solution in a gelatin aqueous solution to obtain silver bromide. In each emulsion, sodium iridium (IV) hexachloride was added in an amount of 10 ⁻⁵ mol per mol of silver halide at the stage where crystals grew to 0.05 μm from the final grain surface. The soluble salt was removed by a conventional method to obtain a silver halide emulsion having the following characteristics.

Then, the chemical sensitizer (ST) was added to the above silver halide emulsion in an amount shown below per mol of silver halide, and the sensitizing dye and supersensitizer shown below were added at 60 ° C. Then, the chemical sensitization was performed by aging to the optimum sensitivity point.

At the end of chemical sensitization, the stabilizer ST shown below was used.
1 is added, and an antibacterial agent is further added to 3 mol per mol of silver halide.
Each silver halide emulsion was obtained by adding 0 mg.

[0170] Em-1 Em-2 Em- 3 silver halide composition _{AgBr 99. 9 I 0.1 AgBr 99.8} I 0.2 AgBr 99.8 I 0.2 average particle size 0.50 .mu.m 0.41 .mu.m 0.41 .mu.m crystalline cubic cubic cubic Particle size distribution Monodisperse Monodisperse Monodisperse Chemical sensitizer T: 0.2 mg ST: 0.2 mg ST: 0.2 mg Sensitizing dye SD1: 7 mg SD2: 20 mg SD3: 12 mg Supersensitizer SS1: 100 mg SS1: 400 mg SS1: 100 mg Stabilizer ST1: 600 mg ST1: 600 mg ST1: 600 mg The structural formula of each compound used above is shown below.

[0171]

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[0172]

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[0173]

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[0174]

[Chemical 21]

[0175]

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The obtained heat-developable photosensitive material-1 was wound into a roll and stored at 23 ° C. at a relative humidity of 30 to 60% for 2 days, and then at a relative humidity of 30 to 60% at 35 ° C. for 6 days to harden it. Filmed.

The saturated water absorption of the photothermographic material is about 1 per m ^{2 of the} photothermographic material from the difference between the weight when the photothermographic material is immersed in pure water at 40 ° C. for 3 minutes and the weight after drying. It was 13 ml. The membrane surface pH (measurement method described later) was about 7.3.

The photothermographic material-1 which had been exposed by a spectral spectrum sensitometer was immersed in pure water at 40 ° C. for 2 seconds, and then superposed on the dye image-receiving material-1 and developed by heating at 90 ° C. for 30 seconds. The photothermographic material and the dye image-receiving material were peeled off immediately after the completion of development. From the spectral sensitivity spectrum obtained for the dye image-receiving material, the maximum sensitivity wavelength of Em-1 (cyan layer) is about 840 nm and that of Em-2 (yellow layer) is about 695 n.
m and Em-3 (magenta layer) were about 790 nm.

Next, the heat-developable photosensitive material-1 was exposed to a white wedge and then combined with the dye image-receiving materials-1 to 14 and subjected to the heat-development treatment in the same manner as described above. As a result, Table 1
Were obtained.

[0180]

[Table 1]

[0181]

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From the results shown in Table 1, the image-receiving materials 6 to 9 of the present invention containing both the compounds represented by the general formula (1) and the general formula (2) showed a dye image showing a low Dmin without decreasing the Dmax. It turns out that

Example 2 The photosensitive silver halide emulsion of the photothermographic material-1 used in Example 1 was Em-4 for Em-1 and Em- for Em-2.
5, Em-3 was changed to Em-6.

The same silver halide grains as in Em-2 of Example 1 were used as the silver halide grains of each silver halide emulsion.

Then, the amount of chemical sensitizer (ST) shown below per mol of silver halide and the sensitizing dye shown below were added to the silver halide grains, and optimum sensitivity points were obtained at 60 ° C. It was aged and chemically sensitized.

At the end of the chemical sensitization, the stabilizer ST1 used in Example 1 (the amount shown below) and the antifungal agent in the amounts used in Em-1 to Em-3 of Example 1 were added. A silver halide emulsion was obtained.

Em-4 Em-5 Em-6 Chemical sensitizer ST: 0.3 mg ST: 0.3 mg ST: 0.3 mg Sensitizing dye SD4: 100 mg SD5: 80 mg SD6: 150 mg Stabilizer ST1: 600 mg ST1: 600 mg ST1: 600 mg A photothermographic material-2 was prepared in the same manner as the photothermographic material-1, except that the following points were changed from the photothermographic material prepared in Example 1.

First layer: Em-1 was replaced with Em-4.

Second layer: Reducing agent-2 and equimolar reducing agent-3
Same as the photothermographic material-1 except that it was replaced with.

Third layer: Fifth layer of photothermographic material-1 (however, Em-3 was replaced by Em-5) Fourth layer: Reducing agent-2 was replaced by equimolar reducing agent-3. Other than the same as the fourth layer of the photothermographic material-1.

Fifth layer: Third layer of photothermographic material-1 (however, Em-2 is replaced with Em-6) Sixth layer: Same as the sixth layer of photothermographic material-1.

The structural formulas of the above additives used are shown below.

[0193]

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The resulting heat-developable photosensitive material-2 was exposed to a white wedge, and a heat development treatment was carried out in the same manner as in Example 1 by using the dye image-receiving materials-1 to 14. Minimum concentration (Dmi
n) and maximum density (Dmax) were determined. Table 2 shows the results
Shown in

[0195]

[Table 2]

From the results shown in Table 2, as in Example 1, the dye image receiving material containing both the compounds of the general formulas (1) and (2) had a low minimum density without lowering the maximum density (Dmax). It can be seen that an excellent dye image can be obtained at (Dmin).

Example 3 The photothermographic material-2 of Example 2 was processed at 40 ° C. and relative humidity of 60.
% For 5 days and then treated in the same manner as in Example 2. The results are shown in Table 3.

[0198]

[Table 3]

From the results shown in Table 3, when the image-receiving material of the present invention was used, Dmax was stable even when the photosensitive part was stored for a long time.
And Dmin.

Example 4 In the dye image-receiving materials 6 to 9 used in Example 1, the third
Potassium bromide was added to the layer in an amount of 0.1 per 1 m ² of the dye image receiving material.
Dye image receiving materials 6a to 9a added in millimoles were prepared in the same manner as in Example 1. Then, the heat-developable photosensitive material-1 prepared in Example 1 was used to carry out the same treatment as in Example 1 for evaluation. The results are shown in Table 4.

[0201]

[Table 4]

As is clear from the results in Table 4, by adding potassium bromide to the dye image-receiving material of the present invention, the minimum density (Dmin) was hardly increased and the maximum density (Dm) was increased.
It can be seen that ax) rises and the discrimination is improved.

[0203]

The dye image-receiving material according to the present invention reduces the fog of silver development in the unexposed area and improves the silver development rate in the exposed area when heat-developed using the heat-developable color light-sensitive material. Maximum density (Dma
An excellent dye image can be obtained at a low minimum density (Dmin) without decreasing x), and an excellent image in which photographic performance does not fluctuate even when the film hardness of the photothermographic material fluctuates.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaru Tsuchiya 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (4)

[Claims] 1. A diffusion transfer type heat-developable color photosensitive material containing a photosensitive silver halide and a dye-donating substance which forms or releases a diffusible dye, and a dye-image receiving material used in combination during heat development and dye transfer. And a hydrophilic binder, a dye mordant, and a compound represented by the following general formula (1) and a nitrogen-containing heterocyclic compound represented by the following general formula (2) on a support. . Embedded image [In the formula, Y represents an atomic group necessary for forming a 5- or 6-membered ring, and may form a condensed ring. R ₁ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group, R ₂ is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, and an aryl group, —S
_{O 3 H, -COOR ', -} CONHR', - NHCOR ',
-SO ₂ NR'R ", -. NHSO represents a ₂ R ', or -SR' where R 'and R" each represents a hydrogen atom, an alkyl group or an aryl group. However, at least one of R ₁ and R ₂ has at least one water-soluble group selected from a carboxyl group, a sulfo group or a sulfonamide group as a substituent. ] [Chemical 2] [In the formula, W represents = N- or = C (R ₅ )-, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄
And R ₅ is a hydrogen atom, an amino group, —COOR ₁₁ , —N
It represents HCOR ₁₂ , -CONH ₂ or an alkyl group having 1 to 4 carbon atoms. R ₁₁ represents a hydrogen atom or an alkyl group, and represents an R ₁₂ alkyl group. However, R ₃ , R ₄ and R ₅
The total number of carbon atoms is 0 to 4. ] 2. The dye image receiving material according to claim 1, wherein the dye image receiving material further contains a compound represented by the following general formula (3a) or (3b). Embedded image [In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and this nitrogen-containing heterocycle is -COOM.
It may have a substituent in addition to the group. M represents an alkali metal or a substituted or unsubstituted guanidinium ion, amidinium ion or quaternary ammonium ion. [Formula 4] [In the formula, Ar represents a substituted or unsubstituted phenyl group or pyridyl group, respectively, and M is M in the general formula (3a).
Is the same as ] 3. The dye image-receiving material according to claim 2, wherein the heat development and the dye transfer are performed in the same step and a small amount of water is supplied from the outside. 4. The dye image receiving material according to claim 1, wherein the dye image receiving material further contains 0.01 to 1 mmol of water-soluble bromide per 1 m ² of the dye image receiving material. material.