JPH0720620A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat-developable color photosensitive material low in fog and restrained from occurrence of uneven processing by incorporating a reducing agent in a nonphotosensitive layer formed on the outside of a photosensitive layer. CONSTITUTION:The heat developable color photosensitive layer has at least one photosensitive layer containing a combination of a photosensitive silver halide emulsion and a dye donor on a support and further at least >=3 nonphotosensitive layers on the outside of the photosensitive layer and farthest from the support. One of these nonphotosensitive layers other than the outermost layer and not adjacent to the photosensitive layer, contains the reducing agent, such as known in the field of the heat-developable photosensitive materials, or a reducing agent precursor having not reducing action but displaying it in the course of development stage by action of a nucleophilic reagent or heat, in an amount of 10<-5>-10<-2>mol/m<2>, preferably, 5X10<-5>-5X10<-3>mol/m<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material having low fog and no uneven processing.

[0002]

2. Description of the Related Art Recent advances in office automation have led to advances in commercial imaging equipment, the advent of electronic still cameras, the spread of video and facsimile, advances in computer graphics, advances in image sensors and advances in digital processing technology for original images. Along with this, there is an increasing demand for obtaining a color hard copy from image information that has been converted into an electrical signal.

Various methods such as electrophotography, ink jet, thermal transfer, and silver salt photography are known as methods for obtaining a color hard copy. However, the inkjet and thermal transfer methods are still insufficient in terms of image quality, and the development of a system capable of high image quality and simple and quick processing has been awaited. On the other hand, since the photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photographic method in photographic characteristics such as sensitivity and gradation control, it has been widely used conventionally. In recent years, a technique has been developed that can easily and quickly obtain an image by changing the image forming processing method of a light-sensitive material using silver halide from the conventional wet processing using a developing solution or the like to dry processing such as heating. Came.

Photothermographic materials are known in the art, and regarding the photothermographic material and its process, for example, 553 of the foundation of photographic engineering (published by Corona Publishing Co. in 1979).
~ 555 pages, 40 pages of video information published in April 1978, Nebuletts, Handbook of Photography and Reprography, 7th Edition (Nebletts, Handbook of Photography and
Reprography 7th Ed.) Van Nostrand Reinhold Compan
y), pages 32-33, U.S. Pat. No. 3,152,904.
No. 3,301,678, 3,392,020
No. 3,457,075, British Patent No. 1,131,
108, No. 1,167,777 and Research.
Disclosure, June 1978, pages 9-15,
(RD-17029). All of these generate or release a dye by heating to form an image-like distribution of the dye, and are characterized in that the image-like distribution of the dye can be obtained in a short time.

Conventional light-sensitive materials have spectral sensitivities of blue, green, and red, and in order to obtain an image using image information converted into an electric signal on such a light-sensitive material, a color CRT is used.
It is common to use a (cathode ray tube) as an exposure light source, but a CRT is unsuitable for obtaining a large size print. Further, as a writing head capable of obtaining a large-sized print, a light emitting diode (LE
D) and semiconductor lasers have been developed. However, none of these optical writing heads that efficiently emit blue light has been developed. Therefore, for example, a light emitting diode (LE
When using D), near infrared (800 nm), red (67 nm)
It is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red and yellow by a light source combining three light emitting diodes of 0 nm) and yellow (570 nm). "Nikkei New Material" September 14, 1987 issue 47-
It is described on page 57 and is partly in practical use. Also,
Japanese Patent Application Laid-Open No. 61-137149 discloses a system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at each wavelength with a light source combining three semiconductor lasers emitting light of 880 nm, 820 nm and 760 nm. Has been done.

By the way, in the heat-developable color light-sensitive material, how to suppress fog during heat-development is an important point. In particular, it has been found that in a heat-developable color light-sensitive material using a reducing dye-donor compound, the dye-donor compound is susceptible to oxygen oxidation during heat development and slightly releases the dye regardless of exposure. Therefore, there is known a technique of adding a reducing agent to a light-sensitive material in order to suppress the unnecessary oxygen oxidation, and JP-A-60-198540 and JP-A-6-198540.
2-2014434, 62-85241 and the like. Also, if these compounds are simply added to the layer containing the photosensitive silver halide, the silver halide is reduced, that is, fog is caused, and the fog is increased. A technique for preventing addition is described in Japanese Patent Application No. 3-291866. However, for example, when the layers are arranged from the uppermost layer to a layer containing a reducing agent of the present invention / a layer containing no reducing agent / a layer containing a photosensitive silver halide (the following layer abbreviations), there is a certain processing unevenness. It was found to occur. This unevenness is a blackish-like defect, and the cause of occurrence is not clearly known. This is likely to occur when a metal such as silver is inadvertently mixed into the water applied to the photosensitive material. As a mechanism,
It is presumed that these silvers are used as physical development nuclei and the reducing agent in the uppermost layer reduces the silver complex generated in the photosensitive material at the time of laminating and developing, and the silver is transferred to the dye fixing material. Therefore, there arises a problem that it is necessary to suppress the fogging and the unevenness of the processing.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable color light-sensitive material which has low fog and suppresses the occurrence of processing unevenness.

[0008]

The object of the present invention is to provide a heat-developable color light-sensitive material having on a support at least one light-sensitive layer containing at least a light-sensitive silver halide emulsion in combination with a dye-donor compound. At least three or more non-photosensitive layers are provided outside the photosensitive layer farthest from the support, and in the non-photosensitive layer, a layer which is not adjacent to the photosensitive layer and is not the outermost layer contains a reducing agent. Was achieved by a heat-developable color light-sensitive material.

The specific structure of the present invention will be described in detail below. As the reducing agent used in the non-photosensitive layer of the present invention, those known in the field of photothermographic materials can be used. Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the present invention include US Pat. No. 4,500,626, columns 49 to 50, US Pat. No. 4,483,914, columns 30 to 31, and US Pat.
0,617, 4,590,152, JP-A-60-
140335, pages (17)-(18), ibid. 57-40245.
No. 56-138736, No. 59-178458.
No. 59-53831, No. 59-182449,
59-182450, 60-119555, 60-128436 to 60-128439, 60-198540, 60-181742.
No. 61-259253 and No. 62-244044.
No. 62-131253 to 62-131256
No. 78 to 96 of EP 220 746 A2
There are reducing agents and reducing agent precursors described on pages and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.
When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be added, if necessary, in order to promote electron transfer with a developable silver halide as the diffusion resistant reducing agent. A combination of precursors can be used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of the above-mentioned reducing agents as long as it does not substantially move in the layer of the light-sensitive material, and preferably hydroquinones. , Sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donor compounds having diffusion resistance and reducing property described later. The addition amount of the reducing agent used in the non-photosensitive layer is 10 ^-5 mol / m ² -1
0 ^-2 mol / m ² , particularly preferably 5 x 10 ^-5 mol / m ^{2 to} 5
× 10 ⁻³ mol / m ² . Specific examples of the compound are shown below, but the invention is not limited thereto.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

The photothermographic material of the present invention basically has a photosensitive silver halide emulsion and a dye-donating compound (which may also serve as a reducing agent as described later) on a support, Furthermore, if necessary, an organic metal salt oxidizing agent, etc. can be added. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The photothermographic material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical coupler. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or any other shape. Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1)
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used in an unripened state, but is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver. In the present invention, together with the photosensitive silver halide,
An organic metal salt can also be used together as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include U.S. Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 10 mol per mol of photosensitive silver halide.
Preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver. Various antifoggants or photographic stabilizers can be used in the present invention. For example, RD17643
(1978) pages 24 to 25, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or JP-A-59.
The mercapto compounds and metal salts thereof described in JP-A-111636, the acetylene compounds described in JP-A-62-87957, and the like are used. The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, JP-A-59-180550 and JP-A-60-140335,
The sensitizing dyes described in RD17029 (1978) pages 12 to 13 and the like can be mentioned. These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A-63
No. 23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or in U.S. Pat. Nos. 4,183,756 and 4,2,4.
No. 25,666, before or after nucleation of silver halide grains. The addition amount is generally 10 per mol of silver halide.
It is about ^-8 to 10 ^-2 mol. A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing material. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives or cellulose derivatives, starch, gum arabic,
Natural compounds such as polysaccharides such as dextran and pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds can be mentioned. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃
Homopolymers of vinyl monomers having M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, manufactured by Sumitomo Chemical Co., Ltd.) Sumika gel L-5H) is also used. These binders can be used in combination of two or more. Further, as the acid-treated gelatin used in the present invention,
Nitta Gelatin's "950 Gelatin", Nip Gelatin's "ABA Gelatin", Kuroda Gelatin's "Croda-
It can be arbitrarily selected and used from "A148" and the like.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less. The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material include various polymers for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. A latex can be included. Specifically, JP-A Nos. 62-245258 and 62-62
Any of the polymer latices described in JP-A-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect is obtained. can get. In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or vice versa, that is, a dye-donor compound is used. Include.

As an example of the dye-donating compound that can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers are described in T.W. H. J
by Ames, “The Theory of the P”
photographic Process "Fourth Edition 29
Pages 1-334 and 354-361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

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

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. The following items (1) to (4) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide. To form a negative dye image).

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972 are described. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

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

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used.

As an example thereof, US Pat. No. 4,139,
No. 389, No. 4,139,379, JP-A-59-18.
Compounds which release diffusible dyes by nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107.
JP-A-59-101649 and 61-88257.
, RD24025 (1984) and the like, which release a diffusible dye by an electron transfer reaction in the molecule after reduction, West German Patent No. 3,008,588A,
JP-A-56-142530, US Pat. No. 4,343,
893, 4,619,884, etc., compounds that cleave a single bond after reduction to release a diffusible dye, electron acceptors described in US Pat. No. 4,450,223, etc. Nitro compounds, which later release diffusible dyes,
Examples thereof include compounds described in US Pat. No. 4,609,610 which release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used.

Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,7.
Compounds (1) to (3) described in No. 83,396,
(7) to (10), (12), (13), (15),
(23) to (26), (31), (32), (35),
(36), (40), (41), (44), (53)-
(59), (64), (70), Public Technical Report 87-619
9 are compounds (11) to (23) and the like.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, and U.S. Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like.

A compound (DRR compound) which is reducible to silver halide (or organic silver salt) and releases a diffusible dye when its partner is reduced. In the present invention, this DR
Preference is given to using R compounds. Typical examples thereof are US Pat. Nos. 3,928,312 and 4,053,312.
No. 4,055,428, No. 4,336,322
JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, 51-104343, R
D17465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116537, 57-179840, and U.S. Pat. No. 626 and the like. D
Specific examples of the RR compound include the above-mentioned US Pat.
The compounds described in Columns 22 to 44 of No. 0626 can be mentioned. Among them, the compounds (1) to (3), (10) to (13), (16) described in the above-mentioned U.S. Pat. ) ~
(19), (28) to (30), (33) to (35),
(38) to (40) and (42) to (64) are preferable.
The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition, as a dye-donor compound other than the coupler and the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
5,957, Research Disclosure, 19
1976, pp. 30-32, etc.), leuco dyes (U.S. Pat. Nos. 3,985,565, 4,022,617, etc.) can also be used. Hydrophobic additives such as dye donating compounds and diffusion resistant reducing agents are described in US Pat. No. 2,322,02
It can be incorporated into the layer of the light-sensitive material by a known method such as the method described in No. 7. In this case, JP-A-59-
83154, 59-178451, 59-17.
No. 8452, No. 59-178453, No. 59-178.
No. 454, No. 59-178455, No. 59-1784.
A high boiling point organic solvent as described in No. 57 and the like can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Also, 1 g per 1 g of binder
cc or less, more preferably 0.5 cc or less, and particularly 0.3 cc or less is suitable. JP-B-51-39853, JP-A-51
A dispersion method using a polymer described in JP-A-59943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used.
For example, JP-A-59-157636, (37) to (3)
8) The surfactants listed on page 8 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52. In the present invention, a non-diffusible filter dye may be contained for the purpose of improving sharpness. If necessary, a filter dye having absorption in the infrared region can also be used. Details of such filter dyes are described in Japanese Patent Application No. 2-137885 and Japanese Patent Application Laid-Open No. 4-2172.
No. 43, No. 4-276744, No. 5-45834 and the like. In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. The relationship between the photosensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer are described in US Pat. No. 4,500,626, No. 57.
The relationships described in the column can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (3)
2) to (41), the mordants described in JP-A-62-244.
No. 043, No. 62-244036, etc. can be mentioned. Also, U.S. Pat. No. 4,463,07
A dye-accepting high molecular compound as described in No. 9 may be used. If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer. In particular, it is useful to provide a protective layer. A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing material. As an example thereof, JP-A-62-2
Examples thereof include those described on pages (26) to (28) of No. 53159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A No. 62-245260, that is, -COOM or-
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more. In the case of adopting a system in which a small amount of water is supplied for thermal development, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more suitably 7 g or less.

In the constituent layers of the light-sensitive material and the dye-fixing material, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the peelability between the light-sensitive material and the dye-fixing material. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (U.S. Pat. No. 3,352,6
No. 81), benzophenone compounds (JP-A-46-
2784) and others, JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256 (27)-(29), 63-19924.
No. 8, JP-A-1-75568, and JP-A-1-74272. Examples of useful anti-fading agents are disclosed in JP-A-62-215272 (125) to (137).
Page. The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing material from the outside such as a light-sensitive material. . The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. As an example, K. Veenkatar
aman ed "The Chemistry of Sy"
“Neticic Dyes”, Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based compounds.
The fluorescent whitening agent can be used in combination with an anti-fading agent.

As a hardener used in the constituent layers of the light-sensitive material and the dye-fixing material, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157). In the constituent layers of the light-sensitive material and the dye-fixing material, a coating aid, a peeling property improving, a sliding property improving,
Various surfactants can be used for the purpose of preventing static charge and promoting development. Specific examples of the surfactant are disclosed in JP-A-62-1
No. 173463, No. 62-183457 and the like. The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Typical examples of the organic fluoro compound include fluorine-containing surfactants and fluorine oils described in JP-B-57-9053, columns 8 to 17, JP-A-61-29444, JP-A-62-135826 and the like. The hydrophobic fluorine compound such as the oily fluorine-based compound or the solid fluorine compound resin such as tetrafluoroethylene resin.

A matting agent can be used for the light-sensitive material and the dye-fixing material. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness and preventing Newton's rings but also for making the surface of the dye fixing material (image surface) non-glossy. In addition, the constituent layers of the light-sensitive material and the dye fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256 (2).
6) to (32). In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye-fixing material. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For details of these, see US Pat. No. 4,678,739, No. 3,
It is described in columns 8-40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are U.S. Pat. No. 4,511,493 and JP-A-62-65038.
No. etc. In a system in which heat development and dye transfer are simultaneously performed in the presence of a small amount of water, a base and / or
Alternatively, the base precursor is preferably contained in the dye-fixing material in order to improve the storage stability of the light-sensitive material. In addition to the above, European Patent Publication 210,660, US Pat.
No. 40,445, a combination of a sparingly soluble metal compound and a compound capable of undergoing a complex forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound),
The compounds which generate a base by electrolysis as described in JP-A-61-232451 can also be used as the base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing material for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base after proper development to lower the concentration of the base in the film to stop the development or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32). In the present invention, a support that can withstand the processing temperature is used as the support for the light-sensitive material and the dye-fixing material.
Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers via an electric signal, a CRT, liquid crystal display, electro There is a method of outputting to an image display device such as a luminescence display and a plasma display, and exposing directly or through an optical system. As a light source for recording an image on a photosensitive material, as described above, a light source described in US Pat. No. 4,500,626, column 56, such as natural light, a tungsten lamp, a light emitting diode, a laser light source, and a CRT light source, may be used. it can. Further, as the light emitting diode of the light source used for exposing the heat-developable color photosensitive material of the present invention,
GaAsP (red), GaP (red, green), GaAsP
(Red, yellow), GaAs (infrared), GaAlAs (infrared,
Various materials such as red), GaP (red, green, yellow) and SiC (blue) can be used. It is also possible to use an infrared-visible conversion element that converts the infrared light of the infrared light emitting diode into visible light with a phosphor as described above. As such a phosphor, a phosphor activated with a rare earth is preferably used, and as the rare earth, Er ³⁺ , Tm ³⁺ , Yb ³⁺ or the like can be used. As a specific example of the semiconductor laser that can be used in the present invention, as a light emitting material, In
_1-x Ga _x P (up to 700 nm), GaAs _1-x P _x (6
10 to 900 nm), Ga _1-x Al _x As (690 to 9)
00 nm), InGaAsP (1100 to 1670 n)
m) and a semiconductor laser using a material such as AlGaAsSb (1250 to 1400 nm). Irradiation of light to the color light-sensitive material in the present invention is carried out by using the above-mentioned semiconductor laser and by using Nd: YAG crystal with GaAs _x
It may be a YAG laser (1064 nm) excited by a P _(1-x) light emitting diode. Further, in the present invention, the second harmonic generation element (SHG element) is for converting the wavelength of the laser light into a half by applying a nonlinear optical effect, and for example, as a nonlinear optical crystal, CD ^*. Examples thereof include those using A and KD ^* P (see “Laser Handbook”, edited by The Laser Society, December 15, 1982, pages 122 to 139). Further, it is possible to use a LiNbO ₃ optical waveguide element of Li ⁺ to form an optical waveguide by ion exchange with H ⁺ in LiNbO ₃ crystal (N
IKKEI ELECTRONICS, July 1986 1
4th, No. 399, pages 89-90).

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used. The light-sensitive material and / or the dye-fixing material may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye. As the transparent or opaque heating element in this case, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C to about 25 ° C.
It can be developed at 0 ° C., but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development image step is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. Although the transfer of the dye occurs only by heat, a solvent may be used to accelerate the transfer of the dye.
Further, JP-A-59-218443 and JP-A-61-2380.
As described in detail in No. 56, etc., a method of heating in the presence of a small amount of solvent (particularly water) and performing development and transfer simultaneously or continuously is also useful. In this method, the heating temperature is 5
The boiling point of the solvent is preferably 0 ° C. or higher and, for example, 50 ° C. or higher and 100 ° C. or lower when the solvent is water.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent. These solvents can be used by a method of applying them to the dye fixing material, the photosensitive material or both. The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

As a method of applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Alternatively, the solvent may be contained in a microcapsule or the like, and may be incorporated in the light-sensitive material or the dye-fixing material or both in advance. Further, in order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is built into the photosensitive material or the dye fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer,
It is preferably incorporated in the dye fixing layer and / or the adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive material and / or the dye fixing material. As a heating method in the developing and / or transferring step, contact with a heated block or plate,
For example, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, or passage through a high temperature atmosphere. A method of applying a pressure condition for applying pressure when superimposing a light-sensitive material and a dye-fixing material and bringing them into close contact is disclosed in JP-A-61-14724.
The method described on page 4, page 27 can be applied. Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-1.
77547, 59-181353, 60-18
The apparatus described in No. 651, Japanese Utility Model Laid-Open No. 62-25944 and the like are preferably used.

[0041]

【Example】

 Example 1 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [Fifth layer (emulsion for 680 nm photosensitive layer)] Solution (I) and (II) having the composition shown in Table 2 in an aqueous solution having the composition shown in Table 1 which is well stirred. The solutions were simultaneously added over 13 minutes, and 10 minutes after that, solutions (III) and (IV) having the compositions shown in Table 2 were added over 33 minutes.

[0043]

[Table 1]

[0044]

[Table 2]

Further, 13 minutes after the addition of the solution III was started, 150 cc of a 0.35% aqueous solution of a sensitizing dye was added over 27 minutes.

[0046]

[Chemical 3]

After washing with water and desalting (the precipitation agent a was used at a pH of 4.1) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 3. The yield of the obtained emulsion is 6
It was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2% at 30 g and an average grain size of 0.20 μm.

[0048]

[Chemical 4]

[0049]

[Table 3]

[0050]

[Chemical 5]

[0051]

[Chemical 6]

Photosensitive silver halide emulsion (2) [Third layer (emulsion for 750 nm photosensitive layer)] Solution (I) and (II) having the composition shown in Table 5 in an aqueous solution having the composition shown in Table 4 which is well stirred. The solutions were added simultaneously over 18 minutes, and 10 minutes after that, the solutions (III) and (I
Solution V) was added over 24 minutes.

[0053]

[Table 4]

[0054]

[Table 5]

After rinsing with water and desalting (pH was set to 3.9 using a precipitating agent b) by a conventional method, calcified lime-treated ossein gelatin (calcium content: 150 PPM) was used.
22 g) and redispersed at 40 ° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added, pH is 5.9 and pAg is 7. 8
Adjusted to. Then, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 6. At the end of the chemical sensitization, a sensitizing dye was added as a methanol solution (solution having the composition shown in Table 7). After chemical sensitization, the temperature was lowered to 40 ° C., 200 g of a gelatin dispersion of a stabilizer described later was added, and the mixture was stirred well and then stored. The yield of the obtained emulsion was 938 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0056]

[Table 6]

[0057]

[Chemical 7]

[0058]

[Table 7]

[0059]

[Chemical 8]

Photosensitive silver halide emulsion (3) [First layer (emulsion for 810 nm photosensitive layer)] Solution (I) and (II) having the composition shown in Table 9 in an aqueous solution having the composition shown in Table 8 which is well stirred. The solutions were added simultaneously over 18 minutes, and 10 minutes after that, the solutions (III) and (I
Solution V) was added over 24 minutes.

[0061]

[Table 8]

[0062]

[Table 9]

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

[0064]

[Table 10]

A method for preparing a gelatin dispersion of colloidal silver will be described.

The liquid having the composition shown in Table 12 was added to the aqueous solution having the composition shown in Table 11 which was well stirred for 24 minutes. After washing with water using the precipitating agent a, 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. Average particle size is 0.02μm and yield is 512g
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0067]

[Table 11]

[0068]

[Table 12]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

Gelatin dispersions of the yellow dye-donor compound, the magenta dye-donor compound and the cyan dye-donor compound were prepared according to the formulations shown in Table 13. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution, and the aqueous phase component heated at about 60 ° C. was added and mixed with stirring, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added to this and stirred to obtain a uniform dispersion.
Further, a gelatin dispersion of a cyan dye-donating compound was added to an ultra loca module (ultra loca module manufactured by Asahi Kasei: ACV
-3050), dilution with water and concentration were repeated, and the amount of ethyl acetate was reduced to 17.6 times the amount of ethyl acetate in Table 13.

[0071]

[Table 13]

A gelatin dispersion of reducing agent was prepared according to the recipe in Table 14. That is, each oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes to 100
Dispersion was carried out at 00 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0073]

[Table 14]

A gelatin dispersion of the stabilizer was prepared according to the formulation in Table 15. That is, each oil phase component was dissolved at room temperature, the water phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed, and then a homogenizer was used for 10 minutes at 10,000 r
dispersed at pm. Water was added to this and stirred to obtain a uniform dispersion.

[0075]

[Table 15]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 16. That is, after mixing and dissolving each component, a glass mill with an average particle size of 0.75 mm
Acid separated for a minute. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.
The one having a thickness of 25 μm was used. )

[0077]

[Table 16]

Next, a method for preparing a gelatin dispersion of the matting agent added to the protective layer will be described. A liquid prepared by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and dispersed by stirring at high speed. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0079]

[Chemical 9]

[0080]

[Chemical 10]

[0081]

[Chemical 11]

[0082]

[Chemical 12]

[0083]

[Chemical 13]

[0084]

[Chemical 14]

[0085]

[Chemical 15]

[0086]

[Chemical 16]

[0087]

[Chemical 17]

[0088]

[Chemical 18]

[0089]

[Chemical 19]

A photothermographic material 100 shown in Table 17 was prepared using the above.

[0091]

[Table 17]

[0092]

[Table 18]

[0093]

[Chemical 20]

[0094]

[Chemical 21]

[0095]

[Chemical formula 22]

[0096]

[Chemical formula 23]

[0097]

[Chemical formula 24]

Next, as shown in Table 18, the seventh layer of the light-sensitive material 100 was added.
Photosensitive materials 101 to 105 were prepared in the same manner except that a reducing agent was added as shown in FIG. Further, the seventh layer of the light-sensitive material 100 has a two-layer structure of a seventh upper layer and a seventh lower layer shown in Table 19 and the reducing agent is added to the seventh lower layer as shown in Table 18 in the same manner. Materials 106-110 were made. In each light-sensitive material, the reducing agent was added as the same gelatin dispersion as shown in Table 14. The amount of the reducing agent used was R-1 = 7.5 g R-2 = 8.3 g R-3 = 17.0 g R-9 = 20.0 g R-13 = 11.3 g as a dispersion composition.

[0099]

[Table 19]

[0100]

[Table 20]

Next, each color was simultaneously exposed under the conditions shown in Table 20 by using the optical system exposure apparatus shown in FIG. 2 of Japanese Patent Application No. 4-281442, and 14 cc /
m ² of water was supplied by a wire bar, and then the dye fixing material and the dye fixing material were superposed so that the membrane surface was in contact. Using a heat drum whose temperature was adjusted so that the water-absorbed film had a temperature of 83 ° C., after heating for 35 seconds, the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material.

[0102]

[Table 21]

For the evaluation of Dmin, the white background portion was measured by X-RITE (status A).

The unevenness of processing was evaluated by supplying 0.1 ppm of an aqueous silver nitrate solution to the light-sensitive material instead of water, and checking the unevenness in a white background which was not exposed. Table 21 shows the above evaluation results.

[0105]

[Table 22]

As shown in the results of Table 2, a protective layer having three or more layers, which is a layer which is not adjacent to the photosensitive layer,
Further, it can be seen that by containing a reducing agent in the layers other than the uppermost layer, a heat-developable color light-sensitive material with low fog and uniform processing can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 30, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

The object of the present invention is to provide a heat-developable color light-sensitive material having on a support at least one light-sensitive layer containing at least a light-sensitive silver halide emulsion in combination with a dye-donor compound. Having at least three or more non-photosensitive layers outside the photosensitive layer farthest from the support,
A heat-developable color light-sensitive material characterized by containing a reducing agent in a layer which is not adjacent to the light-sensitive layer and is not the outermost layer among the non-light-sensitive layers.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52. In the present invention, a non-diffusible filter dye may be contained for the purpose of improving sharpness. If necessary, a filter dye having absorption in the infrared region can be used. Details of such filter dyes are described in Japanese Patent Application No. 2-137885 and Japanese Patent Application Laid-Open No. 4-21724.
3, No. 4-276744, No. 5-45834 and the like. In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the photosensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing material for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32). In the present invention, a support that can withstand the processing temperature is used as the support for the light-sensitive material and the dye-fixing material.
Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses are used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Sensitive Layer)] Aqueous solutions having the compositions shown in Table 1 and (I) and (II) having the compositions shown in Table 2 are stirred well. Solution) was added simultaneously over 13 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 2 were added over 33 minutes.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 5 are added to an aqueous solution having the composition shown in Table 4 which is well stirred. ) Solution was added simultaneously over 18 minutes, and 10 minutes after that, solution (III) and (I
Solution V) was added over 24 minutes.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

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

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0072

[Correction method] Change

[Correction content]

A gelatin dispersion of the reducing agent R-1 is shown in Table 14.
Was prepared according to the prescription. That is, each oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes.
Dispersion was performed at 000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

[0073]

[Table 14]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

A photothermographic material 101 shown in Table 17 was prepared using the above.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

[0091]

[Table 17]

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction content]

Next, as shown in Table 18, the seventh layer of the light-sensitive material 101 was added.
Photosensitive materials 100 and 102 to 105 were prepared in the same manner except that no reducing agent was added or the type and amount of the reducing agent were changed as shown in FIG. In addition, the seventh
Photosensitive materials 106 to 110 were prepared in the same manner except that the layer had a two-layer structure of a seventh upper layer and a seventh lower layer shown in Table 19 and a reducing agent was added to the seventh lower layer as shown in Table 18.
In each light-sensitive material, the reducing agent was added as the same gelatin dispersion as shown in Table 14. The amount of the reducing agent used was R-1 = 7.5 g R-2 = 8.3 g R-3 = 17.0 g R-9 = 20.0 g R-13 = 11.3 g as a dispersion composition.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

Next, each color was simultaneously exposed under the conditions shown in Table 20 by using the optical system exposure apparatus shown in FIG. 2 of Japanese Patent Application No. 4-281442, and 14 cc /
m ² of water was supplied by a wire bar, and then the dye fixing material and the dye fixing material were superposed so that the membrane surface was in contact. Using a heat drum whose temperature was adjusted so that the water-absorbed film had a temperature of 83 ° C., after heating for 35 seconds, the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material.

Claims (1)

[Claims] 1. A heat-developable color light-sensitive material having at least one light-sensitive layer containing at least a light-sensitive silver halide emulsion and a dye-donor compound in combination on a support,
At least three or more non-photosensitive layers are provided outside the photosensitive layer farthest from the support, and in the non-photosensitive layer, a layer which is not adjacent to the photosensitive layer and is not the outermost layer contains a reducing agent. A heat-developable color photosensitive material.