JPS62953A - Formation of color image - Google Patents

Abstract

PURPOSE:To prevent unevenness in development and transfer, and growth of bacteria and mold by transferring a diffusive dye produced or released from a dye donor in response or reverse response to the reaction of reduction of silver ions to silver, from a photosensitive element through the medium of water to a dye fixing element in the presence of a bacteria and mold inhibitor. CONSTITUTION:The heat-developable color photosensitive material has the photosensitive element formed on a support containing at least photosensitive silver halide, a binder resin, and the dye donor capable of producing or releasing the diffusive dye in response or reverse response to the reaction when silver ions are reduced to silver by heat development, and the diffusive dye formed by imagewise exposure and heat development, is transferred from the photosensitive element through the medium of water to the dye fixing element in the presence of at least one kind of a bacteria and mold inhibitor, such as a thiazolylbenzimidazole derivative. As the water to be used, drinking water, general industrial water, and so on, are used, and a water softener is added together with said inhibitor. The water may be added anytime before the dye transfer, and a good-quality image can be obtained by drying the water remaining on the surface not absorbed with the coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention uses water to transfer diffusible dyes produced or released during development in a photosensitive element to an image receiving element to form a color image. The present invention relates to a method, and more specifically, to a color image forming method that prevents uneven transfer caused by precipitates and suspended matter caused by water and bacteria and mold that occur in photographic elements (light-sensitive elements and image-receiving elements). The present invention particularly relates to a color image forming method using thermal development.

[Conventional technology]

For information on how to obtain color images through heat development,
Many proposals have been made. US Patent No. a53L286
No. 3761,270, No. 402L240,
Belgian Patent No. 802, No. 19, Search Disclosure Magazine, September 1975, pages 31 and 32, etc., describe a method for forming a yellow image through the combination of an oxidized developer and a coupler, and its removal. Developers are listed.

In addition, this method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described on pages 54-58 (
RD-16966).

Furthermore, regarding the method of forming positive color images using the heat-sensitive maple bleaching method, see, for example, Research Desktop Magazine, April 1976 issue, pages 30-32 (RD-14433).
), December 1976 issue, pages 14-15 (RD-15
227), US Patent No. 423fi957, and others describe useful methods of bleaching dyes.

Further, regarding methods of forming color images using leuco dyes, for example, US Pat. Nos. 398Fx565 and 40
It is described in No. 22617, etc.

However, in these color image forming methods, during long-term storage of the formed color image, discoloration and coloring of the white background occur due to coexisting silver halide, silver complex, developer, etc. A new color image forming method using thermal development that has improved these drawbacks is disclosed in JP-A-57-179840, JP-A-57-186774, JP-A-57-198458, JP-A-57-207250, and JP-A-5.
No. 8-58543, No. 58-79247, No. 58-1
) No. 6537, No. 58-149046, No. 59-48
No. 764, No. 59-65839, No. 59-71046
No. 59-87450, No. 59-88730, etc.

When photosensitive silver halide and/or organic complex salts are reduced to scissors by thermal development, a mobile dye is generated or released in response to or inversely to this reaction, and this mobile dye is This is a method of transferring to a dye fixing element.

Such an image forming method requires a step of forming an image-shaped mobile dye by heating and a step of moving this dye to a dye fixing element, but these steps can be performed simultaneously to speed up the processing, A simplified thermal development image forming method is disclosed in JP-A-59-218443.

[Problem that the invention seeks to solve]

In these methods, for example, JP-A-59-181346, JP-A-59-181347,
No. 59-181353, No. 59-181354, No. 59-218443, Patent Application No. 1983-135936
As described in the above issue, a small amount of water is supplied from the storage container to the dye-fixing element or the photosensitive element to accelerate the transfer or development of the dye. There is a problem in that precipitates and suspended matter caused by mold and mildew are mixed in, and this interferes with dye transfer and development, resulting in uneven images. Bacteria and mold that grow on the photosensitive element and dye-fixing element during storage also cause problems. Furthermore, the obtained color image (dye transfer image) also has the problem that bacteria and mold grow during long-term storage, damaging the image.

[Purpose of the invention]

The purpose of the present invention is to prevent the above-mentioned drawbacks, that is, the generation of sediments and floating substances in water as a transfer aid or development accelerator during storage, and to obtain excellent dye images without uneven development or uneven transfer. Our goal is to provide the best possible color images.

Another object of the present invention is to suppress the growth of bacteria and mold on the dye images obtained.

[Means for solving problems]

The present inventors have conducted various studies to solve the above problems, and as a result, have found that the above objects can be achieved by the present invention described below.

That is, the present invention provides a method for treating a diffusible dye produced or released from a dye-donating substance in response to or inversely to the reaction in which silver ions are reduced to silver by development in the presence of at least one antibacterial and anti-pie agent. , is a force 2-image forming method characterized by transferring from a photosensitive element to a dye fixing element using water as a medium.

The present invention will be explained in detail below.

The antibacterial and antibacterial agent used in the present invention may be any agent as long as it does not adversely affect photographic performance, but specific examples include thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, and bromophenols. compounds, thiocyanic acid and isothianic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds, cyclohexy A/phenol compounds, Antibacterial and antibacterial agents such as imidazole and hypenzimidazole compounds, sulfamide compounds, active halogen compounds such as chlorinated sodium isocyanurate, chelating agents, sulfite compounds, and antibiotics such as knitillin, etc.
946 (1965); JP-A-57-8
No. 542, No. 58-105145.

No. 59-126533, No. 55-1) 1942.

and various antifungal agents described in No. 57-157244; antibacterial and fungicidal agents described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi (Sankyo Publishing, 1981), Yoshiyuki Inoue @J, AntibaatAn
tifung Agents Vow 1). Ji
The antibacterial and fungicidal agents described in 5 p. 207 to 223 can be used.

Specific examples are shown below, but the invention is not limited to these.

1,5-chloro-2methyl-4-inthiazoline-3-
2. 2-(4-thiazolyl)-benzibadazole 3, methyl inthianate 4, 3.5-dichloro-4'-fluorothiocarbanilide 5. 4-chloro-35-dimethylphenol 6, 24
6-) Dichlorophenol L Sodium dehydroacetate & Sulfanilamide 9,: 145-) Salicylanilide 108 Potassium sorbate 1), Benzalkonium chloride 912.1-Zolomo 3-chloro-a5-dimethylhydantoin 13, Monochloro acetamide 14, heptanopromoacetamide 15, monoiodoacetamide 16, benzimidazole 17 cyclohexylphenol 1 & 2-octyl-isothiazolin-3-one 19, ethylenediaminetetraacetic acid 20, nitrilo-N,N,N-)limethinephosphonic acid 2
L 1-hydroxyethane-1,1--,% phosphonic acid 2z ethylenediamine-N, N, Nt, N/
-tetramethylenephosphonic acid 23, chlorinated sodium incyanurate 24. 2-methyl-4-inthiazolin-3-one 25, 10.10'
-Oxybisphenoxyarsine 26.1.2-benzisothiazolin-3-one In the present invention, the antibacterial agent is added to any one or more of the photosensitive element, the dye fixing element, and the water to be applied. I can do it.

There is no particular limit to the amount of anti-bacterial agent added, but when adding it to feed water, it is preferably 1 x 10 to 100 ml per 1 part of water.
1. Q mole, preferably 1x10~2x
It is 10 mole. When added to a photosensitive element and/or dye fixing element, 1 m'a! u) IXI
O~5X10 moxe, preferably 1x10~
lXl0 mole.

The water used in the present invention is not limited to so-called 1-pure water, but includes water in the widely conventional sense.

The water used in the present invention includes general drinking water, industrial water, and the like. For water used as general drinking water, for example, there are water quality standards for tap water in the United States and water quality standards set by the World Health Organization (WHO), and water that meets these standards corresponds to heather as referred to in the present invention. . Furthermore, water commonly used in various industries also corresponds to the water referred to in the present invention.

Water quality standards used in various industries are described, for example, in Sanitary Engineering Handbook, published by Asakura Shoten, 1967, p. 356. Water that meets the above criteria can be used as water in the present invention, whether it is underground water, river water, or to which chemicals (e.g., caustic soda, caustic potash, lower alcohols, etc.) have been intentionally added.

In the present invention, in addition to the antibacterial agent described above, various water softeners, such as organic phosphonic acid compounds, sodium behexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of these polyphosphoric acids, are used. Polyphosphoric acid compounds represented by: ethylenediaminetetraacetic acid, nitrotriacetic acid, triethylenetetramitometaacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, It is preferable to add aminopolycarboxylic acids typified by diaminobrognoltetraacetic acid and their alkali metal salts. There is no particular limit to the amount added, and it is determined appropriately depending on the hardness of the water, but usually, when added to feed water, water 1) 0 JO 19 to 309, preferably 0.0
It is used in the range of 19 to 109. When added to a photosensitive element and/or dye fixing element, 0.01W to 5%
9/l, preferably in the range of 0.1η to 19/-.

Methods for applying water to photographic elements include, for example, a roller coating method as described in JP-A-59-181353, or a wire-bar coating method as described in JP-A-59-181.
A method of applying water to a photographic element using a water-absorbing member as described in No. 354, JP-A-59-181348.
As described in the above issue, water is applied by forming a bead between a water-repellent roller and a photographic element; other methods include the detubing method, the extrusion method, the method of applying water by ejecting it as a jet from pores, and the method of applying water by spraying it as a jet from pores; Various methods can be used, such as a method of applying in a compressed manner.

Water may be applied at any time before the dye transfer. That is, water is applied to the photosensitive element and/or the dye fixing element during or after development. In addition, after applying water in the above process, if there is water remaining on the surface of the photosensitive element or dye fixing element without being absorbed into the coating layer, it may be squeezed out by applying pressure with a roller or the like.
In order to obtain a high-quality dye image without bleeding, it is preferable to remove it by blowing it off with wind or drying it with hot air.

When a light-sensitive element having a layer that generates or releases a diffusible dye and a dye-fixing element having a mordant layer are formed on separate supports, water is supplied to the former or the latter, and then the coated surfaces are connected to each other. From the viewpoint of speed and simplicity, it is particularly preferable to overlap the two so that they are in contact with each other, and to transfer all the diffusible dye produced or released at the same time as development from the former to the latter. It is preferable to apply this heat removal because development and dye transfer proceed rapidly.

Heating means in this step include heating by passing between hot plates or heating by contacting with hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635
), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. 43-rO791), heating by passing through hot air (for example, Japanese Patent Application Laid-Open No. 53-327)
37), heating by passing it through an inert liquid kept at a constant temperature, heating by passing it along a heat source using a roller, bolt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. can. Additionally, one or both photographic elements may include graphite,
Layers of electrically conductive material such as carbon black, metal, etc. may be applied in layers, and electrical current may be passed through the electrically conductive layers to heat them directly.

The heating temperature applied in the image forming method of the present invention can be in the range from the temperature in the heat development step to room temperature when the transfer step is started after the heat development step, but in particular, it is 60° C. or higher, and in the heat development step, transfer is possible. It is preferable that the temperature is lower by 10°C or more. Further, when the heat development step and the transfer step are performed simultaneously, the temperature is preferably 60° C. or higher and lower than the boiling point of the supplied water. The pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact varies depending on the materials used, but is 0.1~
100 yu/- preferably 1~50kl? /- is appropriate (for example, as described in Japanese Patent Application No. 58-55691).

Methods for applying pressure to both of the above include a method of tracing between paired rollers, a method of pressing using a plate with good smoothness, etc.
Various methods can be used.

Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

In the present invention, in addition to water, dye transfer aids other than water can be used. In a system in which the transfer aid is supplied from the outside, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, or diisobutylketone is used as the dye transfer aid other than water. Dye transfer aids may be used in a manner that wets the photographic element with the transfer aid.

If the transfer aid is incorporated into the photographic element, there is no need to provide external transfer aids other than water. Preferably, there is a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the photosensitive element or dye fixing element.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

The method of the present invention provides a photographic element having a layer containing a diffusible dye, in which the diffusible dye is reduced to silver in response to or inversely to the reaction in which silver halide is reduced to silver using a developer solution at a temperature near room temperature. It can also be applied when using a so-called color diffusion transfer photosensitive material that generates or emits light (in this case,
The antibacterial and antibacterial agent can be contained in both the photosensitive material and the developer.)

However, in the method of the present invention, when at least photosensitive silver halogenide, a binder and silver ions are reduced to silver by thermal development on a support as a photosensitive element, diffusion occurs correspondingly or inversely to this reaction. This embodiment is particularly suitable when a heat-developable color photosensitive material containing a dye-providing substance that generates or releases a diffusive dye is heated after image exposure to form a diffusible dye in the form of an image, so this embodiment will be described in detail below. .

Silver 10genide that can be used in the above heat-developable color light-sensitive material includes silver chloride, silver bromide, silver iodide, silver chlorobromide,
Any of silver chloroiodide, silver iodobromide, and silver chloroiodobromide may be used. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside. In addition, the thickness of the particles is 0.5 μm or less and the diameter is at least 0.6 pm.
Tabular grains having an average aspect ratio of 5 or more or monodispersed emulsions having a nearly uniform grain size distribution can also be used in the present invention.

Two or more types of halogenated Ia having different crystal habit, halogen composition, particle size, particle size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes.

The grain size of the silver halide used is such that the average grain size is 0.
．． 0.001 μm to 10 μm is preferable, and 0.00 μm to 10 μm is preferable.
A thickness of 1 μm to 5 μm is even more preferred.

In the above heat-developable color photosensitive material, an organic metal salt oxidizing agent may be used in combination with the photosensitive silver halide.

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent. −
1) Organic thioether derivatives described in No. 386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (■, II/) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Tardel water washing method or the precipitation method can be applied.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization method 1, reduction sensitization method, noble metal sensitization method, etc. can be used alone or in combination. These chemical sensitizations can also be performed in the presence of nitrogen-containing heterocyclic compounds (
JP-A No. 58-126526, No. 58-215644).

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1.eta. to 10 g/- in terms of silver.

In the present invention, the organic metal salt t-oxidizing agent, which is relatively stable to light, can be used together with the photosensitive silver halide. In this case, the photosensitive silver halide and the metal salt must be in contact with each other or at a close distance. Among such organic metal salts, organic silver salts are particularly preferably used. When an organic metal salt is used in combination in this way, the temperature of the heat-developable photosensitive material is 60°C or higher, preferably 80°C or higher.
When heated to a temperature of .degree. C. or higher, the organometallic oxidizing agent is also considered to participate in redox using the silver halide latent image as a catalyst.

Specific examples of useful organic silver salt oxidizing agents include JP-A-58-5
Examples include those described in No. 8543, page (19), lower left column to page (20), upper right column.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This system using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of the developer and coupler are 1
For example, T-H, James, “TWe theo
ry of thephotographic pro
cess 1I4th, 'f2a, page 1291~
Pages 334 and 354-361, Makoto Kikuchi
It is described in detail in "Photo Chemistry", 4th edition (Kyoritsu Shuppan), 284-295 E.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds are described in Research Disclosure magazine, May 1978 issue, pages 54-58, (RD-16966).

Furthermore, azo dyes used in the heat-developable silver dye targeting method can also be cited as examples of dye-donating substances.

Specific examples of azo dyes and bleaching methods are disclosed in US Pat. No. 423
No. 5957, Research Disclosure Magazine, 1976
It is described in the April issue, pages 30-32 (RD-14433).

Also, U.S. Patent No. 398 fi565, U.S. Patent No. 4.02z
Leuco dyes described in No. 617 and the like can also be cited as examples of dye-donating substances.

Another preferred example of the dye-donating substance is a compound having the function of releasing or diffusing a diffusible dye in an imagewise manner.

This type of compound can be represented by the following general formula (L).

(Dye-X)n-Y (L engineering) Dy
5s represents a dye group or a dye precursor group;
A compound represented by n-Y causes a difference in diffusivity, or Dye-releases and causes a difference in diffusivity between the released Dye and (Dye -X) n-Y. represents a group having the properties, n is 1
or 2, and when n is 2, the two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula [L], for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Pat. No. 3,134,764;
It is described in the same No. 3362.819, the same No. 3597, 200, the same No. 3544545, the same No. 3482.972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51-63618, etc., and a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring is disclosed in JP-A-51-63618. 1972-1) L62
It is stated in No. 8 etc. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred.

Furthermore, in these methods, development and dye release or diffusion occur in parallel, so it is very difficult to obtain an image with a high SZN ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have dye-releasing ability, and is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains unoxidized. A system for releasing a diffusible dye has also been devised, and specific examples of dye-donating substances used therein are disclosed in JP-A No. 53-1) Q827;
No. 10J54-13Q927, No. 56-164342, and No. 533 to No. 53-3.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer has been patented in the UK. No. 1,33Q524, Special Publication Showa 48-3'4
No. 165, U.S. Pat. No. 3,443,940, etc., and U.S. Pat. No. 3, U.S. Pat.
227, No. 550, etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised.

Representative examples are shown below along with literature. Definitions in the general formula are described in each literature.

U.S. Patent No. 392FL312 etc. U.S. Patent No. 4053312 etc. U.S. Patent No. 4055x428 etc. U.S. Pat. -104343 JP 51-104353 JP 51-104343 N H8Oz -Dy e Research Disclosure Magazine 17465 U.S. Patent No. 3725062 U.S. Patent No. &72-1) 3 U.S. Patent No. 3443939 58-1) No. A537 The characteristics required for the image forming dye are 1) having a hue suitable for color reproduction, 2) having a large molecular extinction coefficient,
3) stability against light, heat, and other additives such as a dye release aid contained in the system; and 4) ease of synthesis. Specific examples of preferable image-forming dyes satisfying these conditions include Japanese Patent Application Laid-Open No. 58-58543.
In addition to the compounds described in the lower right column of page No. (8) to the upper right column of page (1), cyan image forming compounds of the following formula, etc., compounds expressed by the following general formula (A) There are dyes that can be metal chelated.

Specific examples of the dye of general formula (A) and the dye-donating substance having this dye include, for example, JP-A-53-35533 and JP-A-53-35533;
7-1) No. 1534, No. 57-1) No. 1535, No. 57
-1) No. 9346, No. 57-185040, No. 57-
No. 185433, No. 57-158637, No. 57-1
No. 81546, No. 57-182738, No. 59-14
No. 9362, No. 59-15448, No. 59-1645
No. 53, U.S. Pat. No. 419fi994, N4207.1
04, 414F%641, 4147.544, 414 to 642, 41)%643, 428
7.292, 434 to 161-4357, 41
No. 0, No. 435 Shiguchi No. 1, No. 4357, No. 412, etc. Specific examples of the dye of general formula (A) include: yellow magenta so, ha2 02NH2 cyan CH3CH-8o□NH.

etc., but are not limited to these.

Among the various dye-providing substances described above, those in which the diffusible dye released or produced are hydrophilic dyes are particularly preferred. Here, the term "hydrophilic dye" refers to one having a hydrophilic group (eg, carboxyl group, sulfo group, etc.).

If a hydrophilic heat solvent is used for such diffusible dyes,
Transfer can be performed without externally supplying water, but it is preferable to supply water as in the present invention because the transfer time is shorter.

Specific examples of dye-donating substances used in the present invention are described in the patent documents listed above.

Since it is not possible to list all the preferred compounds here, some of them will be shown as examples. For example, the dye-donating substances represented by the general formula (LI) include those described below.

L knee I LI-2 L knee 3 L knee 4 L knee 5 H LI-5 H QC16H33 (nl L knee 7 G LI-g HL knee 9 0H I-IQ L knee 1) l-12 L knee 13 H L Knee 14 HL Knee 15 L] Knee 15 H The compounds described above are merely examples, and the present invention is not limited thereto.

In the present invention, the dye-donating substance is U.S. Pat.
They can be introduced into the layers of the light-sensitive material by known methods such as the method described in No. 2.027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthanolic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
Tricresyl phosphate.

dioctyl butyl phosphate), citric acid ester (
(e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl lacrylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate),
High boiling point organic solvents such as trimesates (e.g. tributyl trimesate), ° or organic solvents with a boiling point of 30°C to 160°C, such as lower alkyl acetates such as ethyl acetate, butyl butyrate, ethyl propionate, secondary butyl Alcohol, methyl isobutyl ketone, β
- After being dissolved in ethoxyethyl acetate, methylselonupacetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance tm in the aqueous colloid, and examples of these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g per 1 g of the dye-donating substance used.
It is as follows.

In the present invention, it is preferable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducibility but exhibit reducibility through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane amine complexes, hydroquinones, amine phenols, In addition to fcols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., T. D. James, '''Th
theory of the photography
ic prOc88B”4H1, Ea, 291-334
Reducing agents listed on the page can also be used. In addition, JP-A-56
Reducing agent precursors described in No. 13fi736, No. 57-4Q245, and US Pat. No. 433Q617 can also be used.

Combinations of various developers can also be used, such as that disclosed in U.S. Pat. No. 3,039,869.

Image formation accelerators can be used in the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive materials. Physicochemical functions include bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or It is classified as a compound that interacts with silver ions. However, these groups of substances generally have multiple functions9 and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function.
Although specific examples of each are shown, this classification is for convenience only, and in reality, one compound often has multiple functions.

(a) Base Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metabolites. Acid salts; ammonium hydroxides; hydroxides of quaternary alkylammonium; hydroxides of other metals, etc.; examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); )
; Aromatic amines (N-alkyl substituted aromatic amines,
N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamino)7enyl]methanes),
Examples include heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 8 or more are particularly preferred.

(bJ Base Precursor Base precursors include salts of organic acids and bases that decompose by decarboxylation by heating, and decompose by reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement to release amines. Preferably used are compounds that undergo some kind of reaction upon heating and release a base. Preferred base precursors include trichloroacetic acid salts described in British Patent Nos. 99 and 949, and U.S. Patent No. 406Q4.
Salt of α-sulfonylacetic acid described in No. 20, patent application No. 1983-
55.700, 2-carboxycarboxamide derivatives described in U.S. Pat. Nos. 408 to 496, thermally decomposable acids using an alkali metal or alkaline earth metal in addition to an organic base as the base component. (Japanese Patent Application No. 58-69597), hydroxyl carbamates described in Japanese Patent Application No. 58-43860 using Rossen rearrangement, and Japanese Patent Application No. 58-31゜614 which generates dinitrile by heating. Examples include the fludoxime carbamates listed above. In addition, base precursors described in British Patent Nos. 99 & 945, US Patent No. 322Q846, JP-A-50-22625, British Patent No. 207Q480, etc. are also useful.

(C) Nucleophilic compounds water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols It is also possible to use salts or precursors of the above-mentioned compounds.

(dl oil) A high-boiling organic solvent (so-called plasticizer) used as a solvent during emulsification and dispersion of hydrophobic compounds can be used.

(e) Hot solvents Solid at ambient temperature, melting near the development temperature and acting as a solvent, including ureas, urethanes, amides, pyridines, sulfonamides, sulfones, sulfoxides, esters, and ketones. 40 for compounds of the class, ether class
Those that are solid at temperatures below ℃ can be used.

Pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547, JP-A-59-57
Examples include polyalkylene oxides described in No. 231.

(g) Silver 19 is a compound imide 9 that interacts with silver ions, nitrogen-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols and thioureas described in Japanese Patent Application No. 57-222247. , thioethers.

The image formation accelerator may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, a dye fixing layer, or any layer adjacent thereto. The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support.

Image formation accelerators can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases formic acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, and mercapto compounds that undergo a substitution reaction with a coexisting base upon heating. For acid precursors, for example, Japanese Patent Application No. 58-2
Examples include oxime esters described in Japanese Patent Application No. 16928 and Japanese Patent Application No. 59-48305, and compounds that release acids through Rossen rearrangement described in Japanese Patent Application No. 59-85834, which undergo a substitution reaction with a base by heating. Examples of the electrophilic compounds that cause electrophilic reaction include the compounds described in Japanese Patent Application No. 85836/1983.

The above-mentioned development stoppers are particularly effective when a base precursor is used, which is preferable.

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.

Among them, isothiuroniums represented by 2-hydroxyethylinthiuronium trichloroacetate described in U.S. Patent No. 3301.678, U.S. Patent No. 3668
Bis(isothiuroniums) such as 1,8-(a6-thioxaoctane)bis(isothiuronium trichloroacetate) described in No. 670, West German Patent Publication No. 21627
Thiol compounds described in No. 14, US Pat. No. 40122
Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate) and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in No. 60;
Compounds having 2-carboxycarboxamide as an acidic moiety, such as amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazolium phenylsulfonylacetate, are preferably used.

Furthermore, 7-zole thioethers and blocked azolinthione compounds described in Belgian Patent No. 76-071, 4-aryl-1-carbamyl-2-tetrazoline-5-thione compounds described in U.S. Pat. No. 3,893,859, and other U.S. Pat. No. 3,833,041. , No. 3844788, No. 3877, and No. 940 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are compounds such as L2.4-triazole, IH-tetrazole, thiocracil and L34-thiadiazole. Examples of preferred toning include 5-amino-L34-thiadiazole-2-thiol, 3-mercapto-LZ4-) lyazole, bis(dimethylcarno-2-mil) disulfide, 6-methylthiouracil, 1-phenyl-2-tetraazole. I77-5
-Thion, etc. Particularly effective toning agents are compounds capable of forming black images.

The binders used in the photothermographic material may be contained alone or in combination.

A hydrophilic binder can be used for this binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives, starch, etc.
These include natural substances such as polysaccharides such as gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

Is this binder IW? Atta. The coating amount is preferably 20 g or less, preferably 109 or less, more preferably 79 or less.

, 2 The ratio of the high boiling point organic solvent dispersed together with a hydrophobic compound such as a dye-donating substance and the binder in Ingu is 1 cc or less of solvent per 1 g of binder, preferably 1 cc or less of solvent, preferably 5 ee or less, and more preferably 0 , 3 cc or less is suitable.

In the heat-developable photosensitive material, an inorganic or organic hardener gold may be contained in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.), dioxane derivatives (23-dihydroxydioxane, etc.), Active vinyl compound (L35-)lyacrylyl-hexahydro-a-)! J azine, 43-vinylsulfonyl-2-propanol, 1,2-his(hynylsulfonylacetamido)ethane, etc.), active norogen compounds (2,4-
7-chloro-6-hydroxy-a-triacyl, mucohalogen ets, mucochloric acid, mucophenoxychloroic acid, etc.) can be used alone or in combination.

The support used for the light-sensitive material and color patch fixing material in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, but also cellulose acetate film, cellulose nitrous film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene pre-7 Includes talate films and their related film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. Polyesters described in US Pat. No. 3,634,089 and US Pat. No. 72,070 are preferably used.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
When containing a dye-donating substance represented by
Because the dye-donating substance is colored, irradiation prevention substances, noration prevention substances, or each
Although it is not so necessary to incorporate dyes into light-sensitive materials, in order to improve the sharpness and tone of images,
Filter dyes, absorbent substances, etc. described in US Pat. No. 3,692, US Pat. No. 3,253,921, US Pat. In addition, these dyes are preferably thermally decolorizable; for example, as described in US Pat.
No. 19, No. 374 to No. 009, No. 361fi432
Preference is given to dyes such as those described in No.

The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an A
It can contain an H layer, a release layer, etc. For various additives, see Research Disclosure Magazine Vow-17.
0, Additives described in No. A17029 of June 1978, such as plasticizers, sharpness improving dyes, JL dyes,
There are stock additives such as sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and anti-fading agents.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, the photosensitive material used in the present invention consists of at least three layers of halogenated scissors each sensitive to a different spectral region. It is necessary to have an emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. A combination of a light-sensitive emulsion layer and an infrared light-sensitive emulsion layer, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, etc.
and a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer. In addition, the infrared light-sensitive emulsion layer is 700 n! It refers to an emulsion layer that is sensitive to light of E1 or higher, particularly to light of 740 nm or higher.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer has a dye-donating substance that releases a yellow hydrophilic dye, a magenta hydrophilic dye that releases or It is necessary to contain either one of the dye-providing substance to be formed and the total release of cyan hydrophilic dye or the dye-providing substance to be formed. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues.

If desired, two or more dye-providing substances having the same hue may be mixed and used. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may be provided with auxiliary layers such as a film-retaining layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary.

In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion.

Further, this protective layer may contain a mordant, a UV absorber, and the like. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent for preventing color mixture, a UV absorber, and a white pigment such as 1'10□. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye so as to obtain the desired spectral sensitivity.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder.

Examples of materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide. Thin films can be made. In the latter method, conductive particles such as metal particles, carbon black, and graphite are dispersed in rubber, synthetic polymers, and gelatin to create a resistor with desired temperature characteristics. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, etc.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat generating element/support/photosensitive element support/heat generating element/sensitive element support/heat generating element/intermediate layer/photosensitive element support/photosensitive element/heat sensitive element support/photosensitive element/intermediate layer/heat generating element In the present invention As well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, back layer, and other layers are prepared for each layer, and are applied using the dipping method, air knife method, curtain coating method, or U.S. Pat. No. 368L294. The sensitized material can be prepared by sequentially coating onto a support by various coating methods such as the hopper coating method described in the specification, and drying.

Further, if necessary, U.S. Patent No. 2,76L791 MJ
3:1ilF and 2 hiz or more can also be applied simultaneously by the method described in British Patent No. 837.095.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used. In general, various light sources such as tungsten lamps, mercury lamps, halogen lamps such as iodine-9 lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light-emitting diodes (LEDs) are generally used for color printing. Can be used.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. When water is applied during thermal development, the upper limit of the heating temperature is approximately the boiling point of water.

The photographic element (dye fixing material) having a mordant layer used in the present invention has at least one layer containing a mordant, and when the mordant layer (dye fixing layer) is located on the surface, if necessary, Furthermore, a protective layer can be provided.

Furthermore, an absorbing layer or a layer containing a dye transfer aid may be provided in order to sufficiently contain a dye transfer aid, or to control the dye transfer aid, if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The mordant used in the dye fixing material used in the present invention is preferably a polymer containing one vinyl monomer unit representing a tertiary amino group or a quaternary ammonio group represented by the general formulas (X) to (Xlll).

General Formula (X) (1) [In the formula, R1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. L represents a divalent linking group having 1 to 20 carbon atoms. E represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom. n is O or R4 is 5 [wherein R□, "L, and n represent the same as in the general formula (X). R4 and R5 are the same or different alkyl groups having 1 to 12 carbon atoms, respectively, Alternatively, it represents an aralkyl group having 7 to 20 carbon atoms, and R4 and R5 may be interconnected to form a complete cyclic structure together with the nitrogen atom. n is O or 1. General formula (X[ [) % Formula % [In the formula, R0, L, n represent the same as the general formula LX]. G is a quaternized hetero ring containing a nitrogen atom having a double bond with a carbon atom as a constituent component. Xe represents a monovalent anion.

n is O or 1. ] General formula (XIII) [In the formula, R□, L, and n are the same as in general formula (X) and represent gold. R4 and R5 represent the same as in general formula (XI).

R6 is selected from the same as R4, R5't-. xe represents the same thing as general formula (Xll).

R4, R5, and R6 may be interconnected to form a cyclic structure together with the nitrogen atom. n is O or 1. ] In the general formulas (X) to (Xlll), R□ is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, It represents an n-hexyl group, etc., and a hydrogen atom or a methyl group is particularly preferred.

L is a divalent linking group having 1 to about 20 carbon atoms, such as an alkylene group (e.g., methylene, ethylene, trimethylene, hexamethylene, etc.), a phenylene group (e.g., O-), a unicine group, p-phenylene group, m-phenylene group, etc.), A represents about 12 alkylene groups.

), -Co2-1-CO□-R3- (However, L R3 represents an alkylene group, phenylene group, or arylene alkylene group.), -CONH-R3- (However, R3 represents the same as above.), -CON-R3- (However, R□, R
3 represents the same as above. ), f12- -C02-CH2CH2-1-CO2-CH2CH2C
H2-1-CONflCH2-1-CONHCH2CH
2-1-CONHCI32CH2CH2- and the like are particularly preferred.

In the general formula (X), E is particularly preferably a petro ring containing a nitrogen atom having a double bond with a carbon atom, such as an imidazole ring (eg, a ring, or a pyridine ring).

Preferred specific examples of the polymer containing one vinyl monomer unit having a tertiary amine group represented by the general formula (X) are described in U.S. Pat. No. 4,282,305, U.S. Pat. The following mordants are included:

(Number 2 moles) In the general formula (XI), R4 and R5 are alkyl groups having 1 to 12 carbon atoms, such as unsubstituted alkyl groups (methyl group, ethyl group, n-propyl group, n-butyl group, n -amyl group, hexyl group, n-nonyl group, n-decyl group, n-
dodecyl group, etc. ), a substituted alkyl group (methoxyethyl group, 3-cyanopropyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydrocarbon diethyl group, 2-butenyl group, etc.), or an aralkyl group having 7 to 20 carbon atoms. groups, such as unsubstituted aralkyl groups (benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.), substituted aralkyl groups (4-methylbenzyl group, 4-isopropylbenzyl group, 4-methoxybenzyl group, 4-( 4-methoxyphenyl)benzyl group,
3-Chloro is a ndyl group, etc. ) etc.

Further, as an example in which R4 and R5 are interconnected to form a cyclic structure together with a nitrogen atom, preferred specific examples of polymers containing one vinyl monomer unit having a tertiary amine group represented by the general formula (Xl) include the following: Things can be mentioned.

(Number 2 molti) In the general formula (Kari), Go represents a heterocycle which is quaternized and contains a nitrogen atom having a double bond with carbon as a constituent, and an example thereof is k13M in imidazolium salt.

Midazolium salts and pyridinium salts are particularly preferred.

Here, R4 is the same t-representation as in general formula (XI), and methyl, ethyl, and benzyl groups are particularly preferred.

In the general formula (Kari), (Xln), Xe represents an anion,
For example, halogen ions (e.g., chloride, bromide, iodine), alkyl sulfate ions (e.g., methyl sulfate, ethyl sulfate), alkyl or aryl sulfonate ions (e.g., methanesulfonic acid,
Examples include ethanesulfonic acid, phosphoric acid, benzenesulfonic acid, p-)toluenesulfonic acid), acetate ion, and sulfate ion, with chloride ion and p-)toluenesulfonic acid ion being particularly preferred.

Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary ammoniobase represented by the general formula (X[[) include British Patent No. 2.051) 4101;
No. 093041, No. 1.594961, U.S. Patent No. 4
No. 124386, 41)! 'x No. 124, 4273
No. 853, No. 445Q224, JP-A-48-2822
The following may be mentioned, including the mordant described in No. 5.

le H3 -Tooe (Number Two Moles) In the general formula (Xln), as an example where R4 and R5 are interconnected to form a cyclic structure with the nitrogen atom, le, R4,
Examples of forming a cycyclic structure with R5 and R6 and general formula tXn
Preferred specific examples of the polymer containing one vinyl monomer unit having a quaternary ammonio group represented by l) include:
U.S. Patent No. 370190, U.S. Patent No. 389a088, U.S. Patent No. 3
The following may be mentioned, including the mordant described in No. 95a995.

l CA! e Ole (Number: Molch) Others, U.S. Patent No. 254 & 564, U.S. Patent No. 2.484
No. 430, No. a148,061, No. 375a81
Vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in U.S. Pat. No. 4, etc.; U.S. Pat.
2F%538, a polymer mordant capable of crosslinking with gelatin etc. as disclosed in British Patent No. 1.277.453; US Patent No. 395F%995, British Patent No. 2.72
No. 1,852, No. 279be063, Japanese Unexamined Patent Publication No. 1983-1
) No. 5228, No. 54-145529, No. 54-12
Aqueous sol-type mordant disclosed in US Pat. No. 6027, etc.: Water-insoluble mordant disclosed in US Pat. A reactive mordant capable of covalently bonding with the dye disclosed in Kutsubo; furthermore, U.S. Pat.
No. 709,690, No. 855 to No. 378, No. 364
No. 2.482-, No. 3481 (No. 706, No. 3)
No. 557.066, No. 327 L 14171, F
1 & 271,148, JP 50-71332, JP 53-30328, JP 52-155528, JP 53
Examples include mordants disclosed in Japanese Patent No. 125 and No. 53-1024.

Others, US Patent No. 267! 'x No. 316, same No. 288
Mention may also be made of the mordants described in No. 2.156.

The mixing ratio of the polymer mordant and gelatin and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, the image forming process to be used, etc. However, the mordant/gelatin ratio is 20/80-80/20 (weight ratio), and the mordant application amount is 02 to 159/m', preferably 0.5 g to
8g/n? It is preferable to use it in The molecular weight of the polymer mordant of the present invention is from LOOO to 100QOOO, especially IQO.
OO to 20QOOO is preferred.

By using a polymer mordant and metal ions in combination, the dye transfer density can be increased.

This is particularly effective when using a dye-donating compound that releases a dye capable of metal chelation as described above.

In this case, a mordant may or may not be used.

These metal ions are added to the dye fixing layer containing the mordant, or to the upper and lower layers adjacent to the dye fixing layer. The metal ion used here is desirably colorless and stable against heat and elements. That is, cu”, Zn”, N1
Polyvalent ions of transition metals such as 21, Pt", Pa", and C02+ ions are preferred, and Zn is particularly preferred. This metal ion is usually added in the form of a water-soluble compound, such as ZnSO4, ZntCH3CO2)2, and the amount added is 0.01 to 59/rI? , preferably 0.1~
1.59/lt? It is.

The dye fixing material used in the present invention may be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary, in addition to the above-mentioned layer.

One or more layers of the above 71il may include a base and/or base precursor to promote dye transfer, a hydrophilic heat solvent, an anti-fading agent to prevent color mixing of the dyes, and an Ul.
/Absorbent, a dispersed vinyl compound for increasing the dimensional stability, a fluorescent brightener, etc. may be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, water-soluble polyvinyl compounds such as dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Synthetic polymeric substances etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In addition to the above, the dye fixing material may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated not only in the dye fixing material but also in the photosensitive material. The structures of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer are described, for example, in U.S. Patent No. 2.983606, U.S. Pat. It is described in No. 559, etc.

Example 1 This article describes how to make a benzotriazole silver emulsion.

289 parts of gelatin and 13.29 parts of benzotriazole to 3 parts of water
001) Dissolves in Lj. This solution was maintained at t-40'CIC and stirred. Add 179t of silver nitrate to this solution and 100ml of water.
Add the solution dissolved in it over 2 minutes.

The benzotriazole silver emulsion is pH't-adjusted, allowed to settle, and excess salt is removed. After that, pH? 6.30
Accordingly, a benzotriazole silver emulsion with a yield of 400 g was obtained.

This article describes how to prepare silver halide emulsions for the fifth and first layers.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 39 mJ of sodium chloride in 1,000 mJ of water and keeping it warm at 75°C) contains a 600 mJ aqueous solution containing sodium chloride and potassium bromide and an aqueous solution of silver nitrate (600 mJ of water). (0.59 mol of silver nitrate dissolved in the solution) were added at the same time and at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (
50 mol of bromine) t-prepared.

After washing with water and desalting, sodium thiosulfate 51)9, 4-hydroxy-6-methyl-L33a, and 20η of 7-chitrazaindene were added to perform chemical sensitization at 60'C. The yield of emulsion was 6009.

Next, we will explain how to prepare a silver halide emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing gelatin 209 and sodium chloride 39'' in water 1000 and kept at 75°C) contains an aqueous solution 6001R1! containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (water 60
0mA! 0.59 mol of silver nitrate dissolved in gold) was simultaneously added to 40. Added at equal flow rate over Q period. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol of bromine) with an average grain size of 0.35 .mu.m was prepared.

After washing with water and desalting, 5 kg of thiosulfate and 7 K of 4-hydroxy-6-methyl-Laaa, 7-titrazaindene were added to carry out chemical sensitization at 60°C. The yield of emulsion was 600 g.

Next, a method of preparing a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-donating substance (A) i59, surfactant: 2-ethyl-hexyl succinate sodium sulfonate 0.59. ) Liisononyl phosphate 1
0 g'l: Weigh, add 30 mJt of ethyl acetate, approx.
Heat and dissolve at ℃ to make a homogeneous solution. After stirring and mixing this solution and 10% filo09 of lime-treated gelatin, the mixture was dispersed using a homogenizer for 10 minutes at 1) 0000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-donating substance was prepared in the same manner as described above, except that the magenta dye-donating substance (B)'i was used and tricresyl phosphoryl If7,5S) was used as a high boiling point solvent. Had made.

A cyan dye-providing substance (c)y was prepared in the same manner as the yellow dye dispersion.

With these, a color photosensitive material having a multilayer structure as shown in Table 1 was prepared.

Dye-donating substance (A) (B) QC,, H33 (H) (C) OC16H33) (D-1) (D-2) u)-3) Next, create a dye fixing material having a dye fixing layer. Let's talk about the direction.

First, gelatin hardener H-1 (0.75g), H-2 (
0,259) and 155 liters of water and 1-group surfactant W-1 (5d), and 10 liters of lime-treated gelatin
*'e Mixed uniformly. This mixed solution was placed on a support laminated with polyethylene in which titanium oxide was dispersed.
After applying it uniformly to form a wet film of 100 m, it was dried.

Gelatin hardener H-1 CH2-CH8O2Cfi2Q)Nfi-CH20H2
Nu CH2-302C) I-CH2 gelatin hardener H
-2 CH2-CHBO2CH2CONHCH2-CH2CH
2NHCOCH,5o2CH-C:H2 surfactant w-
1 Next, 15 g of a polymer with the following structure and 5 g of polyvinylpyrrolidone (degree of polymerization 3000) were dissolved in 180 ml of water,
5th group surfactant W-2 (15d), 5th group surfactant W-
3 (2 m7) and 10 cm of lime-treated gelatin 1009 were uniformly mixed. This mixed solution was uniformly applied onto the above-mentioned coating material to form a wet film of 85 μm. This sample was dried to obtain a dye fixing material (A).

Surfactant W-2 Surfactant W-3 3H7 in Polymer 802 Next, the color photosensitive material having the multilayer structure was uniformly exposed for 1 second at 500 lux using a tungsten light bulb.9.

Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 140°C.

Next, water having the composition shown in Table 2 was prepared, and after allowing it to naturally age in a beaker at 30°C for 30 days, it was applied to the membrane side of the dye fixing material. Each was fed in an amount of 720 ml.

Thereafter, this dye-fixing material and the photosensitive material that had been heat-treated were placed on top of each other so that their film surfaces were in contact with each other, and after heating for 6 seconds on a heat block at 80°C, the dye-fixing material was peeled off from the photosensitive material, and the dye A black image was obtained on the fixed material.

It was investigated whether or not there were speckle-like unevenness in this black image. The difference between the normal black image density and the black density of the uneven area is 0.
Shimla was evaluated by visual inspection if it was 4 or more. The spot-like unevenness that occurs here is an unevenness on the order of a nod, and when the proportion of the unevenness on the entire surface is 0, it is t-0, when it is 5 to 101, it is total Δ, and when it is 10 or more, it is x. Indicated. The results are shown in Table-2.

Example 2 IW? Our Shikushi 2 x IQmo
1) Prepare a dye fixing material by containing 5
After storage at 30°C and relative humidity of 80°C for 60 days, the supplied water was fresh tap water.The gold-sensitive material used in Example 1 was treated in the same manner as in Example 1. Almost the same results as 1 (Table 2) were obtained.

It has been found that the effects of the compound of the present invention vary greatly whether it is contained in the feed water or in the dye-fixing material.

Example 3 A color photosensitive material 301 having a multilayer structure shown in Table 3 was prepared using the emulsion used in the photosensitive material of Example 1 and the gelatin dispersion of the dye-providing substance.

Next, we will discuss how to prepare the dye fixing material.

63 g of gelatin, 130 g of a mordant having the following structure, 409 guanidine carbonate and 1300 d of guanidine carbonate were dissolved in water, coated on a paper support laminated with polyethylene to a wet film thickness of 45 μm, and dried.

Mordant Further on top of this, 35g of gelatin, L2-bis(vinylsulfonylacetamidoethane) 1.059t-800a
A dye fixing material (gold) was prepared by coating and drying a solution of tj dissolved in water to a wet film thickness of 17 μm.

The compounds of the present invention shown in Table 4 were added to the sixth layer of the photosensitive material 301, respectively. Photosensitive material 302 having exactly the same composition as 301 except that it was contained so that the ratio was 2×10m01θ
~305t'' was created.

Using tungsten light bulbs for the photosensitive materials 301 to 305,
Uniform exposure was performed for 1 second at 500 lux.

Distilled water placed in separate storage tanks (capacity: 100 d each) for each light-sensitive material was applied to the emulsion surface of each light-sensitive material using a wire spar, excess water was squeezed out using a roller, and the water was returned to the storage tank. The emulsion surface of the light-sensitive material and the film surface of the dye-fixing material were superimposed so that they were in contact with each other.

The film was heated for 25 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90°C.

Thereafter, when the light-sensitive material was peeled off from the dye-fixing material, a black dye image was obtained on the dye-fixing material.

The water in each storage tank was reused, and each photosensitive material was continuously treated in the same manner up to 1 d, and then stored at -30°C in the storage tank for 30 days. Thereafter, the photosensitive material was processed in the same manner once again using the preserved water, and it was examined whether or not there were irregularities in the form of spots in the black image on the dye-fixing material. The results are shown in Table 4 using the same criteria as in Example 1.

From the above results, it was found that addition of the compound of the present invention exhibits a remarkable effect even in an image forming method in which a developing step and a transfer step are integrated.

Claims (2)

[Claims] (1) A diffusible dye produced or released from a dye-donating substance in response to or inversely to the reaction in which silver ions are reduced to silver by development is treated in the presence of at least one antibacterial and anti-bacterial agent. , a color image forming method characterized by transferring from a photosensitive element to a dye fixing element using water as a medium. (2) Claim 1, wherein the diffusible dye is produced or released by thermal development.
Color image forming method described in Section 1.