JPH0743876A - Image forming method - Google Patents

Abstract

PURPOSE:To provide a method for easily and rapidly forming a color image by using a processing solution easy in management and a photosensitive material superior in raw stock stability. CONSTITUTION:The color image is formed by using the photosensitive material containing at least photosensitive silver halide, a reducing agent, a dispersion- resistant dye donor capable of releasing a dispersible dye in reverse correspondence with development of silver halide and a binder on a support and processing this photosensitive material in an alkaline solution of >=8 in pH, then processing it in a bleaching bath and a fixing bath or a bleach-fixing bath or only in the fixing bath, and further rinsing and drying it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method, and more particularly to a color image forming method which uses a silver halide light-sensitive material and is capable of easily controlling a processing solution.

[0002]

BACKGROUND OF THE INVENTION A general method for forming a color image from a photographic light-sensitive material, for example, a color photographic light-sensitive material, is halogenation in the presence of a color coupler capable of reacting with an oxidant of a developing agent to form a dye. It is a method of obtaining an azomethine or indoaniline dye by developing a silver light-sensitive material with an aromatic primary amine developing agent. This color development method is basically 1935 LD Mannes & L. Go
It was invented by dowsky and has been subsequently improved in various ways, and is used in the industry in the world today.

The processing steps of a color photographic light-sensitive material are basically composed of the following five steps. (1) Color development process (2) Bleaching process (3) Fixing process (4) Washing process (5) Drying process

The bleaching step and the fixing step can be carried out simultaneously. That is, it is a bleach-fixing step (so-called brix), in which developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering described above, the actual development process includes auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image. Accompany it. For example, a hardening bath for preventing excessive softening of the photosensitive film during processing, a stopping bath for effectively stopping the development reaction, an image stabilizing bath for stabilizing the image, or a removing bath for removing the backing layer of the support. A process such as a membrane bath may be mentioned.

[0005]

Usually, an aromatic primary amine developing agent is dissolved in an alkaline aqueous solution and used in a color developing solution. When the aromatic primary amine developing agent can be incorporated in the light-sensitive material, the development can basically be carried out only with an aqueous alkali solution. This allows
The developer can be easily prepared, the change in the composition of the developer can be reduced, and the management can be facilitated. Further, there are many advantages such as that the BOD of the waste liquid is remarkably reduced and the waste liquid can be easily treated. However, in general, incorporating an aromatic primary amine developing agent in a light-sensitive material causes desensitization of the light-sensitive material during storage, generation of fog or stain, and insufficient coloration due to processing. It has many drawbacks and has not yet been put to practical use.

(Object of the Invention) The first object of the present invention is to provide a color image forming method which is easy to prepare a processing solution, has a small change in composition of the processing solution, and is easy to manage. The second object is to provide a color image forming method that facilitates waste liquid treatment. Thirdly, it is to provide an image forming method in which the raw storage property of the light-sensitive material is good and a stable color image can be obtained for a long period of time.

[0007]

The various objects of the present invention are as follows.
A light-sensitive material having at least a photosensitive silver halide, a reducing agent, a diffusion-resistant dye-donor compound that releases a diffusible dye corresponding to the development of a silver halide and a binder on a support is used as an alkaline aqueous solution having a pH of 8 or more. After processing with
It was achieved by a method of forming an image by treating with a bleaching solution, a fixing solution (or a bleach-fixing solution) or a fixing solution alone, followed by washing with water and drying.

The present invention will be described in more detail below. Specific examples of the diffusion-resistant dye-donor compound that releases a diffusible dye in response to the development of silver halide used in the present invention include the following compounds.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972, and Japanese Patent Publication No. 3-68. No. 387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. 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 also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
No. 396, Open Technical Report 87-6, 199, JP-A-64-1
As described in No. 3,546, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. As another example,
U.S. Pat. Nos. 4,139,389 and 4,139,37
9, JP-A-59-185, 333, JP-A-57-84,
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat. No. 4,232,107 and JP-A-59-101,6.
49, 61-88,257, RD24,025.
(1984) which releases a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-14.
2,530, U.S. Pat. Nos. 4,343,893, 4,619,884, and the like, a compound which cleaves a single bond to release a diffusible dye after reduction, U.S. Pat. Examples include nitro compounds described in U.S. Pat. No. 450,223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610, which release a diffusible dye after electron acceptance, and the like. To be

Further, as more preferable ones, European Patent No. 220,746, Open Technical Report 87-6,199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201,6.
No. 53, No. 63-201, 654, No. 64-13, 5
No. 46, etc., a compound having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, one molecule described in JP-A-1-26,842. A compound having SO ₂ -X (where X is as defined above) and an electron-withdrawing group within the molecule, and a PO-X bond (where X is as defined above) within one molecule described in JP-A-63-271344. And a compound having an electron-withdrawing group, JP-A-63-271341
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. In addition, JP-A-1-161,237
The compounds described in JP-A No. 1-161, 342, which release the diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group can also be used.

Among the above dye-donating compounds, the compounds represented by the following general formula [I] are particularly preferable.

[0013]

[Chemical 2]

In the general formula [I], EAG represents an electron-accepting group, X represents an oxygen atom (-O-), a sulfur atom (-S).
-) or nitrogen atom (-N (R ³⁾ -) represents a.
R ¹ , R ² and R ³ each represent a mere bond or a group other than a hydrogen atom. R ¹ , R ² , R ³ and EAG may combine with each other to form a ring. Time is N-
Through the subsequent reaction using the cleavage of the X bond as a scratch, D
It represents a group that releases ye, and t represents an integer of 0 or 1. Dye represents a diffusible dye. Also, the solid line is the connection,
The broken line indicates that at least one of them is connected. Specific examples of R ¹ , R ² , R ³ , EAG, Time, Dye and specific examples of the dye donating compound are described in European Patent No. 2
20,746, U.S. Pat. No. 4,783,396, Open Technical Report 87-6,199, JP-A-64-13,546.
No. etc.

The coating amount of the dye-providing compound in the present invention is 1 m ² per 0.01 to 20 mmol, preferably 0.0
It is 5 to 10 millimoles, and is 0.1 to 20 times mol, preferably 0.25 to 5 times mol, of the total silver amount per unit area. The dye-donating compound can be contained in the light-sensitive layer containing the light-sensitive silver halide or other layers (intermediate layer, reducing agent-containing layer, protective layer, etc.). In particular, in order to improve the sensitivity, it is desirable to add it to the lower layer adjacent to the photosensitive layer containing the corresponding silver halide. The dye-providing compounds may be used alone or in combination of two or more.

As the reducing agent used in the present invention, those known in the field of silver halide photosensitive materials can be used. Further, the above-mentioned reducing dye-providing compound (such as a dye developing agent) is also included (in this case, other reducing agents may be used in combination). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, and 4,83.
9,272, 4,330,617, 4,59
0,152, 5,017,454, 5,13
9,919, JP-A-60-140,335 (1)
7) to (18), ibid. 57-40, 245, ibid. 56-.
138,736, 59-178,458, 59
-53,831, 59-182,449, 59
-182,450, 60-119,555, 6
0-128,436, 60-128,439, 60-198,540, 60-181,742,
61-259,253, 62-201,434.
No. 62-244,044, 62-131,25
No. 3, No. 62-131, 256, No. 63-10, 15
No. 1 and No. 64-13,546 (40) to (57)
Page, JP-A-1-120,553, 2-32,338.
No. 2-35, 451 and 2-234, 158,
There are reducing agents and reducing agent precursors described in JP-A 3-160,443, EP 220,746, pages 78 to 96, 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, a diffusion resistant reducing agent (electron donor) is added to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide. It is desirable to use an electron transfer agent and / or electron transfer agent precursor having a higher mobility in combination. Particularly preferred electron transfer agents (precursors) are the above-mentioned US Pat. No. 5,139,919 and European Patent Publication No. 418,743.
No. 1-138,556, 3-102,34.
1-phenyl-3-pyrazolidones or aminophenols described in No. 5. In addition, JP-A-2-230,14
As described in No. 3 and No. 2-235,044, a method of stably introducing into the layer is preferably used.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the light-sensitive material.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
0827, US Pat. Nos. 5,032,487, and 5,
The compounds described as electron donors in Nos. 026,634 and 4,839,272, and dye-donor compounds having diffusion resistance and reducing property described later are included. Further, an electron donor precursor as described in JP-A-3-160,443 is also preferably used.

Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixture, improving color reproduction, improving white background, and preventing silver transfer to the dye fixing material. Specifically, European Patent Publication Nos. 524,649 and 357,04.
No. 0, JP-A-4-249,245 and 2-64,63.
3, 2-46,450, JP-A-63-186,2.
The reducing agent described in No. 40 is preferably used. In addition, Japanese Examined Patent Publication No. 3-63,733, Japanese Patent Laid-Open Nos. 1-150,135, 2-110,557, 2-64,634, and 3-
Development inhibitor releasing reducing compounds such as those described in EP 43,735 and EP 451 833 are also used. In the present invention, the total amount of reducing agents added is 0.01 to 20 mol, and particularly preferably 0.1 to 10 mol, per mol of silver.

Hydrophobic additives such as dye-donor compounds and antidiffusive reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555
470, 4,536,466, 4,536,4
No. 67, No. 4,587, 206, No. 4, 555, 47
No. 6, No. 4,599,296, Japanese Examined Patent Publication No. 3-62,25
A high-boiling point organic solvent as described in No. 6 or the like is optionally used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C.,
Can be used. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. In addition, Japanese Patent Publication No.
A method of dispersing by a polymer described in JP-A-853 and JP-A-51-59,943 and a method of adding a fine particle dispersion described in JP-A-62-30,242 can also be used. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,636 (37) to (38)
The compounds listed as the surfactants in the above-mentioned Research Disclosure can be used.

The light-sensitive material used in the present invention basically has a light-sensitive silver halide emulsion, a reducing agent, a binder and a dye-donating compound on a support. These components are often added to the same layer, but they may be added separately in different 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 electron transfer agent is preferably incorporated in the light-sensitive material, but may be added to the activator bath.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. . For example, JP-A-59-180,550 and JP-A-64-13,546, 6
2-253,159, European Patent Publication No. 479,167.
Combination of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer, infrared-sensitive layer combination, red-sensitive layer, infrared-sensitive layer (I), red There is a combination of the outer photosensitive layer (II). Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers as required, as described in JP-A-1-252954. In the light-sensitive material of the present invention, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between the silver halide emulsion layers and as the uppermost layer and the lowermost layer. May be provided, and various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure as described in the above patent, US Pat. No. 5,051,33
An undercoat layer as described in JP-A No. 5-167,838
No. 6, intermediate layers having a solid pigment as described in JP-A-61-20943, JP-A-1-120553, 5-
Nos. 34,884 and 2-64,634, an intermediate layer containing a reducing agent or a DIR compound, US Pat.
17,454, 5,139,919, JP-A-2-
An intermediate layer having an electron transfer agent as described in JP-A No. 235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer combining these may be provided. The support is preferably designed to have an antistatic function and a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion which can be used in the present invention is
It 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 fogging. Also,
It may be a so-called core-shell emulsion in which the inside of the grain and the surface of the grain have different phases, or silver halide having a different composition may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and the method of mixing the monodisperse emulsions and adjusting the gradation as described in JP-A-1-167,743 and 4-223,463 is preferably 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 one having a regular crystal such as a cube, octahedron, or tetrahedron, a sphere, an irregular crystal system such as a flat plate having a high aspect ratio, or a twin plane. It may be one having such crystal blood vessels, a composite system thereof, or the like. Specifically, US Pat. No. 4,500,626
No. 50, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17,643 (December 1978), pages 22-23, No. 18,716 (1979).
Nov., 648, same No. 307, 105 (198)
Nov. 9, pp. 863-865, JP-A-62-253,
159, 64-13,546, JP-A-2-23.
No. 6,546, No. 3-110,555, and Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Gl.
Chemie et Phisique Photographique, Paul by afkides
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Che
mistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman).
et al., Making and Coating Photographic Emulsion,
Any of the silver halide emulsions prepared by the method described in Focal Press, 1964) can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, the Nudel water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid). The precipitation method using sodium) or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more kinds. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-4-126629 are preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thioether compound and JP-B No. 47-1 are used as silver halide solvents.
The organic thioether derivatives described in 1,386 or the sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Monte
, 1697), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chem
istry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZeli).
kman et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964) and the like.
That is, any of the acidic method, the neutral method, and the ammonia method may be used, and as the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. In order to obtain a monodisperse emulsion, a reverse mixing method in which grains, which are preferably used in the simultaneous mixing method, are formed in the presence of excess silver ions can also be used. A so-called controlled double jet method in which the pAg in the liquid phase in which silver halide is produced is kept constant can also be used as one form of the simultaneous mixing method.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and 55-158). 124, U.S. Pat. No. 3,650,757). Further, the stirring method of the reaction liquid may be any known stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily according to the purpose. The preferred pH range is 2.2 to 8.5, more preferably 2.5 to 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in the emulsion for a conventional type light-sensitive material, gold, platinum, A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253,159). Further, an antifoggant described below can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
The method described in No. 0,446 can be used. . The pH during the chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.
It is 0 to 10.5, and more preferably 6.8 to 9.0.
The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to provide the photosensitive silver halide used in the present invention with green-sensitive, red-sensitive and infrared-sensitive color sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . Further, if necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, US Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of wavelength adjustment of supersensitization or spectral sensitization. . 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-63-23, 145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or a solution of a surfactant. The addition amount is generally 10 ^-8 to 10 per mol of silver halide.
^-It is about ² mol.

Additives used in such steps and photographic additives usable in the light-sensitive material of the present invention are RD No. 17,643, No. 18,716 and N.
No. 307, 105, and the corresponding parts are summarized in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868, strong Color sensitizers-p. 649 right column 4. Fluorescent brighteners p. 24 648 p. Right columns p. 868 5. Fogging prevention 24-25 p. 649 right columns 868-870 p. Agents, stabilizers 6. light absorbers, 25 Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Dye image Page 25 650 Page Left column 872 Stabilizer 8. Hardener 26 Page 651 Left column 874-875 9. Binder 26 pages 651 left column 873 to 874 10. Plasticizer, 27 pages 650 right column 876 lubricants 11. Coating aids, 26 to 27 pages 650 right column 875 to 876 surfactants 12 . Static page 27 page 650 right column page 876-877 inhibitor 13. matting agent page 878-879

A hydrophilic binder is preferably used as the binder of the constituent layers of the photosensitive material. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13.
Examples thereof include those described on pages (71) to (75) of No. 546. 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,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Also, U.S. Pat. No. 4,960,681, Japanese Patent Laid-Open No.
2-245,260 and the like, superabsorbent polymers, that is, homopolymers of vinyl monomers having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or the vinyl monomers, or other vinyl monomers. A copolymer with a 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. A combination of gelatin and the above binder is particularly preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin and so-called demineralized gelatin having a reduced content of calcium etc. according to various purposes, and it is also preferable to use them in combination. The amount of binder applied is ² per 1 m 2.
It is preferably 0 g or less, particularly 10 g or less, and further 7 g to
0.5 g is preferred.

A plasticizer or a slip agent can be used in the constituent layers of the light-sensitive material. Specifically, the research disclosure and JP-A-62-245,253 are used.
Some are listed in the issue. Further, for the above purpose, 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. As an example, Shin-Etsu Silicone Co., Ltd.
Published "modified silicone oil" technical data P6-18B
The various modified silicone oils described in (4), especially carboxy modified silicone (trade name X-22-3710) are effective. Further, JP-A-62-215,953 and 63-
The silicone oil described in No. 46,449 is also effective.

An anti-fading agent may be used in the light-sensitive material.
Examples of the anti-fading agent include an antioxidant, an ultraviolet absorber, or a metal complex of a certain type.
Dye image stabilizers and ultraviolet absorbers described in the disclosure are also useful. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A No. 61-159,644 are also effective. As an ultraviolet absorber, a benzotriazole compound (US Pat. No. 3,533,794) is used.
No.), 4-thiazolidone compounds (US Pat. No. 3,
352,681, etc.), benzophenone compounds (JP-A-46-2,784, etc.), and other JP-A-54-4.
No. 8,535, No. 62-136, 641 and No. 61-8
There are compounds described in No. 8,256. In addition, JP-A-6
The ultraviolet absorbing polymer described in 2-260,152 is also effective. As the metal complex, US Pat. No. 4,241,
155, No. 4,245,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A-62-17.
4,741 and 61-88,256 (27) to (2
9), 63-199,248, JP-A-1-75,
There are compounds described in Nos. 568 and 1-74,272.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the light-sensitive material. For example,
K. Veenkataraman edition `` The Chemistry of Synthetic D
yes ”, compounds described in Volume V, Chapter 8, JP-A-61-143752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent or an ultraviolet absorber.
Specific examples of these anti-fading agents, ultraviolet absorbers, and fluorescent whitening agents are described in JP-A-62-215272 (125) to (1).
37), JP-A-1-161,236 (17) to (4)
3) page.

As the hardener used in the constituent layers of the light-sensitive material, the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042 can be used.
No. 59-116,655, 62-245.
No. 261, No. 61-18, 942, JP-A-4-21.
Examples include hardeners described in No. 8,044. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g, per 1 g of coated gelatin.
5 to 0.5 g is used. The layer to be added may be any of the layers constituting the light-sensitive material or the dye-fixing material, or 2
You may divide and add in more than one layer.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the light-sensitive material. Specific examples thereof include Research Disclosure, US Pat. No. 5,089,378.
Issue 4,500,627, Issue 4,614,702
, JP-A-64-13,546, pages (7) to (9),
(57)-(71) and (81)-(97), U.S. Pat. Nos. 4,775,610 and 4,626,500.
No. 4,983,494, JP-A-62-174,7.
47, 62-239, 148, 63-264,
No. 747, JP-A Nos. 1-150, 135 and 2-11.
No. 0,557, No. 2-178,650, RD17,6
43 (1978), pages (24) to (25), and the like. These compounds are 5 per mol of silver.
X10 ^-7 to 1 x 10 ^-1 mol is preferable, and further 1 x 10
^-6 to 1 × 10 ^-2 mol is preferably used.

Various surfactants can be used in the constituent layers of the light-sensitive material for the purposes of coating aid, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant include Research Disclosure and JP-A-62-173.
463, 62-183, 457 and the like. The constituent layers of the light-sensitive material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and the like. As a typical example of the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. 8 to 17 columns, JP-A Nos. 61-20944 and 62-62.
Examples thereof include a fluorine-based surfactant described in No. 135826 and the like, or an oily fluorine-based compound such as fluorine oil or a hydrophobic fluorine compound such as a solid fluorine compound resin such as tetrafluoroethylene resin.

For the light-sensitive material, adhesion prevention, improvement of sliding property,
A matting agent can be used for the purpose of providing a non-glossy surface. Matting agents such as silicon dioxide, polyolefins and polymethacrylates are disclosed in JP-A-61-88256.
JP-A-63-274944 and JP-A-63-274, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page (29).
There are compounds described in No. 952. In addition, the compounds described in the above Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, a heat-solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like may be contained in the constituent layers of the light-sensitive material. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, JP-B-2-51,496 and the like.

As the support of the light-sensitive material, the paper described in "Basics of Photographic Engineering-Silver Salt Photo-" edited by The Photographic Society of Japan, published by Corona Co., Ltd. (1979) (223) to (240). ,
Examples include synthetic polymers (films). In particular,
Made from polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg triacetyl cellulose) or these films containing pigments such as titanium oxide, and polypropylene Film-process synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as required. In addition to this, JP-A-62-253,159 (2
9) to (31), JP-A-1-161,236 (1
4) to (17), JP-A-63-316,848, JP-A-2-22,651, JP-A-3-56,955, US Pat. No. 5,001,033, and the like. Can be used. The surface of these supports may be coated with a hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. Specifically, the supports described in JP-A-62-220246 can be used. Further, the surface of the support is preferably subjected to various surface treatments and undercoats for the purpose of improving the adhesion with the hydrophilic binder.

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 light emitting diode for image information via an electric signal, various lasers (laser diode,
Scanning exposure by emitting light such as gas laser (Japanese Patent Application Laid-Open No. 2-129,625, Japanese Patent Application No. 3-338,1)
No. 82, No. 4-9,388, No. 4-281,442, etc.), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, or directly or There is a method of exposing through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., US Pat. No. 4,500,626, column 56, JP-A-2-53,37.
The light sources and exposure methods described in No. 8 and No. 2-54,672 can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and electrolysis, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (K
DP), lithium iodate, inorganic compounds represented by BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives,
For example, a nitropyridine-N-oxide derivative such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462 and JP-A-62-210432.
The compounds described in No. 10 are preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera, or the like, Nippon Television Signal Standard (NTS
A television signal represented by C), 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 or CAD can be used.

In the image forming method of the present invention, the development processing of the silver halide light-sensitive material comprises the steps described above, but a method of forming an image composed of a dye and metallic silver without performing a bleaching step (desilvering step). May be The developing treatment used in the present invention is different from the conventional developing treatment in that the developing bath is an alkaline aqueous solution bath (activator bath), and the other steps can be used as they are.

The pH of the activator is 8 or more, preferably 9 to 14. The activator used in the present invention is basically only an alkali agent, but may contain an appropriate amount of an antifoggant, a development accelerator, an antioxidant, a water softener, an organic solvent and the like.

Examples of the alkaline agent include hydroxides, carbonates, bicarbonates, borates, phosphates and the like of alkali metals such as sodium, potassium, lithium and cesium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, Hydroxides, carbonates, bicarbonates, borates, phosphates, etc. of quaternary alkylammonium such as triethylbenzylammonium, amidines,
Organic bases such as cyclic amidines, guanidines, cyclic guanidines, aliphatic amines, aromatic amines and heterocyclic amines, and their carbonates, bicarbonates, borates,
Examples thereof include phosphate. These compounds can be used alone or in combination. The concentration of the alkaline agent is 0.001 mol to 3 mol per liter, preferably 0.01 to
It is 1 mol.

In the present invention, particularly preferred alkaline agents are the compounds mentioned above or above, and those containing at least 0.01 mol per liter. Specific examples of the organic base of are listed in Chemical formulas 3 to 5, but of course are not limited thereto.

[0047]

[Chemical 3]

[0048]

[Chemical 4]

[0049]

[Chemical 5]

Antifoggants used in activators include bromides such as sodium bromide, potassium bromide or ammonium bromide, iodides such as potassium iodide and sodium iodide, and chlorides such as sodium chloride and potassium chloride. And the known organic antifoggants. Examples of organic antifoggants include 6-nitrobenzindazole described in U.S. Pat. No. 2,496,940, U.S. Pat.
No. 656,271, 5-nitrobenzimidazole, diaminophenazine and o-phenylenediamine described in the Journal of the Photographic Society of Japan, Vol. 11, page 48 (1948), mercaptobenzimidazole, methylbenzthiazole, mercaptobenzoxazole, Thiouracil, benztriazole, 5-methylbenztriazole, and the heterocyclic compounds described in JP-B-46-41,675 are mentioned. In addition, "Scientific Photobook", Vol. 119 (Maruzen, published in 1959) and RD No. 17, 64 mentioned above.
3, those described in No. 18, 716, and No. 307, 105 can also be used.

Development accelerators which can be added to the activator include US Pat. Nos. 2,648,604 and 3,67.
1,247, Japanese Patent Publication No. 49-9,503 and various other pyridinium compounds and other cationic compounds,
Cationic dyes such as phenosafuran, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9504
No. 2,533,990 and 2,531,
No. 832, No. 2,950,970, No. 2,577,1
No. 27, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, JP-B-44-
9,509, organic solvent described in Belgian Patent 682,862, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, and others LF
Photographic Processing Chemistry by A. Mason
(Photographic Processing Chemistry) Pages 40-43 (Focal Press; London 1966)
Also included are accelerators detailed in.

Examples of the water softener include sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, polyphosphoric acid compounds represented by potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid. , Iminodiacetic acid, N- (hydroxymethyl) ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, or an aminopolycarboxylic acid represented by an alkali metal salt thereof or a salt thereof, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1, A phosphonic acid represented by 1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), or an alkali metal salt thereof or a salt thereof can be used. The amount added varies depending on the hardness of the water, but is usually about 0.1 to 10 g / liter.

As the antioxidant, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like can be added.

If necessary, the activator may contain organic solvents. For example, ethylene glycol, hexylene glycol, diethylene glycol,
Methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethylsulfoxide, and other Japanese Patent Publication Nos. 47-33,378 and 44-9,
Compounds described in No. 509 are included. The amount of addition is widely varied depending on the composition of the activator, but is 50% or less of the liquid used, and usually 10% or less.

In addition, an optical brightening agent and a surfactant can be added to the activator. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is preferably 0.01 g to 5 g / liter. As the surfactant, various ones such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid polyalkyleneimine can be used.

In the present invention, the treatment temperature of the activator solution is 20 to 70 ° C., preferably 30 to 60 ° C., most preferably 35 ° C. to 50 ° C. Processing time is 20 seconds to 5
Minutes, preferably 30 seconds to 2 minutes. It is preferable that the replenishing amount is small, but 10 to 600 ml is appropriate per 1 m ^{2 of the} light-sensitive material, preferably 30 to 200 ml, more preferably 5
It is 0 to 150 ml.

Examples of the "substance capable of adsorbing the diffusible dye" usable in the present invention include activated carbon, carbon black, cation or anion exchange resin, silica gel, alumino silica gel, activated alumina, and the like in the form of physical adsorption. ,
Any commonly known organic adsorbent can be used regardless of whether it is chemisorption. A brief example is given of some of the above adsorbents. Activated carbon; registered in JIS K-1474-75 and has physical adsorption ability. There are powder and granules.
Manufacturers include Sanwa Carbon, Tsurumi Coal, Fujisawa Chemicals, Hokuetsu Carbon, Clera Chemicals, Takeda Pharmaceuticals, Wako Pure Chemicals and others. Ion exchange resin; strong commercial cation exchange resin- (Amberlite) Amberlite IR
-120B (Organo), (Douex) Dowex (Muromachi Kagaku). Weakly acidic cation exchange resin- (Amberlite) Amberlit
e IRC-50, Diaion WK Strongly basic anion exchange resin- (Amberlite) Amberl
ite IRA-401, (Amberlite) Amberlite I
RA-410, Diaion SA-11A, Diaion SA-20A, (Douex) Dowex I, (Douex) DowexZ. Weakly basic anion exchange resin- (Amberlite) Amberl
ite IR-4B, (Amberlite) Amberlite IR-
45, Diaion WA20, (Douex) Dowex
3. It is known that a substance is adsorbed by chemisorption by a dissociative group. The diffusible dye generated according to the present invention is mainly a dissociative dye, and an anion exchange resin is preferably used to adsorb this. Other alumina, alumino-silica gel, and silica gel that can be used include those commercially available from Sumitomo Aluminum, Mizusawa Chemical, Catalysis, Wako Pure Chemical Industries, and other companies.

In order to bring the above "substance capable of adsorbing a diffusible dye" into contact with an activator, it may be inserted into a mesh bag or container capable of holding it and immersed in an activator bath, a column or the like. Alternatively, the activator solution may be circulated between the bath and the column. Further, it may be processed into a sheet with an appropriate binder and immersed in an activator bath.

A desilvering process is performed after the activator process. In the desilvering process, the bleaching process and the fixing process may be carried out individually or simultaneously (bleach-fixing process). Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. Further, when a dye image and a silver image are obtained together as described above, when the amount of coated silver is very small such as 100 mg / m ² or less, only the fixing process may be performed except the bleaching process.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron (I
II) organic complex salts (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediamine tetraacetate
(III) Complex salt, and iron 1,3-diaminopropane tetraacetate (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. A bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is used at a pH of 3-8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. be able to. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pK
a) is a compound of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, in the fixing solution and the bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ', N') are used for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
And Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide bond;
Thiazolidine derivatives described in No. 29; US Pat. No. 3,7
Thiourea derivatives described in JP-A No. 06,561;
Iodide salt described in 16235; West German Patent No. 2,74
The polyoxyethylene compounds described in No. 8,430; the polyamine compounds described in JP-B-45-8836; the bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 20 seconds to 2 minutes. The processing temperature is 20 ° C to 70 ° C, preferably 35 ° C to 60 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring are disclosed in JP-A Nos. 62-183460 and 62-183.
No. 461, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in the solution. And the emulsion surface are brought into contact with each other to make the emulsion surface turbulent, thereby further improving the stirring effect, and increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the agitation improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the processing of the light-sensitive material in the present invention is disclosed in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

In the present invention, the color light-sensitive material is generally subjected to a washing step after desilvering. A stabilizing process may be performed instead of the water washing process. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-148 have been used.
All known methods described in No. 34 and No. 60-220345 can be used. Further, a washing process-stabilizing process may be carried out in which a stabilizing bath containing a dye stabilizer and a surfactant, which is represented by processing of a color light-sensitive material for photographing, is used as a final bath. Water washing and stabilizing solutions include hard water softeners such as inorganic phosphoric acid, polyaminocargonic acid, organic aminophosphonic acid; metal salts such as Mg salt, Al salt, Bi salt; surfactants; hardeners, etc. Can be included.

The amount of washing water in the washing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a dye-donating compound), the application, and the washing water temperature, the number of washing tanks (the number of stages), a countercurrent, a forward flow, etc. It can be set in a wide range under various other conditions. Further, as a solution to problems such as bacterial growth and adherence of produced floating substances to a light-sensitive material which occur when the amount of washing water is greatly reduced in a multi-stage countercurrent system, it is described in JP-A-62-288838. The method of reducing calcium ions and magnesium ions can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The washing water has a pH of 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C.
20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds
A range of 5 minutes is selected. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, other stabilizing agents include boric acid and pH adjusting buffers such as sodium hydroxide;
1-Hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; an antisulfurizing agent such as an alkanolamine; an optical brightening agent; a mildewproofing agent and the like can be contained. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the present invention, the processing method and the processing additive applied for processing the light-sensitive material are described in JP-A-5-58200.
Those described in, for example, 88326 and EP 0,355,660A2 are preferably used.

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 A method for preparing a dispersion of an electron transfer agent will be described. 10 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of the following anionic surfactant were added to 100 ml of a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0073]

[Chemical 6]

[0074]

[Chemical 7]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. That is, each oil phase component is about 60
Dissolve it in a uniform solution by heating it to ℃
The heated aqueous phase component was added to the mixture, stirred and mixed, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0076]

[Table 1]

[0077]

[Chemical 8]

[0078]

[Chemical 9]

[0079]

[Chemical 10]

[0080]

[Chemical 11]

[0081]

[Chemical 12]

[0082]

[Chemical 13]

[0083]

[Chemical 14]

[0084]

[Chemical 15]

[0085]

[Chemical 16]

Next, a method for preparing a photosensitive silver halide emulsion will be described. Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (in 500 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 3 parts of sodium chloride)
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.), 20 parts of solution (I) and solution (II) in Table 2 were simultaneously added.
Added at equal flow rate for 1 minute. After 6 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes. Also (II
10 minutes after the addition of the solutions (I) and (IV) was started, an aqueous solution of a gelatin dispersion of a dye (1 g of gelatin in 105 ml of water, 70 mg of the following dye (a), 139 mg of the following dye (b), and the following dye (c) ) Containing 5 mg and kept at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (2) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0088]

[Chemical 17]

[0089]

[Table 2]

[0090]

[Chemical 18]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 800 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.), 30 parts of the liquids (I) and (II) in Table 3 were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) in Table 3 were simultaneously added at an equal flow rate for 15 minutes. Also (II
2 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1.1 g of gelatin in 95 ml of water, 76 mg of the above dye (a), 150 mg of the above dye (b), and the above dye) (C) 5 mg and kept at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0093]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride in 690 ml of water).
solution (I) and solution (II) in Table 4 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 32 minutes. Also (II
I), 1 minute after the end of the addition of the (IV) solution, an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 100 ml of water and 250 mg of the following dye (d) and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0096]

[Table 4]

[0097]

[Chemical 19]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 60 ° C.), and the liquids (I) and (II) in Table 5 were simultaneously added to 20 times.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) shown in Table 5 were added simultaneously at the same flow rate for 20 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 75 ml of water and 180 mg of the dye (d) and kept at 45 ° C.) was added together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0100]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 4 in 690 ml of water).
g and the above chemical (A) (15 mg) and the mixture was kept at 52 ° C.), the solutions (I) and (II) in Table 6 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes. Also (II
One minute after the addition of the solutions (I) and (IV) was completed, an aqueous solution of the dye (water 9
235 mg of the following dye (e) in 5 ml and 5 ml of methanol
And 120 mg of the following dye (f) and kept at 45 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0103]

[Table 6]

[0104]

[Chemical 20]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 65 ° C.), the liquids (I) and (II) shown in Table 7 were simultaneously added to 10 parts.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table 7 were added simultaneously at the same flow rate for 30 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of the dye (water 6
155 mg of the above dye (e) in 6 ml and 4 ml of methanol
And 78 mg of the above-mentioned dye (f) and kept at 60 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0107]

[Table 7]

A photosensitive material 101 shown in Table 8 was prepared using the above.

[0109]

[Table 8]

[0110]

[Table 9]

[0111]

[Table 10]

[0112]

[Chemical 21]

[0113]

[Chemical formula 22]

[0114]

[Chemical formula 23]

[0115]

[Chemical formula 24]

The photosensitive material 101 was exposed through a wedge whose density continuously changed, and the following processing was performed. Treatment process Activator development 40 ° C 1 minute Bleach fixing 40 ° C 1 minute Water wash 20 ° C 2 minutes Stabilization 20 ° C 30 seconds Dry 70 ° C 2 minutes

Activator solution Tetramethylammonium hydroxide (25%) 80 ml Water is added to make 1 liter. pH 13.3 Bleach-fix solution Ammonium thiosulfate 130 g Sodium metabisulfite 14 g Anhydrous sodium sulfite 3 g EDTA / ferric ammonium salt 65 g Water is added to make 1 liter. pH 6.8 Stabilizing solution Anhydrous sodium carbonate 2.1 g Anhydrous sodium bicarbonate 1.7 g Water is added to make 1 liter. pH 9.5

The maximum and minimum densities of the processed light-sensitive materials were measured by a transmission type X-Rite densitometer, and the results are shown in Table 9. Further, the photosensitive material 101 is set to 50 ° C. and relative humidity 60%
Table 9 also shows the results of measuring the concentration after the same treatment as above for 1 week.

[0119]

[Table 11]

According to the present invention, it was found that an image having a low minimum density and a high maximum density can be obtained by a simple process, and the raw storability of the light-sensitive material is good.

Example 2 The same photosensitive material and processing solution as in Example 1 were used except that the composition of the activator solution was changed to the following (1) to (4). The results of the concentration measurement are shown in Table 10. Activator solution Sodium hydroxide 0.25M Add sodium bicarbonate to adjust pH to 12.5. Activator solution Sodium hydroxide 0.25M Tetramethylammonium chloride 0.25M Sodium bicarbonate is added to adjust the pH to 12.5. Activator solution Sodium hydroxide 0.25M Sodium chloride 0.25M Add sodium bicarbonate to adjust pH = 12.5. Activator solution Organic base (22) of the present invention (0.25) Add 0.25M sodium bicarbonate to adjust pH to 12.5. Activator solution Potassium hydroxide 0.25M benzyl alcohol 0.10M Sodium bicarbonate was added to adjust the pH to 12.5. Activator solution Organic base (33) of the present invention (0.25) Add 0.25M sodium bicarbonate to adjust the pH to 12.5.

[0122]

[Table 12]

It was found that the treatment using the quaternary alkylammonium salt of the present invention, the organic base and the activator salt containing the salt of the organic base can give an image with good discrimination.

Example 3 A black-and-white light-sensitive material 102 shown in Table 11 was prepared using the dye-donating compound, electron transfer agent, electron donor, silver halide emulsion and the like used in Example 1. Exposure, treatment and density measurement were carried out in the same manner as in Example 1 except that the fixing treatment of the following formulation (40 ° C. for 1 minute) was carried out instead of the bleach-fixing treatment. The maximum density was 3.2 and the minimum density was 0.2. 11 black and white images were obtained.

Fixing solution Ammonium thiosulfate 130 g Sodium metabisulfite 14 g Anhydrous sodium sulfite 3 g Water is added to make 1 liter. pH = 6.8

[0126]

[Table 13]

[0127]

[Table 14]

According to the present invention, it was found that a black and white image having excellent discrimination can be obtained.

Example 4 In the process of Example 3, the light-sensitive material 102 was repeatedly processed in an amount of 0.02 m ² per 1 liter of the activator to 1 m ² , and the activator solution was colored and the minimum density of the image was increased. Therefore, when granular activated carbon was placed in a mesh-shaped saran bag having an opening of 10 microns and inserted into the activator solution, coloring was almost eliminated, and an increase in the minimum density of the image was significantly suppressed. It was found that stable treatment can be achieved for a long period of time by using a substance such as activated carbon that adsorbs the diffusible dye that is eluted in the activator solution.

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

[Procedure amendment]

[Submission date] December 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 10 seconds
It is 3 minutes, more preferably 20 seconds to 2 minutes. The processing temperature is 20 ° C to 70 ° C, preferably 35 ° C to 60 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stain after processing is effectively prevented.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

In the present invention, the color light-sensitive material is generally subjected to a washing step after desilvering. A stabilizing process may be performed instead of the water washing process. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-148 have been used.
All known methods described in No. 34 and No. 60-220345 can be used. Further, a washing process-stabilizing process may be carried out in which a stabilizing bath containing a dye stabilizer and a surfactant, which is represented by processing of a color light-sensitive material for photographing, is used as a final bath. Water washing and stabilizing solutions include hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; metal salts such as Mg salt, Al salt and Bi salt; surfactants; hardeners, etc. Can be included.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 800 ml of water).
g and 30 mg of the above-mentioned chemical (A) were added and kept at 65 ° C.), 30 parts of the liquids (I) and (II) in Table 3 were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) in Table 3 were simultaneously added at an equal flow rate for 15 minutes. Also (II
2 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1.1 g of gelatin in 95 ml of water, 76 mg of the above dye (a), 150 mg of the above dye (b), and the above dye) (C) 5 mg and kept at 50 ° C.) was added over 18 minutes. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 10, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The image forming method of the present invention can be used for a color negative for photographing, a color print, a printing plate, a micro color filter and the like. Hereinafter, the present invention will be described in more detail. Specific examples of the diffusion-resistant dye-donor compound that releases a diffusible dye in response to the development of silver halide used in the present invention include the following compounds.

Claims (5)

[Claims] 1. A light-sensitive material having on a support at least a light-sensitive silver halide, a reducing agent, a diffusion-resistant dye-donor compound which releases a diffusible dye in response to development of a silver halide, and a binder. A method of forming an image by treating with an alkaline aqueous solution having a pH of 8 or more, followed by treatment with a bleaching solution, a fixing solution (or a bleach-fixing solution) or a fixing solution alone, followed by washing with water and drying. 2. The image forming method according to claim 1, wherein the dye-donating compound is represented by formula [I]. General formula [I] [In the formula, EAG represents an electron-accepting group, and X represents an oxygen atom (-O-), a sulfur atom (-S-) or a nitrogen atom (-.
N (R ³⁾ -) represents a. R ¹ , R ² and R ³ each represent a mere bond or a group other than a hydrogen atom.
R ¹ , R ² , R ³ and EAG may combine with each other to form a ring. Time represents a group that releases the Dye through a subsequent reaction using the cleavage of the N—X bond as a scratch.
t represents an integer of 0 or 1. Dye represents a diffusible dye. In addition, the solid line indicates the connection, and the broken line indicates that at least one of them is connected. ] 3. The image forming method according to claim 1, wherein the reducing agent comprises a diffusible electron transfer agent and a diffusion resistant electron donor. 4. An alkaline aqueous solution containing a hydroxide or salt of quaternary alkylammonium; amidines, cyclic amidines, guanidines, cyclic guanidines, aliphatic amines, aromatic amines, heterocyclic amines, etc. 4. The image forming method according to claim 1, which contains at least 0.01 mol / liter of an organic base and a salt thereof. 5. The image forming method according to claim 1, wherein the treatment is performed in a state where the alkaline aqueous solution is in contact with a substance capable of adsorbing the diffusible dye.