JP3238251B2 - Image forming method - Google Patents

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 using a silver halide light-sensitive material and capable of easily managing a processing solution.

[0002]

2. Description of the Related Art A general method for forming a color image from a photographic light-sensitive material, for example, a color photographic light-sensitive material, is to use a halogenated compound in the presence of a color coupler having the ability to react with an oxidized developing agent to form a dye. In this method, an azomethine or indoaniline dye is obtained by developing a silver photosensitive material using an aromatic primary amine developing agent. This color development method was basically based on LD Mannes & L. Go
It was invented by dowsky and has since undergone various improvements and is in use today in the industry worldwide.

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

[0004] The bleaching step and the fixing step can be performed simultaneously. That is, this is a bleach-fixing step (so-called Brix), in which developed silver and undeveloped silver halide are desilvered. In actual development processing, in addition to the above two basic steps of color development and desilvering, auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image are performed. Accompanied. For example, a hardening bath to prevent excessive softening of the photosensitive film during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a removal bath to remove the backing layer of the support. Steps such as a film bath are included.

[0005]

Generally, an aromatic primary amine developing agent is dissolved in an aqueous alkaline solution and used in a color developing solution. If the aromatic primary amine developing agent can be incorporated in the light-sensitive material, development can basically be performed only with an aqueous alkali solution. This allows
Preparation of the developer becomes easier, changes in the composition of the developer are reduced, and management becomes easier. In addition, there are many advantages such as the BOD of the waste liquid is significantly reduced, and the waste liquid treatment is facilitated. However, in general, the incorporation of an aromatic primary amine developing agent in the light-sensitive material causes desensitization of the light-sensitive material during storage, generation of fog or stain, and insufficient color formation due to processing and the like. It has a number of disadvantages and has not yet been put to practical use.

(Object of the Invention) An object of the present invention is to provide a color image forming method in which the preparation of a processing solution is easy, the change in the composition of the processing solution is small, and the management is easy. A second object is to provide a color image forming method in which waste liquid treatment is easy. A third object of the present invention is to provide an image forming method capable of obtaining a color image having good raw storability of a photosensitive material and stable for a long period of time.

[0007]

The objects of the present invention are as follows.
A light-sensitive material having at least a light-sensitive silver halide, a reducing agent, a nondiffusible dye-donating compound that releases a diffusible dye in reverse to the development of the silver halide on a support, and a binder, is an alkaline aqueous solution having a pH of 8 or more. After processing with
A method in which an image is formed by treating with a bleaching solution, a fixing solution (or a bleach-fixing solution) or a fixing solution alone, followed by washing and drying, wherein (1) the reducing agent is a diffusible electron transfer agent and Diffusible
The above-mentioned image form characterized by comprising an electron donor
And (2) a substance in which the alkaline aqueous solution can adsorb a diffusible dye.
The image characterized in that the image is processed in contact with the quality
This was achieved by a forming method .

The image forming method of the present invention can be used for color negatives for photography, color printing, printing plate making, micro color filters, and the like. Hereinafter, the present invention will be described in more detail. Specific examples of the non-diffusible dye-donating compound which releases a diffusible dye in reverse correspondence 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 JP-B-3-68. No. 3,387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

US Pat. No. 4,559,290, EP 220,746 A2, US Pat. No. 4,783,
No. 396, published technical report 87-6, 199, Japanese Unexamined Patent Publication No. 64-1
As described in US Pat. No. 3,546 or the like, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Other examples include
U.S. Pat. Nos. 4,139,389 and 4,139,37
9, JP-A-59-185333, and JP-A-57-84,
No. 453, No. 453, and the like, compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat. No. 4,232,107;
No. 49, No. 61-88, 257, RD24, 025
(1984) and the like, which release a diffusible dye by an electron transfer reaction in the molecule after reduction, West German Patent No. 3,008,588A, JP-A-56-14.
No. 2,530, U.S. Pat. Nos. 4,343,893 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction; Nitro compounds which release a diffusible dye after electron acceptance described in, for example, US Pat. No. 450,223, and compounds which release a diffusible dye after electron reception, described in US Pat. No. 4,609,610, and the like. Can be

[0011] More preferably, European Patent No. 220,746, published technical report 87-6,199, US Patent No. 4,783,396, and Japanese Patent Application Laid-Open No. 63-201,664 are preferred.
No. 53, No. 63-201, 654, No. 64-13, 5
No. 46, etc., a compound having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, a single molecule described in JP-A 1-26,842 A compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group, and a PO—X bond (X is as defined above) in one molecule described in JP-A-63-271,344. And a compound having an electron-withdrawing group, JP-A-63-271341
The compounds 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 (1). Also, JP-A-1-161,237
And a compound capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group described in JP-A Nos.

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

[0013]

Embedded image

In the general formula [I], EAG represents an electron-accepting group, and X represents an oxygen atom (-O-) and 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-
The cleavage of the X bond as a trigger leads to D
represents a group that releases ye, and t represents an integer of 0 or 1. Dye represents a diffusible dye. Also, the solid line indicates the bond,
Dashed lines indicate that at least one of them is bonded. 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, JP-A-87-6,199, JP-A-64-13,546.
No. etc.

In the present invention, the coating amount of the dye-providing compound is from 0.01 to 20 mmol, preferably from 0.0 to 20 mmol per 1 m ^2.
The amount is 5 to 10 mmol, and is 0.1 to 20 moles, preferably 0.25 to 5 moles, per mole of the total silver per unit area. The dye-donating compound can be contained in a photosensitive layer containing a photosensitive 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 include the silver halide in the lower layer adjacent to the photosensitive layer containing the corresponding silver halide. The dye-providing compounds may be used alone or in combination.

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 dye-donating compound having a reducing property (a dye developing agent or the like) is also included (in this case, another reducing agent can be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49-50 and 4,83.
9,272, 4,330,617 and 4,59
0,152, 5,017,454, 5,13
No. 9,919 and JP-A-60-140,335 (1).
7) to (18), pp. 57-40, 245, and 56-
138,736, 59-178,458, 59
Nos. 53,831 and 59-182,449, 59
-182,450, 60-119,555, 6
Nos. 0-128,436, 60-128,439, 60-198,540, 60-181,742,
Nos. 61-259,253 and 62-201,434
Nos. 62-244,044 and 62-131,25
No. 3, 62-131, 256, 63-10, 15
No. 1, Nos. 64-13, 546, (40) to (57)
Page, JP-A-1-120,553 and 2-32,338
No. 2-35,451, 2-234,158,
There are reducing agents and reducing agent precursors described in JP-A 3-160,443 and EP 220,746, pp. 78-96. Various combinations of reducing agents, such as those disclosed in U.S. 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 used in order to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide. It is desirable to use a combination of an electron transfer agent and / or an electron transfer agent precursor having higher mobility. Particularly preferred electron transfer agents (precursors) are described in the aforementioned US Pat. No. 5,139,919 and EP-A-418,743.
No., JP-A-1-138556, and 3-102,34.
No. 5 1-phenyl-3-pyrazolidones or aminophenols. Also, Japanese Patent Application Laid-Open No. Hei 2-230,14
As described in JP-A Nos. 3 and 2-235,044, a method of stably introducing a compound into a layer is preferably used.

The non-diffusible reducing agent (electron donor) used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the photosensitive material among the above-mentioned reducing agents.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
0827; U.S. Pat. Nos. 5,032,487;
Compounds described as electron donors in JP-A Nos. 026,634 and 4,839,272 and dye-donating compounds having a diffusion-resistant and reducing property described later are mentioned. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used.

Further, the above-mentioned reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixing, improvement of color reproduction, improvement of white background, and prevention of silver transfer to the dye fixing material. Specifically, European Patent Publication Nos. 524,649 and 357,04
0, JP-A-4-249,245, JP-A-2-64,63
No. 3, No. 2-46,450, JP-A-63-186,2
The reducing agent described in No. 40 is preferably used. JP-B 3-63,733, JP-A-1-150,135, JP-A-2-110,557, JP-A-2-64,634, and JP-A-3-63,733.
43,735 and EP-A-451,833 may also be used. In the present invention, the total amount of the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
470, 4,536,466, 4,536,4
Nos. 67, 4,587,206 and 4,555,47
No.6, No.4,599,296, Tokubo 3-62,25
No. 6, using a high boiling organic solvent as described in combination with a low boiling organic solvent having a boiling point of 50 ° C to 160 ° C as needed,
Can be used. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating 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. 51-39,
No. 853, a dispersion method using a polymer described in JP-A-51-59,943, and a method of adding as a fine particle dispersion described in JP-A-62-30,242 and the like 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, Nos. (37) to (38)
Page, the surfactants described in the above 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 can also be added in separate layers. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. 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 using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. . For example, JP-A-59-180,550 and JP-A-64-13,546, 6
2-253,159, EP-A-479,167.
No. 3, blue-sensitive layer, green-sensitive layer, red-sensitive layer, green-sensitive layer, red-sensitive layer, infrared-sensitive layer, red-sensitive layer, infrared-sensitive layer (I), red There is a combination of the outer photosensitive layer (II) and the like. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary 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 and above the silver halide emulsion layers and the lowermost layer. May be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, the layer constitution as described in the above patent, US Pat. No. 5,051,33
5, an undercoat layer described in JP-A No. 5-167,838.
And an intermediate layer having a solid pigment as described in JP-A-61-20,943; JP-A-1-120,553;
Intermediate layers having a reducing agent or a DIR compound as described in JP-A-34,884 and JP-A-2-64,634;
17,454,5,139,919;
An intermediate layer having an electron transfer agent as described in JP-A-235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer obtained by combining them can be provided. The support is preferably designed to have an antistatic function and to have a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion that can be used in the present invention includes:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be 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 light fogging. Also,
A so-called core-shell emulsion having a phase in which the inside of the grain is different from that of the grain surface may be used, or silver halide having a different composition may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167,743 and JP-A-4-223,463 is preferably used. . The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and tabular shapes having a high aspect ratio, and those having twin planes. It may be one having such a crystal blood vessel, or a combination thereof or any other. Specifically, US Pat. No. 4,500,626
No. 50, column 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17, 643 (December, 1978), pp. 22-23, and No. 18, 716 (1979).
Nov., 648, p. 307, 105 (198).
Nov. 9, pp. 863-865, JP-A-62-253,
No. 159, No. 64-13,546, JP-A-2-23
No. 6,546, No. 3-110, 555, and Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P.Gl.
by afkides Chemie et Phisique Photographique, Paul
Montel, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Che).
mistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VLZelikman)
et al., Making and Coating Photographic Emulsion,
Focal Press, 1964) and the like can be used.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting for removing excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). 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. The amount of addition 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 contained in the particles, or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637 and JP-A-4-126629 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B No. 47-1
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

Other conditions are described in the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Monte
l, 1697), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chem).
istry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZeli).
kman et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).
That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a reverse mixing method in which grains are preferably used in the presence of silver ions in excess is also preferably used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can also be used.

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-55-142329 and JP-A-55-158, JP-A-55-142329). 124, U.S. Pat. No. 3,650,575). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The light-sensitive 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 sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11055).
No. 5, Japanese Patent Application No. 4-75,798). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. . The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.
0 to 10.5, 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 impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat.
And sensitizing dyes described in JP-A-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. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23,145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a step and the photographic additives that can be used in the light-sensitive material of the present invention are described in the above-mentioned RD Nos. 17,643, 18, 716 and N.
o. 307, 105, and the relevant parts are summarized in the following table. Type of additive 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 23-24, page 648, right column, pages 866-868 Color sensitizers 頁 page 649 right column 4. Fluorescent brightener page 24 page 648 right column page 868 5. Fog prevention 24-25 page 649 right column 868-870 agents, stabilizers 6.Light absorbers, 25 26Page 26 649 Right column Page 873 Filter 〜Page 650 Left column Dye, UV absorber 7.Dye image 25 Page 650 Page Left column 872 Stabilizer 8. Hardener 26 Page 651 Left column 874-875 9. Binder page 26 page 651 left column 873-874 10. Plasticizer, page 27 page 650 right column page 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12 Static 27 pages 650 right column 876-877 Inhibitors 13. Matting agents 878-879

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, protein or cellulose derivative such as gelatin derivative, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer. Also, U.S. Pat. No. 4,960,681,
No. 2-245260, etc., ie, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a vinyl monomer or another vinyl Copolymers with monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination. The amount of binder applied is ² per m 2
0 g or less, preferably 10 g or less, and more preferably 7 g or less
0.5 g is preferred.

In the constituent layers of the photosensitive material, a plasticizer or a slipping agent can be used. Specifically, the above-mentioned Research Disclosure and Japanese Patent Application Laid-Open No. 62-245,253
Some are described in the issue. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane)
Can be used. An example is Shin-Etsu Silicone Co., Ltd.
Published “Modified Silicone Oil” Technical Document P6-18B
And the like, in particular, carboxy-modified silicone (trade name: X-22-3710) is effective. JP-A-62-215953;
The silicone oil described in JP 46,449 is also effective.

An anti-fading agent may be used in the light-sensitive material.
Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes.
Dye image stabilizers and ultraviolet absorbers described in disclosure are also useful. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159,644 are also effective. Benzotriazole compounds (U.S. Pat. No. 3,533,794)
No. 3), 4-thiazolidone-based compounds (U.S. Pat.
352,681), benzophenone-based compounds (JP-A-46-2,784, etc.), and other JP-A-54-4
No. 8,535, No. 62-136, 641, No. 61-8
No. 8,256 and the like. In addition, Japanese Unexamined Patent Publication
The UV-absorbing polymer described in 2-260, 152 is also effective. As the metal complex, U.S. Pat.
No. 155, No. 4,245,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A-62-17
Nos. 4,741 and 61-88,256 (27) to (2)
9), p. 63-199,248, JP-A-1-75,
568 and 1-74,272.

The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination. A fluorescent whitening agent may be used in the photosensitive material. For example,
K. `` The Chemistry of Synthetic D '' edited by Veenkataraman
yes ", Vol. V, Chapter 8, and compounds described in JP-A-61-143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor 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)-(1).
37), JP-A-1-161,236 (17) to (4)
3) It is described on page.

The hardeners used in the constituent layers of the photosensitive material are described in Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042.
JP-A-59-116,655 and JP-A-62-245,
No. 261, No. 61-18, 942, JP-A-4-21
Hardening agents described in JP-A-8,044 and the like can be mentioned. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol-based hardening agent (such as dimethylol urea), or a polymer hardening agent (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 gelatin applied.
5 to 0.5 g are used. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material.
It may be added in layers or more.

In the constituent layers of the light-sensitive material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, US Pat. No. 5,089,378.
Nos. 4,500,627 and 4,614,702
No., JP-A-64-13546, 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
No. 47, 62-239, 148, 63-264,
747, JP-A-1-150,135, 2-11
0,557, 2-178,650, RD17,6
43 (1978), pages (24) to (25). These compounds are available in 5 moles per mole of silver.
X 10 ^-7 to 1 x 10 ^-1 mol is preferable, and 1 x 10
^-6 to 1 × 10 ^-2 mol is preferably used.

In the constituent layers of the light-sensitive material, various surfactants can be used for the purpose of coating aid, improving slipperiness, preventing static charge, accelerating development and the like. Specific examples of surfactants are described in Research Disclosure, JP-A-62-173, and JP-A-62-173.
463, 62-183, 457 and the like. The constituent layer of the photosensitive material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and the like. Representative examples of the organic fluoro compound include JP-B-57-9053.
Nos. 8-17, JP-A-61-20944, 62-62
And fluorinated surfactants such as fluorinated surfactants described in US Pat. No. 135826, oily fluorinated compounds such as fluorinated oil, and solid fluorinated compound resins such as ethylene tetrafluoride resin.

For the photosensitive material, prevention of adhesion, improvement of sliding property,
A matting agent can be used for the purpose of making a matte surface or the like. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 29, benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 952. In addition, the compounds described in the aforementioned 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, the constituent layers of the light-sensitive material may contain a heat solvent, an antifoaming agent, a germicide / antibacterial agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, and JP-B-2-51,496.

As the support of the photosensitive material, paper described in "Basics of Photographic Engineering-Silver halide photography-" edited by The Photographic Society of Japan, Corona Co., Ltd. (1979), pages (223) to (240). ,
Synthetic polymers (films) and the like can be mentioned. In particular,
Polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetyl cellulose), or films containing pigments such as titanium oxide, and further made of polypropylene, etc. Film-processed synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support laminated on one or both sides 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 necessary. In addition, Japanese Patent Application Laid-Open No. 62-253,159 (2)
9) to (31), JP-A-1-161,236 (1)
4) to (17), supports described in JP-A-63-316,848, JP-A-2-22,651, JP-A-3-56,955, U.S. Pat. No. 5,001,033, etc. 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, a support described in JP-A-62-220,246 can be used. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

As a method of exposing and recording an image on a photosensitive material, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Using a copier exposure device to scan and expose the original image through slits, etc., image information via electric signals, light emitting diodes, various lasers (laser diodes,
A method of performing scanning exposure by emitting light from a gas laser or the like (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application No. 3-338
Nos. 82, 4-9, 388, 4-281, 442), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., 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, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source and the like, JP-A-2-53,37.
No. 8, No. 2-54, 672 can be used. Also, image exposure can 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 nonlinear optical material is a material that can exhibit nonlinearity between polarization and electrolysis that appears when a strong optical electric field such as a laser beam is applied, and includes lithium niobate and potassium dihydrogen phosphate (K).
DP), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives,
For example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are preferably used. As a 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. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTS).
A television signal represented by C), an image signal obtained by dividing an original image into a number of pixels such as a scanner, and an image signal created by using a computer represented by CG and 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 above-mentioned steps, but a method of forming an image comprising a dye and metallic silver without performing a bleaching step (desilvering step). It may be. The developing process used in the present invention differs from the conventional developing process only in that the developing bath is a bath of an alkaline aqueous solution (activator bath), and the other steps can be used as they are.

The pH of the activator is 8 or more, preferably 9-14. The activator used in the present invention may be basically an alkaline agent alone, 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 and phosphates of alkali metals such as sodium, potassium, lithium and cesium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like. Amidines such as hydroxides, carbonates, bicarbonates, borates and phosphates of quaternary alkylammoniums such as triethylbenzylammonium,
Cyclic amidines, guanidines, cyclic guanidines, aliphatic amines, aromatic amines, organic bases such as heterocyclic amines and their carbonates, bicarbonates, borates,
Phosphates and the like. These compounds can be used alone or in combination. The concentration of the alkali agent is 0.001 mol to 3 mol per liter, preferably 0.01 to 1 mol.
1 mole.

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

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Examples of the antifoggant used in the activator include bromides such as sodium bromide, potassium bromide and ammonium bromide, iodides such as potassium iodide and sodium iodide, and chlorides such as sodium chloride and potassium chloride. And known organic antifoggants. Examples of organic antifoggants include 6-nitrobenzindazole described in U.S. Pat. No. 2,496,940, and U.S. Pat. Nos. 2,497,917 and 2,497.
656,271, 5-aminobenzimidazole, diaminophenazine, o-phenylenediamine described in The Photographic Society of Japan, vol. 11, p. 48 (1948), mercaptobenzimidazole, methylbenzthiazole, mercaptobenzoxazole, And thiouracil, benztriazole, 5-methylbenztriazole, and heterocyclic compounds described in JP-B-46-41,675. In addition, "Science Photo Book", middle volume, p. 119 (Maruzen, published in 1959) and the aforementioned RD No. 17, 64
3, Nos. 18, 716 and 307, 105 can also be used.

Examples of the development accelerator which can be added to the activator include US Pat. Nos. 2,648,604 and 3,673.
No. 1,247, JP-B-49-9,503, etc., various pyridinium compounds and other cationic compounds,
Cationic dyes such as phenosafuran, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9,504
Nos. 2,533,990 and 2,531,
832, 2,950,970, 2,577,1
Nonionic compounds such as polyethylene glycol and derivatives thereof described in No. 27, polythioethers, etc.
9,509, the organic solvent described in Belgian Patent No. 682,862, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, and other LF
"Photographic Processing Chemistry" by A.Mason
(Photographic Processing Chemistry) pp. 40-43 (Focal Press; London 1966)
Also included are the accelerators detailed in.

Examples of the water softener include sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, and polyphosphate 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, Phosphonic acid represented by 1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid) or an alkali metal salt thereof or a salt thereof can be used. The addition amount varies depending on the hardness of the water, but is usually about 0.1 to 10 g / liter.

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

The activator may contain an organic solvent if necessary. For example, ethylene glycol, hexylene glycol, diethylene glycol,
Methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethyl sulfoxide, and other JP-B Nos. 47-33,378 and 44-9.
No. 509. The amount of addition may vary widely depending on the component composition of the activator, but is not more than 50% of the liquid used, usually not more than 10%.

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

In the present invention, the treatment temperature of the activator solution is 20 to 70 ° C., preferably 30 to 60 ° C., and most preferably 35 to 50 ° C. Processing time is from 20 seconds to 5
Minutes, preferably 30 seconds to 2 minutes. The replenishment amount is preferably as small as possible, but is suitably from 10 to 600 ml, preferably from 30 to 200 ml, and more preferably from 5 to 200 ml per m ^{2 of the} light-sensitive material.
0-150 ml.

Examples of the "substance capable of adsorbing a diffusible dye" that can be used in the present invention include activated carbon, carbon black, a cation or anion exchange resin, silica gel, alumino silica gel, and activated alumina. ,
Any of those generally known as organic adsorbents can be used irrespective of chemical adsorption. Some simple examples of the above adsorbents will be given. Activated carbon; registered in JIS K-1474-75 and has physical adsorption ability. There are powdery and granular forms.
Manufacturers include Sanwa Carbon, Tsurumi Coal, Fujisawa Pharmaceutical, Hokuetsu Carbon, Clera Chemical, Takeda Pharmaceutical, and Wako Pure Chemical. Ion exchange resin; commercially available strong acid cation exchange resin-(Amberlite) Amberlite IR
-120B (organo), (Dowex) Dowex (Muromachi Chemical). 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, (Dowex) Dowex I, (Dowex) DowexZ. Weakly basic anion exchange resin-(Amberlite) Amberl
ite IR-4B, (Amberlite) IR-
45, Diaion WA20, (Dowex) Dowex
3. It is known that a substance is adsorbed by chemical adsorption by a dissociating group. The diffusible dye generated according to the present invention is mainly a dissociative dye, and it is preferable to use an anion exchange resin to adsorb this. In addition, as alumina, alumino-silica gel, and silica gel, those commercially available from Sumitomo Aluminum, Mizusawa Chemical, Catalyst Chemicals, Wako Pure Chemical and other companies can be used.

In order to bring the above “substance capable of adsorbing a diffusible dye” into contact with the activator, the substance may be inserted into a mesh-like bag, container or the like capable of holding the activator and immersed in an activator bath. And the activator liquid 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.

After the activator treatment, a desilvering treatment is performed. In the desilvering process, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. When a dye image and a silver image are obtained together as described above, when the amount of silver applied is very small, such as 100 mg / m ² or less, only the fixing process may be performed without the bleaching process.

Examples of the bleaching agent used in the bleaching solution or 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. Representative bleaches include 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 ether diaminetetraacetic acid, etc.) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediaminetetraacetate
(III) a complex salt and iron 1,3-diaminopropanetetraacetate (I
II) Iron (III) aminopolycarboxylate complex salts such as complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution. The bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is used at a pH of 3 to 8.

Known additives such as a rehalogenating agent such as ammonium bromide or ammonium chloride; a pH buffering agent such as ammonium nitrate; and a metal corrosion inhibitor such as ammonium sulfate are added to the bleaching solution or the bleach-fixing solution. be able to. In the bleaching solution and the bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are acid dissociation constants (pK
Compounds in which a) is 2 to 5.5, 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 iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ′, N ′) are used in the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; defoaming agents; surfactants; polyvinylpyrrolidone; Bleach,
A bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof, if necessary. 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.
Having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July 1978);
No. 29; thiazolidine derivatives described in US Pat.
Thiourea derivatives described in JP-A-6-561;
Iodide salts described in No. 16235; West German Patent No. 2,74
8,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, U.S. Pat.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 10 seconds to
3 minutes, more preferably 20 seconds to 2 minutes. The processing temperature is from 20 ° C to 70 ° C, preferably from 35 ° C to 60 ° C. In a preferable temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A Nos. 62-183460 and 62-183.
No. 461, a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in a liquid And a method in which the photosensitive material is moved while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby further improving the stirring effect, and a method of increasing the circulating flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the 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 increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

In the present invention, an automatic developing machine used for processing a light-sensitive material is described 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 significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

In the present invention, the color light-sensitive material generally undergoes a water washing step after desilvering. A stabilizing step may be performed instead of the washing step. In such a stabilization process, JP-A-57-8543 and JP-A-58-148 are used.
All known methods described in JP-A Nos. 34 and 60-220345 can be used. Further, a washing step and a stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant, which is typified by processing of a color light-sensitive material for photography, is used as a final bath. Examples of the washing and stabilizing solutions include hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; metal salts such as Mg salts, Al salts and Bi salts; surfactants; Can be contained.

The amount of washing water in the washing step is determined by the characteristics of the photosensitive material (for example, depending on the material used such as the dye-donating compound), the use, the washing water temperature, the number of washing tanks (the number of stages), the counter flow, the forward flow, etc. It can be set in a wide range depending on other various conditions. Further, as a solution to problems such as propagation of bacteria and adhesion of generated suspended matter to a photosensitive material which occur when the amount of washing water is greatly reduced in a multi-stage countercurrent method, JP-A-62-288838 discloses a method. A method for reducing calcium ions and magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry". (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

The pH of the washing water is 4-9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally 15 to 45 ° C.
For 20 seconds to 10 minutes, preferably for 30 seconds at 25 to 40 ° C.
A range of 5 minutes is selected. Examples of the dye stabilizer 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, the stabilizing solution may further include a buffer for adjusting pH such as boric acid or sodium hydroxide;
1-hydroxyethylidene-1,1-diphosphonic acid; chelating agents such as ethylenediaminetetraacetic acid; antisulfurizing agents such as alkanolamines; fluorescent whitening agents; The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the present invention, as a processing method and a processing additive applied for processing a light-sensitive material, those described in
No. 88326, EP 0,355,660 A2 and the like are preferably used.

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is 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 nonyl phenyl ether as a dispersant, and 0.5 g of the following anionic surfactant were added to 100 ml of a 5% aqueous gelatin solution, and glass beads having an average particle size of 0.75 mm were milled. And ground for 60 minutes. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle size of 0.35 μm.

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Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. The cyan, magenta, and yellow dye-donating compounds and the gelatin dispersion of the electron donor were adjusted according to the formulations shown in Table 1, respectively. That is, each oil phase component is reduced to about 60
To a uniform solution by heating to about 60 ° C
The heated aqueous phase component was added to the mixture, and the mixture was stirred and mixed, and then dispersed with a homogenizer at 12,000 rpm for 13 minutes. Water was added thereto and stirred to obtain a uniform dispersion.

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[Table 1]

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Next, how to prepare a photosensitive silver halide emulsion will be described. Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 500 ml of water)
g) and 30 mg of the following chemical (A) were added, and the mixture was kept at 45 ° C.).
Add at an equal flow rate for minutes. Six minutes later, solution (III) and solution (IV) shown in Table 2 were simultaneously added at the same flow rate for 25 minutes. (II
10 minutes after the start of the addition of the liquids (I) and (IV), an aqueous solution of a gelatin dispersion of the dye (1 g of gelatin in 105 ml of water, 70 mg of the following dye (a), 139 mg of the following dye (b), 139 mg of the following dye (c ) Containing 5 mg and kept at 45 ° C) over 20 minutes.

After washing with water and desalting in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.8, and to adjust 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added to optimize chemical sensitization at 68 ° C
Then, the following antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

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[Table 2]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] A 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 thereto, and the mixture was kept at 65 ° C.).
Add at an equal flow rate for minutes. Five minutes later, solution (III) and solution (IV) shown in Table 3 were simultaneously added at the same flow rate for 15 minutes. (II
Two minutes after the start of the addition of the liquids (I) and (IV), an aqueous solution of a gelatin dispersion of the pigment (1.1 g of gelatin in 95 ml of water, 76 mg of the pigment (a), 150 mg of the pigment (b), 150 mg of the pigment (C) containing 5 mg and kept at 50 ° C.) over 18 minutes.

After washing with water and desalting in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.8, and to prepare 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added to optimize chemical sensitization at 68 ° C
Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodispersed 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] A 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)
g) and 15 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 47 ° C.). Solution (I) and solution (II) in Table 4 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 4 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of a gelatin dispersion of the pigment (2.5 g of gelatin in 100 ml of water and 250 mg of the following pigment (d) and kept at 45 ° C.) is collected at a time. Was added.

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

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[Table 4]

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Photosensitive silver halide emulsion (4) [for green-sensitive emulsion layer] A well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride in 700 ml of water)
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 60 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) in Table 5 were simultaneously added at the same flow rate for 20 minutes. Also (I
1) One minute after the completion of the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (1.8 g of gelatin in 75 ml of water and 180 mg of the above-mentioned dye (d) and kept at 45 ° C.) is collected at a time. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and the pAg to 7.6, and to adjust 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 68 ° C. Then, the following antifoggant (1) was added, followed by cooling. 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] A 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)
g) and 15 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 52 ° C.). Solution (I) and solution (II) shown in Table 6 were simultaneously added at the same flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
235 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 120 mg and kept at 45 ° C.) were added all at once.

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

[0103]

[Table 6]

[0104]

Embedded image

Photosensitive silver halide emulsion (6) [for blue-sensitive emulsion layer] A 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 15 mg of the above-mentioned chemical (A), and the mixture was kept at 65 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at an equal flow rate for 30 minutes. Also (I
One minute after the completion of the addition of the liquids (II) and (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 dye (f) and kept at 60 ° C.) were added all at once.

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

[0107]

[Table 7]

Using the above materials, photosensitive materials 101 shown in Table 8 were prepared.

[0109]

[Table 8]

[0110]

[Table 9]

[0111]

[Table 10]

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

The photosensitive material 101 was exposed through a wedge whose density continuously changed, and the following processing was performed. Processing Step Activator development 40 ° C for 1 minute Bleaching and fixing 40 ° C for 1 minute Rinse with water 20 ° C for 2 minutes Stabilization 20 ° C for 30 seconds Drying 70 ° C for 2 minutes

Activator liquid Tetramethylammonium hydroxide (25%) 80 ml Add water to make 1 liter. pH 13.3 Bleaching / fixing solution Ammonium thiosulfate 130 g Sodium metabisulfite 14 g Anhydrous sodium sulfite 3 g EDTA / ferric ammonium salt 65 g Add water to make 1 liter. pH 6.8 Stabilizing solution 2.1 g anhydrous sodium carbonate 1.7 g anhydrous sodium bicarbonate Add water to make 1 liter. pH 9.5

The maximum density and the minimum density of the processed light-sensitive material were measured by a transmission type X-Rite densitometer, and the results are shown in Table 9. Further, the photosensitive material 101 is kept at 50 ° C. and a relative humidity of 60%.
After storing for 1 week under the above conditions, the same treatment was performed and the results of concentration measurement are also shown in Table 9.

[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 simple processing, and that the raw storability of the photographic material is good.

Example 2 The same process was carried out using the same photosensitive material and processing solution as in Example 1 except that the composition of the activator solution was changed to the following. Table 10 shows the results of the concentration measurement. Activator solution Sodium hydroxide 0.25M Sodium bicarbonate was added to adjust the pH to 12.5. Activator solution Sodium hydroxide 0.25M Tetramethylammonium chloride 0.25M Sodium bicarbonate was added to adjust the pH to 12.5. Activator solution Sodium hydroxide 0.25M Sodium chloride 0.25M Sodium bicarbonate was added to adjust the pH to 12.5. Activator solution The organic base (22) of the present invention was adjusted to pH = 12.5 by adding 0.25 M sodium bicarbonate. Activator solution Potassium hydroxide 0.25M Benzyl alcohol 0.10M Sodium bicarbonate was added to adjust the pH to 12.5. Activator solution The organic base (33) of the present invention was adjusted to pH = 12.5 by adding 0.25 M sodium bicarbonate.

[0122]

[Table 12]

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

Example 3 A black-and-white photosensitive 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, processing and density measurement were carried out in the same manner as in Example 1 except that a fixing process (40 ° C. for 1 minute) having the following formulation was performed instead of the bleach-fixing process. Eleven 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]

It has been found that according to the present invention, a black and white image with excellent discrimination can be obtained.

Example 4 When the light-sensitive material 102 was repeatedly processed by 0.02 m ² per liter of the activator until it reached 1 m ² in the processing of Example 3, the activator liquid was colored and the minimum density of the image was increased. Then, when the granular activated carbon was put into a mesh-type saran bag having an opening of 10 μm and inserted into the activator solution, coloring was hardly caused, and an increase in the minimum density of the image was greatly suppressed. It was found that the use of a substance such as activated carbon that adsorbs a diffusible dye eluted in the activator solution enables a long-term stable treatment.

Claims (6)

(57) [Claims] 1. A least a photosensitive silver halide on a support, a reducing agent, a photosensitive material having a nondiffusible dye-providing compounds inverse correspondence to release a diffusible dye development of silver halide and a binder The reducing agent is
Composed of a proton transfer agent and a diffusion-resistant electron donor
A method of forming an image by treating an optical material with an aqueous alkaline solution having a pH of 8 or more, followed by treating with a bleaching solution, a fixing solution (or a bleach-fixing solution) or a fixing solution alone, followed by washing and drying. 2. The image forming method according to claim 1, wherein the dye donating compound is represented by the general formula [I]. General formula [I] [Wherein, 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 Dye via a subsequent reaction, triggered by cleavage of the NX bond,
t represents an integer of 0 or 1. Dye represents a diffusible dye. A solid line indicates a bond, and a broken line indicates that at least one of them is connected. ] 3. The alkaline aqueous solution is a hydroxide or salt of a quaternary alkylammonium; organic bases and an image forming method according to claim 1 or 2, wherein contains a salt thereof at least 0.01 mol / liter. 4. The method of claim 1 to 3 The image forming method according alkaline aqueous solution is treated in contact with a substance capable of adsorbing a diffusible dye. 5. A light-sensitive material comprising at least a light-sensitive silver halide, a reducing agent, a non-diffusible dye-donating compound which releases a diffusible dye in reverse correspondence to the development of silver halide and a binder on a support. An alkaline aqueous solution having a pH of 8 or more , wherein the alkaline aqueous solution can adsorb a diffusible dye.
A method in which an image is formed by processing in a state in which the image is in contact with a substance, followed by processing only with a bleaching solution, a fixing solution (or a bleach-fixing solution) or a fixing solution, followed by washing and drying. 6. The substance capable of adsorbing the diffusible dye is activated carbon, carbon black, a cation or anion exchange resin,
The image forming method according to claim 5, wherein the image forming method is silica gel, alumino silica gel, or activated alumina.