JPH04344642A - Method for processing silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deteriorations of desiverability and color reproduction performance even if the silver concentration in a bleach-fixing solution rises by using an emulsion layer containing silver chlorobromoiodide grains and specifying the silver concentration of the bleach-fixing solution. CONSTITUTION:The silver halide color reversal photographic sensitive material contains in at least one emulsion layer the silver chlorobromoiodide grains mainly comprising silver chloride on the surfaces of the grains. It is preferred that the photosensitive material contains the total silver halide on an amount of <=1.0g/m<2> in terms of silver. This photosensitive maternal is black-and-white developed, and then, color developed, and processed with the bleach-fixing solution containing silver ions in a concentration of <=0.05mol/l.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for processing a silver halide color reversal photographic light-sensitive material, and more particularly to a method for processing a silver halide color reversal photographic light-sensitive material in which the bleach-fixing step of the color reversal processing step can be performed under low replenishment conditions. Regarding the method.

0002

[Prior Art] In general, the standard processing steps for silver halide color reversal photographic materials include black and white development, color development, and then
It consists of each stage of the bleach-fixing process. A color developing solution for forming a color image in color reversal paper processing usually contains benzyl alcohol to promote color development. On the other hand, color developer components are accumulated in the bleach-fix bath due to the color developer components brought in from the previous bath. It becomes difficult to wash out the developer components, especially the color developing agent.
Because of problems such as poor color restoration and generation of magenta stain, it has been difficult to replenish the bleach-fix solution at a low level, especially when processing color reversal paper, for example.

On the other hand, in the above-mentioned processing, reducing the replenishment of the bleach-fixing solution or reusing it through regeneration processing not only provides a cost advantage of reducing the amount of chemicals used, but also reduces pollution due to the reduced amount of waste solution. This leads to a reduction in the load and is good for environmental conservation, but the reduction in replenishment or reuse of this bleach-fix solution results in an increase in the silver ion concentration and halogen ion concentration in the bleach-fix bath. The increase also causes problems such as poor desilvering, leucoization of the cyan dye (poor recoloring), or undesirable staining.

[0004] In bleach-fixing, a bleach accelerator may be used in the bleach-fixing solution, if necessary, in order to promote the effect of bleach-fixing. Specific examples of useful bleach accelerators include U.S. Patent No. 3,893,858, West German Patent No. 1,
No. 290,812, No. 2,059,988, Japanese Unexamined Patent Publication No. 1973
No. 3-32736, No. 53-57831, No. 3741
No. 8, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-
No. 141623, No. 53-28426, Research Disclosure No. 17129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832; No. 53-32735,
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-1
Iodide described in No. 6235; West German Patent No. 966,410
Polyethylene oxides described in Japanese Patent Publication No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434 and Japanese Patent Publication No. 49-5.
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 58-16394
Compounds described in No. 0 can be used.

However, even if these bleach accelerators are used, their improvement effect will be limited if the color developer components accumulate in the bleach-fix solution and the silver ion concentration reaches a high concentration of 0.05 mol/liter or more. It turns out that there is.

[0006]

[Problems to be Solved by the Invention] Therefore, in the color reversal processing step of silver halide color reversal photographic light-sensitive materials, color developing solution components are accumulated or bleach-fixing is performed using a bleach-fixing solution in which silver ions are accumulated. However, it is desirable to develop a processing method that prevents the occurrence of desilvering defects, cyan dye leucoization, staining, etc.

[0007] In the color reversal processing step, the carry-over of the color developing solution into the bleach-fixing bath can be reduced to some extent by improving the means for transporting the photosensitive material, but the accumulation of silver ions can be reduced to some extent. This is an essentially unavoidable problem since the bleach-fixing process is essentially a desilvering process. Particularly, when reducing the replenishment or reusing the bleach-fixing solution in the bleach-fixing process, the concentration of silver ions in the bleach-fixing solution is increased.

In view of the above points, the present invention provides a color reversal process for a silver halide color reversal photographic light-sensitive material, even if the silver ion concentration in the bleach-fix solution increases due to low replenishment or recycling. It is an object of the present invention to provide a method for processing a silver halide color reversal photographic material that does not cause problems such as poor desilvering and poor recoloring.

[0009]

[Means for Solving the Problems] As a result of extensive studies, the present inventor has determined that in the color reversal processing step, even if the silver ion concentration in the bleach-fix solution is 0.05 mol/liter or more, silver halide color reversal photographic material,
It was found that an emulsion layer containing silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains has the effect of improving desilvering and other problems and is acceptable in practice, and the present invention has been achieved. .

Furthermore, the photosensitive material has a total amount of silver halide,
It has been found that when the silver content is 1 g/m2 or less, problems such as desilvering and residual color can be solved. That is, the above object of the present invention is to perform color development after black-and-white development of a silver halide color reversal photographic light-sensitive material having at least one photosensitive image-forming layer containing silver halide grains and an image-forming coupler on a support. , in the color reversal treatment step of subsequent bleach-fixing treatment, at least one emulsion layer of the silver halide color reversal photographic light-sensitive material contains silver chlorobromoiodide grains containing mainly silver chloride on the surface of the grains, and This is achieved by a method for processing a silver halide color reversal photographic light-sensitive material, characterized in that the bleach-fixing solution used in the bleach-fixing process contains silver at a silver ion concentration of 0.05 mol/liter or more.

Furthermore, the silver halide color reversal photographic light-sensitive material has a total silver halide amount and a silver amount of 1.0 g/m
2 or less, the above objective can be better achieved.

The present invention will be explained in detail below. The silver halide emulsion used in the silver halide color reversal photographic light-sensitive material used in the present invention contains silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains in at least one emulsion layer. use. Such an emulsion is called a "surface Cl emulsion." In the present invention, this emulsion may be contained in any color-sensitive layer, but it is preferably contained in the green-sensitive layer or the red-sensitive layer. These emulsions can also be applied in several different or the same color-sensitive layers.

The surface Cl emulsion that can be used in the present invention will be explained below. In the present invention, the surface Cl emulsion specifically refers to the following. In other words, for silver halide grains made of silver chlorobromoiodide, "containing silver chloride mainly on the surface of the grain" means that 0 of the total silver amount from the center of the grain
Content of AgCl between ~50 mol%...x (mol%) AgC between 0 and 50 mol% of the total silver amount from the particle surface
Content of l...y (mol%) A on the particle surface determined by X-ray photoelectron spectroscopy (XPS)
gCl content...z (mol%) Ag on the outside and inside when the particles are divided into half of the total silver amount
When the Cl content ratio (outer AgCl content)/(inner AgCl content) is y/x, the Ag in the three regions x, y, and z is
A "surface Cl emulsion" is defined by the combination of Cl content and ratio thereof as follows. 1. Silver chlorobromoiodide, which mainly contains silver chloride on the surface of the grains, has a silver iodide content of 1 to 10 mol%, and all of y/x>2, y≧1 mol%, and z≧1 mol%. Refers to something that satisfies the following. 2. Preferably, the silver iodide content is 1 to 10 mol%, and y/x>10, y≧10 mol%, z≧10m
ol% (0≦x<10mol%). 3. More preferably, the silver iodide content is 2 to 8 mol%.
and y/x>100, y≧25mol%, z≧
50 mol% (0≦x<1 mol%). 4. Most preferably, the silver iodide content is 2 to 8 mol%, and y/x→∞ (in other words, x=0 mol%)
, y≧50 mol%, and z≧75 mol%.

[0014] The silver chloride content on the grain surface can be determined by measuring the silver halide grains by XPS (X-ray Photo).
This is the average silver chloride content in the surface area of silver halide grains obtained by electron spectroscopy) analysis. This content analysis can be performed, for example, by exciting the core electrons in the 3d orbit of Ag and the 2p orbit of Cl in the silver halide with soft X-rays characteristic of Al, Mg, etc., and analyzing the binding energy. .

The composition of the silver chloriobromoiodide grains to be contained in the emulsion layer of the light-sensitive material used in the present invention is not limited to the above-mentioned example of the surface Cl emulsion in terms of composition other than silver chloride. It may contain up to mol % silver iodide, and may contain from about 2 mol % to about 25 mol % silver iodide. When such silver iodide is contained, a multilayer effect can be obtained. As the silver halide used in the emulsion layer other than the emulsion layer containing the silver chlorobromoiodide grains of the light-sensitive material, any silver halide other than the silver chlorobromoiodide described above may be used.

The photosensitive material used in the present invention has a total silver halide content of 1.0 g/m2.
It is preferable that the content is below 0.7g/m
2 or less is more preferable. However, it is necessary to have a certain amount of silver for image formation, and 0.4g/
It is preferable to contain at least m2.

The silver halide color reversal photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer, each consisting of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, provided on a support. There are no particular restrictions on the number or order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748, 59-113438, 59-113440, 6
1-20037 and 61-20038, such as couplers, DIR compounds, etc., may be included, and a commonly used color mixing inhibitor may be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer include a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
As described in JP-A Nos. 57-112751, 62-200350, 62-206541, and 62-206543, a low-sensitivity emulsion layer is placed on the side away from the support, and a low-sensitivity emulsion layer is placed on the side closer to the support. A high-sensitivity emulsion layer may be provided.

In order to improve color reproducibility, US Pat.
, No. 663,271, No. 4,705,744, No. 4,707,436, JP-A-62-160448,
BL, GL, as described in the specification of No. 63-89580,
A multilayer effect donor layer (CL) having a different spectral sensitivity distribution from the main photosensitive layer such as RL may be arranged adjacent to or close to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No. 17643
(December 1978), pp. 22-23, “I. Emulsion preparation a
nd types)”. U.S. Pat. No. 3,574,628;
No. 3,655,394 and British Patent No. 1,413,
Monodispersed emulsions such as those described in No. 748 are also preferred.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, and tetradecahedrons, as well as irregular crystals such as spherical and plate shapes, and twin crystals. It may have crystal defects such as planes, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
c Science and Engineering
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,226, U.S. Pat. No. 4,414,310, U.S. Pat. It can be easily prepared by the method described in, for example, Japanese Patent No. 2,112,157.

The crystal structure may be uniform, or as described above, the inside and outside may have different halogen compositions, or it may have a layered structure, or the crystal structure may be formed by epitaxial bonding to create halogens with different compositions. Silver oxide may be bonded, or compounds other than silver halide, such as silver rhodan or lead oxide, may be bonded. Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643 and the same No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. Additive type
RD17643 RD1871
6 1 Chemical sensitizer
23 pages
Page 648 right column 2 Sensitivity enhancer

Same as above 3
Spectral sensitizer, supersensitizer 23-2
Page 4 Page 648 Right column ~


Page 649 right column 4 Brightener
24 pages

5 Antifoggants and stabilizers 24
~Page 25, page 649, right column~


Page 650 left column 6 Light absorbers, filter dyes, pages 25-26 64
Page 9 right column ~ Ultraviolet absorber

Page 650 left column 7 Stain inhibitor Page 25 right column Page 650 left to right column 8 Dye image stabilizer
25 pages
9 Hardener
26 pages
Page 651 left column 10 Binder
26 pages
Same as above 11
plasticizer, lubricant
Page 27 Page 650 Right column
12 Coating aids, surfactants
Pages 26-27 Page 650 Right column
13 Static inhibitor
Page 27 Same
In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411,9
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 87 and No. 4,435,503.

In the present invention, various color couplers can be used as the image-forming coupler, and specific examples thereof are shown in Research Disclosure (RD) No. 1 mentioned above. 1
No. 7643, VII-C-G.

Examples of yellow couplers include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
No. 4,248,961, Special Publication No. 58-1073
9, British Patent No. 1,425,020, British Patent No. 1,47
Preferred are those described in US Pat. No. 6,760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and are described in US Pat. No. 4,310,619, US Pat. No. 3,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984),
Japanese Patent Publication No. 60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1986
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-1859
No. 51, U.S. Patent No. 4,500,630, U.S. Patent No. 4,5
Particularly preferred are those described in No. 40,654, No. 4,556,630, International Publication No. WO88/04795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308 ,
4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559, Same No. 4,427,767, Same No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, U.S. Patent No. 4,163,
No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,
No. 004,929, No. 4,138,258 and British Patent No. 1,146,368 are preferred. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Pat. No. 4,774,181, and U.S. Pat. No. 4,777,120.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in the above-mentioned issue.

[0033] Examples of couplers whose colored dyes have appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570,
Preference is given to those described in German Patent No. 3,234,533.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
No. 09,320, British Patent No. 4,576,910, British Patent No. 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, patents listed in sections VII to F, JP-A-5
No. 7-151944, No. 57-154234, No. 60
-184248, 63-37346, 63-3
7350, U.S. Pat. No. 4,248,962, U.S. Patent No. 4,7
82,012 is preferred.

As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,42
Competitive couplers such as those described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,310
, 618, etc., JP-A-60-1
D described in No. 85950, JP-A No. 62-24252, etc.
IR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173,302A and EP 313,308A. , R. D. N
o. 11449, 24241, JP-A-61-2012
Bleach accelerator-releasing couplers described in US Pat. No. 47, etc., ligand-releasing couplers described in US Pat. , 774, 181, etc., which emit a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are U.S. Pat.
It is described in No. 027, etc.

Specific examples of high-boiling organic solvents with a boiling point of 175° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-di-ethylpropyl) phthalate, etc.), phosphorus Acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N- diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , trioctyl citrate, etc.), aniline derivatives (N,N-
dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of the latex dispersion process, effects, and latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230, etc.

The color photosensitive material of the present invention is disclosed in US Pat.
No. 379529 and No. 3639417, Japanese Unexamined Patent Publication No. 1983
Hydroquinones that release development inhibiting compounds as described in Research Disclosure No. 4-546 and Research Disclosure No. 4-546. Naphthohydroquinones which release development-inhibiting compounds described in No. 18264 (June 1979) can be preferably used.

[0042] The color photosensitive material of the present invention contains
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5- described in No. 3-257747, No. 62-272248, and JP-A-1-80941. Dimethylphenol, 2-phenoxyethanol, 2-(4-
It is preferable to add various preservatives or antifungal agents such as thiazolylbenzimidazole.

The present invention can be applied to various color reversal photographic materials, including color reversal films for slides or televisions, color reversal papers, and preferably color reversal paper as a representative example. can.

Suitable supports that can be used in the present invention include, for example, the above-mentioned RD. No. 17643, page 28, and the same No. 18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 20 μm or less.
More preferably, it is less than m. Also, membrane swelling rate T (1/2)
is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate T (1/2) can be measured according to a method known in the art. . For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
It can be measured by using a swellometer of the type described in Vol. 2, pp. 124-129, and T(1
/2) is defined as the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds, and the time required to reach the film thickness of T (1/2). Define.

The membrane swelling rate T(1/2) can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

In the processing method of the present invention, the above-mentioned silver halide color reversal photographic light-sensitive material is subjected to color reversal processing after imagewise exposure, and the processing basically involves black and white development using a black and white developer. It consists of a process of subsequent color development followed by bleach-fixing, and a reversal process such as optical fogging or chemical fogging is performed after black-and-white development. Further, steps such as a stop bath and water washing are inserted between these steps as necessary.

Known developing agents can be used as the black and white developer used in the black and white development carried out at the beginning of the color reversal process. As developing agents, dihydroxybenzenes (e.g. hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (e.g. 1
-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), ascorbic acid and U.S. Pat.
, 872, a heterocyclic compound in which a 1,2,3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The amount of these developing agents added is 1 per liter of developer.
It is about x10-5 to 1 mol/liter.

The black and white developer used in the present invention may contain other preservatives (for example, sulfites, bisulfites, etc.) as necessary.
, buffering agents (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (e.g. polyethylene glycols,
esters), pH adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, antifoaming agents, hardeners, viscosity-imparting agents, etc. can be contained.

The black and white developer used in the present invention preferably contains a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. The sulfite and other usable silver halide solvents include KSCN, NaSCN,
K2 SO3 , Na2 SO3 , K2 S2 O5
, Na2 S2 O5 , K2 S2 O3 , Na
2 S2 O3, 2-methylimidazole, etc. can be mentioned.

Further, a development accelerator is used to impart a development accelerating effect, and thioether compounds described in JP-A No. 57-63580 are particularly preferred. SCN- is 0.005 to 0.0 per liter of developer
2 mol, especially 0.01 to 0.015 mol, SO32- is preferably 0.05 to 1 mol, especially 0
．． The amount is preferably 1 to 0.5 mol.

Various antifoggants may be added to the black and white development process of the present invention for the purpose of preventing development fog. Preferred antifoggants include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-5-mercabutotetrazole 2
Mercapto-substituted heterocyclic compounds such as -mercabutobenzimidazole, 2-mercabutobenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants are
This includes substances that are eluted from color reversal light-sensitive materials during processing and accumulate in these developers.

Among these, bromide is preferable for preventing fogging, and the preferable concentration is 1×10 −3 mol to 0.1 m
ol/liter, more preferably 0.01 to 0.05 m
It is about ol/liter.

Furthermore, the black and white developer of the present invention contains a swelling inhibitor (for example, an inorganic salt such as sodium sulfate or potassium sulfate).
or a water softener. As the water softener, those having various structures such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic-inorganic phosphonic acid can be used. Specific examples are shown below, but the invention is not limited to these.

Ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid,
Nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, these water softeners are two types The above may be used in combination. The amount added is preferably 0.1 g to 20 g/liter, more preferably 0.5 g to 10 g/liter.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, and is usually in the range of about 8.5 to about 11.5, but not more than 9.
It is preferably in the range of 5 to 10.5.

The processing time for black and white development is 20 seconds to 3 minutes, preferably 30 seconds to 90 seconds. Processing temperature is 30° to 50°C
, preferably 35°C to 45°C. The amount of replenishment of the black and white developer is about 50 ml to 500 ml, preferably about 50 ml to 330 ml, per m@2 of the photosensitive material.

In the processing of the present invention, after black-and-white development, the film is washed and/or rinsed with water, and then, if necessary, processed in a reversal bath (fog bath), followed by color development processing.

Although a single water washing or rinsing bath may be used, it is more preferable to adopt a multistage countercurrent system with two or more tanks in order to reduce the amount of replenishment. Here, water washing refers to a method in which a relatively large amount of water is replenished, whereas rinsing refers to a method in which the amount of replenishment is reduced to the level of other processing baths. The amount of washing water to be replenished is preferably about 3 liters to 20 liters per m@2 of photosensitive material. In addition, the amount of replenishment of the rinse bath is 50ml to 2
It is preferably about 100 ml to 500 ml, and the amount of water used is significantly reduced compared to the water washing step.

[0060] The rinsing bath of the present invention may also contain, if necessary,
Oxidizing agents, chelating agents, buffering agents, bactericidal agents, optical brighteners, etc. can be added. The fogging bath used in the present invention can contain a known fogging agent. That is, stannous ion-organophosphate complex salt (U.S. Pat. No. 3,617
, 282 specification), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 1983-32616), stannous ion-aminopolycarboxylic acid complex salt (British Patent No. 1,
209,050), stannous ion complex salts, such as
Boron hydride compounds (U.S. Patent No. 2,984,567), heterocyclic amine borane compounds (British Patent No. 1,
011,000), and the like. The pH of this fog bath (reversal bath) ranges widely from the acidic side to the alkaline side, with a pH of 2 to 12.
, preferably from 2.5 to 10, particularly preferably from 3 to 9. Reversal may be performed in a fogging bath or may be performed in re-exposure. It can also be omitted by adding a fogging agent to the color developing bath.

[0061] The color developing solution used in the color development of the present invention is as follows:
Preferred is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used. Typical examples of p-phenylenediamine compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, and 3-methyl-4 -amino-N-
Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates , tetraphenylborate, p-(t-octyl)benzenesulfonate, and the like.

In addition, the concentration and pH of the developing agent in the color developer are very important factors in shortening the development time.
g to about 15 g, more preferably about 3.0 g to about 8.0 g per liter of color developer. Further, the pH of the color developing solution is selected from a range of about 8 to 13, but is usually 9 or more, and most preferably used at a pH of about 9.5 to about 12.0.

The processing temperature of the color developing solution in the present invention is as follows:
The temperature is selected from 20 to 70°C, preferably 30°C to 50°C, and more preferably 31°C to 45°C. Further, in the present invention, various development accelerators may be used in combination as necessary.

Further, as a development accelerator, benzyl alcohol, US Pat. No. 2,648,604, Japanese Patent Publication No. 44
-9503, various pyridinium compounds and other cationic compounds represented by U.S. Patent No. 3,171,247, cationic dyes such as phenosafranin,
Neutral salts such as thallium nitrate and potassium nitrate,
-9304, U.S. Patent No. 2,533,990, No. 2
, No. 531,832, No. 2,950,970, No. 2,
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 577,127,
The thioether compounds described in US Pat. No. 3,201,242 may also be used.

In the color development step of the present invention, various antifoggants may be used in combination for the purpose of preventing development fog. As the antifoggant used in these developing steps, alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants are preferred. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzodriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants include those that are eluted from color reversal photosensitive materials during processing and accumulate in these developers.

[0066] In addition, the color developing solution in the present invention may contain pH buffering agents such as alkali metal carbonates, borates, or phosphates; hydroxylamine, diethylhydroxylamine, triethanolamine, catechol-3,
5-disulfonate, West German Patent Application (OLS) No. 2,6
22,950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol, triethylene glycol; dye-forming couplers;
competitive couplers such as citradinic acid, J acid, H acid; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazosolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, Aminopolycarboxylic acids, 1- Hydroxyethylidene-1
, 1'-diphosphonic acid, Research Disclosure No. 18170 (May 1979), aminophosphonic acids such as aminotris (methylenephosphonic acid), ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, JP-A-52-10272
No. 6, No. 53-42730, No. 54-121127, No. 55-4024, No. 55-4025, No. 55-
No. 126241, No. 55-65955, No. 55-65
No. 956, and Research Disclosure No.
18170 (May 1979), a chelating agent such as a phosphonocarboxylic acid can be contained.

The amount of color developer replenisher to be refilled is 50 ml to 100 ml, preferably 100 ml per m2 of light-sensitive material.
ml to 500 ml. After color development, the color reversal light-sensitive material is then desilvered by bleach-fixing. The desilvering process is usually carried out as follows. 1. (Color development) - Washing - Bleach-fixing 2. (Color development) - Adjustment - Bleach-fixing 3. (Color development) - Bleach fixing 4. (Color development) - Washing - Bleaching - Bleach fixing 5. (Color development) - Bleaching - Bleach-fixing 6. (Color Development) - Washing - Bleaching - Bleach-Fixing - Fixing Among the above steps, 1 and 3 are particularly preferred.

As for the replenishment method in the above processing steps, the replenisher solution for each bath may be individually replenished into the corresponding processing bath as in the conventional method, or in step 5, the overflow solution of the bleach solution is used for bleach-fixing. The bleach-fix bath may be refilled only with the fixer composition. In addition, in step 6, the overflow solution of the bleach solution is introduced into the bleach-fix solution, the overflow solution of the fix solution is introduced into the bleach-fix solution in a countercurrent manner,
A method may be used in which both are allowed to overflow from the bleach-fixing bath.

The bleach-fixing carried out here is one of the characteristics of the processing method of the present invention, in which the silver ion concentration is 0.
．． This is carried out using a bleach-fix solution containing 0.5 mol/liter or more of silver. However, containing silver above a certain concentration does not mean actively adding silver in hopes of achieving a certain effect; in conventional color reversal processing, the bleach-fix solution has a silver ion concentration of 0. If the concentration exceeds .05 mol/liter, desilvering performance deteriorates and color restoration is impaired, so bleach-fixing is not performed in this concentration range. It should be understood that this is a concentration range in which no specific treatment has been performed, and is intended to clarify the difference from the prior art, and is the range in which the unique effects of the present invention have been discovered. It is something.

The bleach-fix solution used in the present invention has the same composition as conventional bleach-fix solutions except for silver ions. The bleaching agent used in the bleach-fix solution or bleaching solution of the present invention is an aminopolycarboxylic acid iron (trivalent) complex salt currently used as a bleaching agent. Representative examples of these aminopolycarboxylic acids and their salts include: A-1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-4 Diethylenetriaminepentaacetic acid A-5 Cyclohexanediamine Tetraacetic acid A-6 cyclohexanediamine tetraacetic acid disodium salt A-7 iminodiacetic acid A-8 1,3-diaminopropane tetraacetic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using the ferric salt and the aminopolycarboxylic acid. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

The bleach-fix solution or bleaching solution containing the ferric ion complex described above may also contain a metal ion complex salt other than iron, such as cobalt or copper. Various bleach-fixing accelerators can be added to the bleach-fixing bath of the present invention, the bleaching bath, or the conditioning bath which is a pre-bath thereof.

Examples of such bleach accelerators include those described in US Pat. No. 3,893,858, British Pat.
Various mercapto compounds as described in Japanese Patent Publication No. 3, Compounds having a disulfide bond as described in Japanese Patent Publication No. 53-95630, Japanese Patent Publication No. 53-985
Thiazolidine derivatives such as those described in Japanese Patent Publication No. 4, isothiourea derivatives such as those described in Japanese Patent Publication No. 53-94927, Japanese Patent Publications No. 45-8506 and Japanese Patent Publication No. 49-26586. Examples include thiourea derivatives such as thiourea derivatives, thioamide compounds as described in JP-A-49-42349, dithiocarbamates as described in JP-A-55-26506, and the like.

Further, as a bleaching accelerator, alkyl mercapto which is unsubstituted or substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group (the alkyl group and the acetoxyalkyl group may have any substitution), etc. Compounds can be used. Examples include tothioglycerin, α,α'-thiodipropionic acid, and δ-mercaptobutyric acid. Additionally, U.S. Patent No. 45528
Compounds described in No. 34 can also be used.

The amount of the compound having a mercapto group or disulfide bond in the molecule used in the present invention, thiazoline derivative or isothiourea derivative to be added to the bleaching solution depends on the type of photographic material to be processed, the processing temperature, and the intended processing. Although it differs depending on the time required for processing, etc., 1 x 10-5-10-1 mol per liter of processing solution is appropriate.
Preferably it is 1 x 10-4 to 5 x 10-2 mol.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution used in the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride, etc. rehalogenating agents. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax,
pH of sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Additives commonly known for use in bleaching solutions can be added, such as one or more inorganic acids, organic acids and their salts having buffering capacity.

In the present invention, the amount of bleaching agent per liter of bleaching solution is 0.1 mol to 1 mol, preferably 0.1 mol to 1 mol.
．． The amount is 2 mol to 0.5 mol. Further, the pH of the bleaching solution is preferably 4.0 to 8.0, particularly 5.0 to 6.5 during use.

In the present invention, the amount of bleach per liter of bleach-fix solution is 0.05 mol to 0.5 mol, preferably 0.1 mol to 0.3 mol. The bleach-fix solution also contains thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sodium thiocyanate, and other fixing agents.
Thiocyanates such as ammonium thiocyanate and potassium thiocyanate, thioureas, thioethers, and the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol to 2 mol, per liter of bleach-fix solution.
It is a mole.

The amount of replenishment of the bleach-fix solution, bleaching solution, etc. in the present invention can be set arbitrarily, but is preferably 30 ml to 900 ml per 1 m 2 of light-sensitive material. More preferably, it is 50 ml to 150 ml.

In the present invention, the fixing agent-containing liquid contains known fixing agents such as ammonium thiosulfate and sodium thiosulfate, sulfites, bisulfites, various buffering agents, chelating agents,
All additives that can be added to the fixer solution, such as sulfinic acids, can be added. The concentration of each component in these fixer-containing solutions can be set so that when mixed with the overflow solution of the bleach bath and diluted, it will reach the concentration required as a bleach-fix solution, and is usually replenished into the fixer bath. It can be made more concentrated than usual. As a result, the amount of liquid discharged also decreases, and the burden of recovery processing can be reduced. The concentration of the fixing agent contained in the fixing agent-containing liquid is preferably 0.5 to 4 mol/liter, more preferably 1 to 3 mol/liter.
mole/liter. Further, the pH of the fixing agent-containing liquid is preferably 6 to 10, more preferably 7 to 9. Further, ferric aminopolycarboxylic acid complex salts, ammonium halides such as ammonium bromide, sodium bromide, and sodium iodide, and alkali metal halides may be added. The pH of the bleach-fixing bath according to the present invention is from 5 to 8, preferably from 6 to 7.5.

In the processing method of silver halide color reversal photographic light-sensitive materials, after the above-mentioned desilvering step, processing steps such as water washing and/or stabilization are generally carried out. A simple treatment method that performs stabilization treatment without washing with water can also be used.

[0082] The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and fungicides that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, drying load, and unevenness. A surfactant or the like can be used to prevent this. Or L. E. West, “
WaterQuality Criteria”Ph
ot. Sci. and Eng. , Vol. 9No.
6p. Compounds described in 344-359 (1965) and the like can also be used. In addition, the water washing process may be repeated 2 times if necessary.
The washing may be carried out using more than one tank, or the washing water may be saved by performing multi-stage countercurrent washing (for example, 2 to 9 stages).

As the stabilizing liquid used in the stabilizing step, a processing liquid for stabilizing the dye image is used. For example, pH3
A solution having a buffering capacity of ~6, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

Further, the stabilization step may be carried out using two or more tanks if necessary, and multi-stage countercurrent stabilization (for example, two or more tanks may be used).
to 9 stages), the stabilizing liquid can be saved and the water washing step can also be omitted.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

[0086]

[Operation] A conventional silver halide color reversal photographic light-sensitive material is subjected to black and white development using a black and white developer, followed by color development.
In the color reversal processing step of subsequent bleach-fixing, if the bleach-fixing solution contains silver with a silver ion concentration of 0.05 mol/liter or more, desilvering performance deteriorates and color restoration failure occurs. Therefore, when at least one emulsion layer is processed using a silver halide color reversal photographic material containing silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains, desilvering performance deteriorates and color restoration occurs. No defects will occur. Even if the silver chloride concentration in the entire emulsion is not high, by making silver chloride exist in a shell shape near the surface of the emulsion grain, for example, even if the silver chloride concentration in the entire emulsion grain is 25 mol%, the silver chloride concentration on the surface can be reduced. If the concentration is higher than that, the silver ion concentration will be high (0.05 mol/
The desilvering property of the bleach-fix solution is improved. The reason for this effect is not clear, but since silver chloride has higher solubility, it is presumed that increasing the concentration of silver chloride on the surface of emulsion grains enhances the desilvering effect.

Furthermore, in the present invention, when the light-sensitive material contains a total amount of silver halide of 1.0 g/m2 or less, the desilvering property is further improved and the extent to which poor color restoration occurs is also reduced. few. This is considered to be one of the reasons why the total amount of halogen silver in the light-sensitive material is small, which reduces the amount of silver remaining after bleach-fixing.

[0088]

[Examples] The present invention will be explained in detail with reference to Examples below, but the present invention is not limited thereto. (Preparation of emulsion) Silver iodobromide emulsion A was prepared as follows. First, aqueous solutions I to III were prepared as shown in Table 1.

[0089]

[Table 1] Emulsion A (AgBrI) As shown in Table 2, Solutions II and III were added to Solution I by the double jet method while maintaining pAg at 7.1 in the first and second stages. After the addition was completed, it was desalted by a known method, Na2 S2 O3 and KAuCl4 were added, and the mixture was chemically sensitized at 70° C. for 50 minutes. Emulsion B (AgBrI) Increase the reactor temperature relative to Emulsion A, and
Particle formation was achieved by decreasing the addition rate in the steps. Details are shown in Table 2. After the addition was completed, the emulsion was desalted in the same manner as Emulsion A, Na2 S2 O3 and KAuCl4 were added, and chemical sensitization was carried out at 70 DEG C. for 50 minutes.

[0090]

[Table 2] Emulsions A and B have average grain sizes of 0.3 μm and 0.7 μm, respectively.
It was a cubic monodisperse agent made of silver iodobromide containing 3.0 mol % of silver iodide with micrometer diameter. Emulsions C to N (AgBrClI) Next, various chlorobromoiodide silver emulsions C to N containing 3.0 mol % of silver iodide were prepared as follows.

First, as shown in Table 3, aqueous solutions IV to IX were prepared separately from solution III.

[0092]

[Table 3] In the preparation of silver chlorobromoiodide emulsions C to N, as shown in Tables 4 and 5, the pAg was maintained at 7.1 in the first, second and third stages for the I solution. Liquid and liquids III to IX were added by double jet method.

Emulsions C, E, G, I, K and M were prepared at the same temperature (65°C) as Emulsion A, and Emulsions D, F, H, J, L
and N were prepared at the same temperature as emulsion B (80°C). After the addition is complete, desalt in the same manner as emulsions A and B, and remove Na2S.
2 O3 and KAuCl4 were added, and chemical sensitization was carried out at 70°C for 50 minutes.

The obtained emulsions C, E, G, I, K and M had an average grain size of 0.3 μm, and the emulsions D, F, H, J, L and N
was a cubic monodispersed emulsion of silver chlorobromoiodide containing 3.0 mol % of silver iodide with an average grain size of 0.7 μm.

[0095]

[Table 4]

[0096]

[Table 5] Structures of these emulsions A to N and the inside/outside of the grains
The content of AgCl on the surface is summarized in a table and classified based on the above regulations, as shown in Table 6.

Furthermore, phenoxyethanol was added as a preservative to emulsions A to N at a ratio of 1.6 g/100 g AgNO3.

[0098]

[Table 6] In Table 6, *Cl content on particle surface (vs. Agmol
%) [ESCA-750 manufactured by Shimadzu Corporation] ** Specified group No. of surface Cl emulsion. corresponds to

(All units other than y/x are mol%) Next, a color reversal photographic material was prepared by coating the following 1st to 12th layers in multiple layers on a paper support laminated on both sides with polyethylene. . 1 on the side where the first layer of polyethylene is applied
5% by weight of anatase titanium oxide as a white pigment,
It also contains trace amounts of ultramarine as a bluish dye.

As the silver halide emulsions contained in one of the third and fourth layers of these samples, appropriate ones were used from among the emulsions A to N as shown in Table 7 below. . (Photosensitive layer composition) The components and coating amounts in g/m2 are shown below. Regarding silver halide, the coating amount is shown in terms of silver. 1st layer (gelatin layer) Gelatin

...1.30 Second layer (antihalation layer) Black colloidal silver

...0.10 gelatin

...0.70 Third layer (low sensitivity red-sensitive layer) Silver iodobromide emulsion A (silver iodide 3 mol% , average particle size 0.3μ, particle size distribution 10%, cubic)

...0.06 Red sensitizing dye (ExS-1, 2
, 3 equivalent amounts) spectrally sensitized with silver iodobromide (silver iodide 4 mol%, average grain size 0.5μ, grain size distribution 15%,
cube)
...0.10 gelatin

...1.00 Cyan coupler (ExC-1)

...0.14 Cyan coupler (ExC-2)

...0.07 Antifading agent (Equivalent amounts of Cpd-2, 3, and 4) ...0.1
2 Coupler dispersion medium (Cpd-6)
...0.0
3 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3)
...0.06 Development accelerator (Cpd-13)
...0.05 4th layer (high sensitivity red sensitive layer) Silver iodobromide emulsion B spectrally sensitized with red sensitizing dyes (Equivalent amounts of ExS-1, 2, and 3) (3 mol% silver iodide) , average particle size 0.7 μ, particle size distribution 15%, cubic)

...0.15 Gelatin

...1.00 Cyan coupler (ExC-1)
...0.20 Cyan coupler (ExC-2)
...0.10 Antifading agent (Equivalent amounts of Cpd-2, 3, and 4)
...0.15 Coupler dispersion medium (C
pd-6)
...0.03 Coupler solvent (So
lv-1, 2, 3 each equivalent)
...0.10 5th layer (middle layer) magenta colloid silver
…
...0.02 gelatin

...1.00 Color mixing prevention agent (Cp
d-7, 16 each equivalent)
...0.08 Color mixing prevention agent solvent (Solv
-4, 5 each equal amount)...
...0.16 Polymer latex (Cpd-8)
...0
．． 10 6th layer (low sensitivity green sensitive layer) Silver chloroiodobromide (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain size) spectrally sensitized with a green sensitizing dye (ExS-4) 0.28μ, particle size distribution 8%, cubic, core iodide type core shell) ...0.04
Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 2.5 mol%, average grain size 0.48μ, grain size distribution 12%, cubic)

...0.06 Gelatin

...0.80
Magenta coupler (Equivalent amounts of ExM-1 and 2)
...0.10 Anti-fading agent (Cpd-9)
...0.10 Stain inhibitor (Equivalent amounts of Cpd-10 and 11)
...0.01 Stain inhibitor (Cp
d-5)
...0.001 Stain inhibitor (C
pd-12)
...0.01 Coupler dispersion medium (Cp
d-6)
...0.05 Coupler solvent (Sol
v-4, 6 each equivalent)
...0.15 7th layer (high sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 3.5 mol%, average grain size 1.0μ ,
Grain size distribution 21%, flat plate (aspect ratio = 9, uniform iodide type))...0.
10 Gelatin

...0.80 Magenta coupler (Ex
M-1, 2 each equivalent amount)
...0.10 Anti-fading agent (Cpd-9)

...0.10 Stain inhibitor (Cpd-10,
11, 22 each equivalent amount) ...0.01
Stain inhibitor (Cpd-5)
...0.001
Stain inhibitor (Cpd-12)
...0.01
Coupler dispersion medium (Cpd-6)
...0.05
Coupler solvent (Solv-4, 6)
...0.15 8th layer (
yellow filter layer) yellow colloidal silver
…
...0.20 Gelatin

...1.00 Color mixing prevention agent (Cp
d-7)
...0.06 Color mixing prevention agent solvent (Solv-4, 5 each equivalent amount)
...0.15 Polymer latex (Cp
d-8)
...0.10 9th layer (low sensitivity blue sensitive layer) Silver chloroiodobromide (silver chloride 2 mol%, silver iodide) spectrally sensitized with blue sensitizing dyes (ExS-5 and ExS-6 in equivalent amounts) 2.5 mol%, average particle size 0.38μ, particle size distribution 8%,
Cubic, core iodide type core shell))


...0.07 Blue sensitizing dye (ExS
silver iodobromide (silver iodide 2
．． 5 mol%, average particle size 0.55μ, particle size distribution 11%, cubic)
...0.10
gelatin

...0.50 Yellow coupler (ExY-1
, 2 each equivalent amount) ...0
．． 20 Stain inhibitor (Cpd-5)
...0
．． 001 Anti-fading agent (Cpd-14)
…
...0.10 Coupler dispersion medium (Cpd-6)
…
...0.05 Coupler solvent (Solv-2)
…
...0.05 10th layer (high sensitivity blue sensitive layer) Silver iodobromide (2.5 mol% silver iodide, average grain Size 1.4μ, particle size distribution 21%, flat plate (aspect ratio = 14))
...0.25 Gelatin

...1.0
0 Yellow coupler (Equivalent amount of ExY-1 and 2)
...0.40 Stain inhibitor (Cpd-5)
...0.002 Anti-fading agent (Cpd-14)
...0.10 Coupler dispersion medium (Cpd-6)
...0.15 Coupler solvent (Solv-2)
...0.10 11th
Layer (ultraviolet absorption layer) Gelatin

...1.50 Ultraviolet absorber (Cpd-1,
2, 4, 15 equivalent amounts) ...1.0
0 Color mixing inhibitor (Cpd-7, 16)
...0.06
Dispersion medium (Cpd-6)
……
0.15 Ultraviolet absorber solvent (Equivalent amounts of Solv-1 and 2) ...0.15 Anti-irradiation dye (Equivalent amounts of Cpd-17 and 18)
...0.02 Anti-irradiation dye (
Cpd-19, 20 each equivalent) ...0.02 1st
2 layers (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0
．． 2μ) ...0.07 Modified poval

...0.02 Gelatin
…
...1.50 Gelatin hardening agent (equal amounts of H-1 and 2)
...0.
17 Furthermore, each layer contains alkanol X as an emulsification and dispersion aid.
C (Du Pont) and sodium alkylbenzenesulfonate, succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink) were used as coating aids. (Cpd-21, 22, 23) was used as a stabilizer in the silver halide or colloidal silver containing layer. The compounds used in the examples are shown below.

[0101]

[Chemical formula 1]

[0102]

[Case 2]

[0103]

[Chemical formula 3]

[0104]

[C4]

[0105]

[C5]

[0106]

[C6]

[0107]

[C7]

[0108]

[Chemical formula 8]

[0109]

[Chemical formula 9]

[0110]

Example 1 In the color reversal photographic light-sensitive material described above, the total amount of silver was the same (silver 1.32 g/m2), and one emulsion of the third layer and the silver halide emulsion contained in the fourth layer were By replacing sample No. 7 as shown in FIG. Samples 1 to 4 (Sample 1 consists of the composition of the photosensitive layer described above) were prepared, and the silver ion concentration of the bleach-fix solution was 0.01 mol/liter (Condition 1).
) and 0.05 mol/liter (condition 2), the desilvering property (residual silver amount) and poor color recovery were evaluated.

The light-sensitive material pieces of Samples 1 to 4 were subjected to wedge exposure using a white light source, and then processed in the following steps. Processing process First development (black and white development) 38℃
75 seconds water
Wash at 38℃
90 seconds
Reverse exposure
100lux or more 60 seconds or more Color development
38℃
135 seconds
Washing with water
38℃ 45 seconds
bleach fixing
38℃
120 seconds
Washing with water
38℃ 135 seconds
Drying


Processing solution composition (first developer) Nitrilo-N,N,N-trimethylenephosphonic acid.

pentasodium salt

0.6g diethylenetriaminepentaacetic acid, pentasodium salt 4
．． 0g potassium sulfite

30.0g Potassium thiocyanate
1.2g
potassium carbonate

35.0g Hydroquinone monosulfonate potassium salt 25
．． 0g diethylene glycol

15.0ml 1-phenyl-4-hydroxymethyl-4-methyl
-3-pyrazolidone
2.0g potassium bromide

0.5g potassium iodide

Add 5.0mg water
1
liter

(pH 9.70) (Color developer) Benzyl alcohol
1
5.0ml diethylene glycol

12.0ml 3,6-dithia-1,
8-octanediol
0.2g Nitrilo-N,N,N-trimethylenephosphonic acid
・Pentasodium salt

0.5g diethylenetriaminepentaacetic acid, pentasodium salt
2.0g sodium sulfite
2.0g
potassium carbonate

25.0g Hydroxylamine sulfate
3.0g N-ethyl-N-(β-methanesulfonamidoethyl)
-3-methyl-4-aminoaniline sulfate
5.0g potassium bromide

0.5g
potassium iodide

Add 1.0mg water

1 liter


(pH 10.40) (bleach-fix solution) 2-mercapto-1,3,4-triazole
1.0g
Ethylenediaminetetraacetic acid, disodium, dihydrate
5.0g Ethylenediaminetetraacetic acid, Fe (trivalent), ammonia
Ni-water salt
80.0
g Sodium sulfite

15.0g Sodium thiosulfate (700g/liter liquid) 1
60.0ml glacial acetic acid

Add 5.0ml water

1 liter

(pH 6.50) Regarding the bleach-fixing solution, two types of solutions having silver ion concentrations of 0.01 mol/liter and 0.05 mol/liter were prepared based on the above formulation, and these were used.

The silver ion concentration in the bleach-fix solution was analyzed using atomic absorption spectrometry. Desilvering properties were evaluated by analyzing the amount of residual silver in the maximum concentration part of the treated sample using fluorescent X-rays. or,
In order to evaluate poor color restoration, the treated sample was treated with the bleach-fix solution containing no silver ions at 38° C. for 3 minutes, and the amount of change in the cyan image after washing and drying was determined. That is, the density before reprocessing is expressed as the color development rate (%), with the point of density 2.0 after reprocessing taken as 100%.

The results are shown in Table 7.

[0114]

[Table 7] Example 2 Sample No. 3, the total silver amount of the photosensitive material can be increased to 1.6 to 0.7 g/m2 without changing the silver amount ratio of each emulsion layer of blue, green, and red sensitive layers. Changed sample No. 5 to 7 as sample No. 3 (total silver amount 1.32g/m
2) were prepared separately, and these samples were also subjected to the same treatment as in Example 1 to evaluate desilvering properties and poor color recovery.

The results are shown in Table 8.

[0116]

[Table 8] As can be seen from Table 7, when the silver ion concentration in the bleach-fix solution was 0.01 mol/liter (condition 1), the surface Cl content of the emulsion contained in the third and fourth layers changed. However, when the silver ion concentration of the bleach-fix solution accumulates to 0.05 mol/liter (condition 2), there is no significant difference in desilvering and restoration defects. The effect of improving the desilvering property and the poor recoloring was remarkable, and when the sample was processed under Condition 2 using the emulsion of the comparative example, the desilvering property and the poor recoloring were practically unacceptable.

In addition, as shown in Table 7, even if the silver chloride content of the entire emulsion grain is not necessarily high, by increasing the silver chloride content on the grain surface, the desilvering property and color recovery can be improved even with the same total silver chloride content. It can be seen that defects can be improved.

Further, as shown in Table 8, if the emulsions have the same composition, the total silver of the light-sensitive material can be adjusted without changing the silver content ratio of each emulsion layer of the blue, green, and red sensitive layers. As the amount is reduced, especially when the total silver amount is 1.0 g/m2 or less, desilvering performance and poor restoration of color are significantly improved in bleach-fixing processing where the silver ion concentration is accumulated at 0.05 mol/liter. I understand that.

[0119]

According to the present invention, when processing a silver halide color reversal photographic light-sensitive material in a color reversal processing step, in the bleach-fixing process during the color reversal processing step,
By reducing replenishment or reusing the bleach-fix solution, it is possible to improve desilvering performance and poor color restoration even when silver ions in the bleach-fix solution accumulate and their concentration increases. In particular, according to the present invention, when the silver ion concentration in the bleach-fix solution is low, the desilvering performance and color development rate (related to poor color restoration) are
Although it is slightly better than when using a conventional photosensitive material that does not contain emulsions, there is not much of a difference, but when the silver ion concentration in the bleach-fix solution increases, it becomes worse when using a conventional photosensitive material. They deteriorate considerably, whereas the present invention containing surface Cl emulsions makes a significant difference in that they remain good and do not deteriorate. For this reason, the present invention
It is suitable and practical for reducing the amount of replenishment or reusing the bleach-fixing solution in the bleach-fixing process in the color reversal process.

Further, in the present invention, when a photosensitive material containing total silver halide in an amount of 1.0 g/m 2 or less is used, desilvering properties and poor color recovery can be further improved.

Claims (2)

[Claims] Claim 1: A silver halide color reversal photographic material having at least one photosensitive image forming layer containing silver halide grains and an image forming coupler on a support is subjected to black and white development, followed by color development, and then bleach-fixed. In the color reversal processing step, at least one emulsion layer of the silver halide color reversal photographic light-sensitive material contains silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains,
A method for processing a silver halide color reversal photographic light-sensitive material, characterized in that the bleach-fixing solution used in the bleach-fixing process contains silver at a silver ion concentration of 0.05 mol/liter or more. 2. The silver halide color reversal photographic light-sensitive material has a total silver halide amount and a silver amount of 1.0 g/m2.
2. The method for processing a silver halide color reversal photographic material according to claim 1, which comprises: