JPS63165848A - Processing of silver halide color photographic sensitive material to obtain dye image having superior graininess - Google Patents

Abstract

PURPOSE:To inhibit yellow fogging during rapid processing by processing a prescribed color photographic sensitive material contg. a quickly reactive yellow coupler with a specified color developing soln. CONSTITUTION:A color photographic sensitive material having <=25mum thickness in a dry state and contg. silver halide particles contg. >=0.5mol.% silver iodide in one or more of the silver halide emulsion layers and further, contg. a quickly reactive yellow coupler having >=0.5 relative coupling rate in one or more of the emulsion layers is processed with a color developing soln. contg. >=1.5X10<-2>mol/l arom. prim. amine color developing agent within 180sec. The yellow coupler may be a compd. represented by formula I [where R14 is H, halogen or the like, each of R15-R17 is H, acylamido or the like and X is a group represented by formula II (where Z2 is a group of nonmetallic atoms capable of forming a desired ring)]. The color developing agent may be a compd. represented by formula III (where R'15 is H, halogen or the like and each of R'16 and R'17 is H, alkyl or the like.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a method for processing a silver halide color photographic light-sensitive material to obtain a dye image with excellent graininess. Regarding the method.

[Background of the invention]

In recent years, efforts have been made to reduce the size of silver halide color photographic materials.

For example, in order to make cameras more compact and more portable, the image size of film has been reduced. However, it is known that doing this will lead to deterioration of the printed image. In other words, as the screen size of color photographic materials becomes smaller, the enlargement magnification becomes thicker to make a print of the same size. This is because the graininess and sharpness of the printed image will deteriorate accordingly.

Therefore, in order to obtain good prints even when the camera is miniaturized, it is necessary to improve the graininess, resolution, and sharpness of the film.

Among these, as a technique for improving graininess, JP-A-55
62454, The Theory of the Photographic Process, by T. H. James.
fthe Photo-graphic Processes
s) Methods for increasing the number of silver halide grains as described in 4th Ed, P620-621, reaction with oxidative products of color developing agents as described in British Patent No. 2.080.640A. A method using a diffusible coupler that forms a diffusible dye with moderate dye bleed, a method of increasing the silver iodide content to 8 mol % or more as described in JP-A No. 60-128443, and others, JP-A No. 59-Sho. -191036
No. 60-3628, No. 60-128440, etc., as well as silver halide color as described in Japanese Patent Publication Nos. 49-15495, 53-7230, 57-155539, etc. Techniques for improving silver halide color photographic materials are known, such as techniques for improving the layer structure of photographic materials.

However, although graininess has certainly been improved by improving the above-mentioned photosensitive materials, it is still far from being sufficient, and in particular, the drawbacks of graininess in extremely small format photosensitive materials such as so-called disk films are This has become a bottleneck for its widespread use, and improvements are desired.

On the other hand, in order to meet the demands of consumers who want to know the results of their photographs quickly, there is a desire to speed up the processing of photographic materials, such as developing them. Report Volume 33, No. 1, Volume 63 (198
On pages 45 to 48 of 2007, there is a report by Arai et al. entitled ``Image improvement of color negative film by rapid processing.'' It was reported that by using a highly active color developing solution and high-temperature rapid processing, the amount of information in the cyan and magenta layers, which are the layers far from the support, increased by about 20% to 30% and the sharpness of the image was improved. However, it has also been shown that image graininess decreases.

For example, in order to speed up the color development process, the color developer is highly activated by heating it to a high temperature, stirring the processing tank strongly, or adding a development accelerator. However, when performing such processing, especially in the case of automatic processors, the turn roller that makes up the color developer tank is dyed with yellow dye, and this dye is transferred to the photosensitive material, resulting in yellow contamination. It has become clear that there is a malfunction that occurs.

The present invention was made to solve both of the above problems, and even if silver halide color photographic light-sensitive materials are rapidly processed,
Furthermore, as a result of various studies on photosensitive materials that can improve graininess, suppress the basically required capri, etc., improve yellow staining, and even improve image quality, the present invention has been developed. It is.

[Purpose of the invention]

The present invention is characterized by providing a method for processing a silver halide color photographic light-sensitive material that is excellent in rapid processing and capable of obtaining dye images with excellent graininess even during the rapid processing. The object of the present invention is to provide a method for processing a silver halide color photographic material in which yellow stain is improved by suppressing the occurrence of yellow fog during rapid processing.

[Structure and operation of the invention]

The above object is to provide a method for color development processing of a silver halide photographic material comprising at least one silver halide emulsion layer on a support, in which the dry film thickness of the silver halide photographic material is 25 μm or less. , at least one of the silver halide emulsion layers contains silver halide grains containing 0.5 mol % or more of silver iodide, and further a fast-reactive yellow coupler having a relative coupling rate of 0.5 or more, The silver halide photographic light-sensitive material contained in at least one silver halide emulsion layer contains an aromatic primary amine color developing agent of 1! By using a method for processing a silver halide color photographic light-sensitive material, which is characterized in that the processing time is 180 seconds or less with a color developing solution containing 1.5 x 10 -2 mol or more per color developer, ten thousand fathoms of darkness could be achieved.

Further, in a preferred embodiment of the present invention, the total amount of silver halide coated on the support is 3/10 Oct11.
It shall be 0 ■ or more.

Next, the above-mentioned photographic material to which the present invention is applied will be explained.

In the silver halide color photographic light-sensitive material used in the present invention, at least one of the silver halide emulsion layers contains 0.00% silver iodide.
It has silver halide grains containing 5 mol % or more, preferably 3 mol % or more, more preferably 5 mol % or more.

The silver halide grains containing 0.5 mol % or more of silver iodide have an average silver halide composition of 0.5 mol % or more.
There is no particular restriction as long as it contains 5 mol% or more, but
When carrying out the present invention, core-shell type silver halide grains or tabular silver halide grains are preferred.

Hereinafter, core-shell type silver halide grains and tabular silver halide grains containing 0.5 mol % or more of silver iodide, which are preferably used in the emulsion layer of the silver halide photographic light-sensitive material according to the present invention, will be explained.

Regarding the core-shell type silver halide grains preferably used as the above-mentioned silver halide grains, for example, JP-A-57
As described in detail in No. 154232, the core-shell type silver halide grains have a core silver halide composition of 0.1 to 40 mol%, more preferably 5 to 40 mol%, most preferably 5 to 40 mol% of silver iodide. 8 to 35 mol% of silver halide, the shell is composed of silver bromide, silver chloride, silver iodide, silver chlorobromide, or a mixture thereof, and the average halogenation of the core-shell type silver halide grains is The silver composition contains 0.5 mol% or more of silver iodide.

Particularly preferably, the shell is a silver halide grain containing 95 mol % or more of silver bromide as a main component.

Further, in the present invention, the core is made of monodisperse silver halide grains, and the shell has a thickness of 0. A preferable effect can be obtained by adjusting the thickness to 01 to 2.0 μm.

The core-shell type silver halide grains contain silver iodide in a total amount of 0.5 mol% or more, preferably 2 to 10 mol%, more preferably 4 to 8 mol%, In particular, silver halide grains containing silver iodide as the core are used, and a shell having the above-described specific thickness is made of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, or a mixture thereof. By coating the core with silver iodide, the high sensitivity characteristics of silver halide grains containing silver iodide are utilized, and the defects of the grains are hidden.

In the silver halide emulsion of the silver halide color photographic light-sensitive material used in the present invention, a silver halide emulsion in which the core grains are monodisperse silver halide grains is used to form the silver halide grains contained therein. By coating the core grains with a shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained.
Such a monodisperse silver halide emulsion can be used as it is with its grain size distribution, or it can be used by blending two or more monodisperse emulsions with different average grain sizes at any time after grain formation. It may be used after being mixed to obtain a predetermined gradation.

The silver halide emulsion of the silver halide color photographic light-sensitive material used in the present invention has a ratio equal to or higher than that of an emulsion obtained by coating a monodisperse core with a distribution width of 20% or less with a shell. It is desirable that the emulsion contains core-shell type silver halide grains out of all the silver halide grains contained in the emulsion. However, other silver halide grains may also be included as long as they do not impede the effects of the present invention. The other silver halide may be of a core-shell type having a silver iodide ratio outside the scope of the present invention, or may be of a type other than the core-shell type, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, the core-shell type silver halide grains contained in the emulsion are at least 65% by weight.
The above are preferably core-shell type silver halide grains of the present invention, and it is desirable that almost all of them are core-shell type silver halide grains.

The present invention includes a case where the silver halide emulsion of at least one silver halide emulsion layer is an emulsion containing tabular silver halide grains having a silver iodide content of 0.5 mol or more. That is, in the silver halide emulsion preferably used in the silver halide emulsion layer of the present invention, the silver halide grains are (1) the core-shell type silver halide grains described above, (2) tabular silver halide grains ( The tabular silver halide grains may be of the core-shell type or of other types, or () be a mixture of the above (■) and (■). too,
Included in the present invention.

The tabular silver halide grains preferably used in the present invention will be explained below.

When tabular silver halide grains are used in the silver halide color photographic light-sensitive material used in the present invention, the grain size of the grains is preferably 5 times or more the grain thickness.
The tabular silver halide grains are disclosed in JP-A-58-113930.
No. 58-113934, No. 58-127921, and No. 58-108532, etc., and the particle size is determined by the particle thickness from the viewpoint of the effect on image quality etc. The particle diameter is preferably 5 times or more, preferably 5 to 100 times, particularly preferably 7 to 30 times, more preferably 0.3 μm or more, and 0.5 to 6
μ- ones are particularly preferably used. When these tabular silver halide grains are contained in at least 50% by weight in at least one silver halide emulsion layer, the desired effects of the present invention are more preferably exhibited, and most of them are all the above-mentioned tabular silver halide grains. In some cases, particularly favorable effects can be achieved. Particularly in the present invention, it is useful when the tabular silver halide grains are core-shell type grains.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore, "thickness" in the present invention is expressed as the distance between the two parallel surfaces constituting the tabular silver halide grain. .

The halogen composition of the tabular silver halide grains is preferably silver iodobromide having a silver iodide content of 0.5 mol% or more, particularly silver iodide content of 3 to 10 mol%. Silver iodobromide is preferred.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known to those skilled in the art.

In the layer containing tabular silver halide grains, the tabular silver halide grains preferably exist in a weight ratio of 40% or more, particularly 60% or more, based on the total silver halide grains in the layer. .

The silver halide color photographic light-sensitive material to which the present invention is applied is not limited to those mentioned above, but may contain tabular silver halide grains as shown below.

For example, JP-A-58-113930 discloses a multilayer color photographic light-sensitive material having a two-layer dye-forming unit having an upper layer containing an emulsion layer containing tabular silver halide grains having an aspect ratio of 8 layers or more than 1. JP-A-58-113934 discloses a multilayer color photographic material using a silver iodobromide or silver bromide emulsion of tabular silver halide grains with an aspect ratio of 8 layers or more of 1 or more in the green-sensitive layer and the red-sensitive layer. , also published in 1988-
No. 113927 discloses a multilayer color photographic material having tabular silver halide grains in which the central region has a lower silver iodide content than the annular region and an aspect ratio of 8:1 or more. The issue has an aspect ratio of 3:1.
A silver halide photographic material containing the above-mentioned tabular silver halide grains and a specific sensitizing dye, which can also be used for color, is further disclosed in JP-A-60-111696, which has an aspect ratio of 3:1 or more. A silver halide color photographic light-sensitive material containing tabular silver halide grains mainly composed of (111) planes is disclosed, and the processing method of the present invention can also be applied to these silver halide color photographic light-sensitive materials.

It is also preferable that the emulsion used contains epitaxially bonded silver halide grains as described in JP-A-53-103725 and the like.

The silver halide color photographic material to which the present invention is applied is
The film thickness when dried is 25μ or less. The film thickness is the film thickness of the photographic constituent layer formed on the support, that is, the film thickness of the photographic constituent layer includes the silver halide emulsion layer (at least 3 layers in the case of a full-color photographic light-sensitive material), and , the total film thickness of all hydrophilic colloid layers such as an undercoat layer, a Haley silane prevention layer, an intermediate layer, a filter layer, and a protective layer, which are formed as necessary. Therefore, the dried photographic constituent layer has the above-mentioned film thickness at the time of drying. Gelatin is often used as the It aqueous colloid, and in this case, the film thickness can be referred to as the gelatin film thickness. The thickness is measured with a micrometer, and in the present invention the total thickness of the photographic constituent layers is 25 microns or less, preferably 20 microns or less, especially 18 microns or less, and most preferably 16 microns or less. From the point of view of photographic performance, a thickness of 8M or more is preferable, and the effect of the present invention is exhibited.

The silver halide color photographic light-sensitive material has a film thickness of 25 μm.
By having such photographic constituent layers, processing with good graininess is possible in a short time.

In addition, in the present invention, the development processing time is 1 as described below.
Favorable results can be obtained within 80 seconds, but by using the photographic constituent layers as described above, the processing time range can be set arbitrarily within a wide range.

In the silver halide color photographic light-sensitive material used in the present invention, at least one of the silver halide emulsion layers contains a fast-reactive yellow coupler having a relative coupling rate of 0.5 or more. The high speed yellow coupler is a yellow coupler whose relative coupling reaction rate ratio is 0.5 or more.

The coupling reaction rate of the couplers is determined by the rate of the coupling reaction between the two couplers M and N, which give different dyes that can be clearly separated from each other, in a dye image obtained by mixing the mixture, adding it to a silver halide emulsion, and color-developing it. It can be determined as a relative value by measuring the amount of pigment.

If we represent the maximum density of coupler M as (DM)wax, the color density at an intermediate stage as DM, and that of coupler N as ((lN)wax,,ON),
The reaction activity ratio RM/RN of the two-force puller is expressed by the following formula.

0M In other words, a straight line obtained by subjecting a silver halide emulsion containing a mixed coupler to various stages of exposure and color development and plotting several pairs of opening and DN on two orthogonal axes. The value of the coupling activity ratio RM/RN can be determined from the slope.

Here, by using a constant coupler N and determining the value of RM/RN for various couplers as described above, the value of the relative coupling reaction rate can be determined.

The value of the relative coupling reaction rate refers to the RM/RN value when the following coupler is used as the above coupler N.

The amount of the fast-reactive yellow coupler added is not limited, but is preferably 2X10-'' to 5X10-' mole, more preferably txio-'' to 5X10-' mole per silver mole of the blue-sensitive yellow image-forming silver halide emulsion layer. x10-1 mol.

The color developing solution used in the above color development is as follows. It was developed at 38°C for 3 minutes and 30 seconds.

<Color developer composition> Benzyl alcohol 15M1 ethylene glycol 15 ad Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g3
-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate
5.5g Fluorescent brightener (4,4'-diaminostilbenzyl sulfonic acid mm form) 1.0g
Potassium hydroxide 2.0g Add water to bring the total amount to 11, and adjust to pt+ 10.20.

The above yellow coupler can have any structure as long as the above relative coupling reaction rate value is 0.5 or more, but a coupler represented by the following general formula (A) can be preferably used.

General formula (A) ■ In the formula, R1 represents an alkyl group or an aryl group, and R2
represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction process.
For example, a phenyl group), but preferably an alkyl group (
L-butyl group), R2 represents an aryl group (preferably phenyl group), and these Rls R
The alkyl group and oryl group represented by t include those having a substituent, and the oryl group of R2 is preferably substituted with a halogen atom, an alkyl group, etc. A group represented by formula (B) or (C) is preferred,
Among general formulas (B), groups represented by general formula (B') are particularly preferred.

General formula (B) 1,・′°″−”′・・.

Unipolar 'Z1 In the formula, Z represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General Formula (C) OR++ In the formula, R11 represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

Represents a group of nonmetallic atoms that can be formed.

A preferred yellow coupler in the above general formula (A) is represented by the following general formula (A').

General Formula (A') In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable.

Also RIS, RI6 and R1? each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamido group, a ureido group, or an amino group. , RIS and R4 are each hydrogen atoms, and R1? is preferably an alkoxycarbonyl group, an acylamide group or an alkylsulfonamide group.

In addition, X represents a group having the same meaning as that shown in the above general formula (A), preferably the above general formula (B) or (C), (
More preferred among B) are groups represented by the above general formula (B').

The yellow coupler may be added to any silver halide emulsion layer, but is preferably added to the blue-sensitive silver halide emulsion layer. The amount added is 2X10-' per mole of silver.
˜2 mol is preferred, more preferably IXl0−”˜
It is 1 mole.

Below, the specific general formula of the yellow coupler according to the present invention (
A-1) General formula (A-2) General formula (A-33 p -Formula (A-5) (Y-23) (RM/RN-1,1) (Y-24) (Rh/RN 凋4.3) (Y-25) (Y-26) Next, the development processing time of the present invention will be described.

In the present invention, the time for processing the silver halide color photographic light-sensitive material with the color developing solution is 180 seconds or less. That is, in the present invention, the time for processing the silver halide color photographic light-sensitive material with the color developer is 180 seconds or less, preferably 150 seconds or less, more preferably 20 to 150 seconds, and even more preferably 30 to 120 seconds. More preferably 40
~100 seconds.

In the present invention, by processing the above-mentioned silver halide color photographic light-sensitive material in the above-mentioned short time, surprisingly,
The graininess of the dye image obtained can be improved.

Furthermore, in the method for processing a silver halide color photographic light-sensitive material of the present invention, the color developing solution is a color developing solution containing an aromatic primary amine color developing agent in an amount of 1.5 Xl0-'' mol or more per 11 of the processing solution. Yes, more preferably 2.0X1
0-” mole or more, more preferably 2.5×10-
A color developing solution containing the above-mentioned developing agent in an amount of 1 g mole or more is preferred.

By activating the photographic light-sensitive material by increasing the concentration of the color developing agent in this manner, it is possible to obtain an image with excellent sharpness and improved graininess through short-time processing as described above.

This is particularly noticeable in magenta dye images.

Hereinafter, the color developing agent of the color developer that can be preferably used in the present invention will be explained.

The aromatic primary amine color developing agent solution used in the preferred color developing solution includes known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, and 5-amino-2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

In the present invention, the aromatic primary amine color developer that is particularly useful in the present invention is because it can better achieve the desired effect and improve the crystal precipitation on the inner wall of the color developer layer of an automatic processor. It is an aromatic primary amine color developer having an amino group having at least one water-soluble group, and particularly preferably a compound represented by the following general formula (1).

General formula (1) In the formula, RIS' represents a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group is a linear or branched carbon atom having 1 carbon number.
~5 alkyl group, which may have a substituent,
RI6' and R1,' represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable, and R1, ' and at least one of R1,' is a
It is a ruyl group or ÷(CH TO+−rR+ s′).

This alkyl group may further have a substituent.

In addition, R,,' represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent an integer of 1 to 5.

Next, compounds represented by the above general formula (1) will be listed, but the invention is not limited thereto.

<Exemplary compounds> NH2 Ht Ht N.H.

N.H.

N1(z N.H.

Hz HI NH2 NH1 N.H.

These p-phenylenediamine derivatives represented by general formula (1) can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, and oxalic acid. Salts, benzene disulfonates, etc. can be used.

In the present invention, among the p-phenylenediamine derivatives represented by the above general formula (1), RI6' and/or R6,' is -F(CH!+T-0-)rR18'(p,
When q, R, and ll' have the same meanings as above, the effects of the present invention are particularly well achieved.

Preferred compounds for use in the color developer used in the present invention include sulfites, hydroxylamine, and development inhibitors. Examples of the sulfite include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc., and it is preferably used in a range of 0.1 to 40 g/l, more preferably in a range of 0.5 to 10 g/l. It is to be used in The above hydroxylamine is hydrochloride,
It is used as a countersalt for sulfates, etc., and is preferably used in the range of 0.1 to 40 g/l, more preferably 0.5 g/l.
~10 g/I! , used within the range of . Furthermore, the above-mentioned development inhibitors include halides such as sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc., as well as organic inhibitors, and the amount of these added is from o, oos to 20 g.
It is preferably used in the range of 0.01 to 5 g/2, more preferably 0.01 to 5 g/2.

Examples of the organic inhibitor preferably used in carrying out the present invention include nitrogen-containing heterocyclic compounds, compounds containing a mercapto group, aromatic compounds, onium compounds, and compounds having an iodine atom in a substituent. The following exemplified compounds are concrete examples of these compounds. However, the compounds that can be used are not limited to the following compounds.

<Exemplary compound> C00C3H? (Z-5) CHs CHzCOOH Furthermore, when carrying out the present invention, patent application No. 61-12781
The general formula (R
The organic inhibitors represented by -1) to (R-XIII) can be used, and the effects of the present invention can be more effectively achieved by using the organic inhibitors in combination with the organic inhibitors described above in the present invention.

Further, the organic inhibitor in the present invention is as described above, but more specifically, it is described in the above-mentioned Japanese Patent Application No. 61-127.
(Z-1) on pages 101 to 113 of the specification of No. 81
(Z-3), (Z-6), (Z-8) to (Z-13),
(Z-15) ~ (Z-17), (Z-19), (
Z-22) ~(Z-25), (Z-29), (Z
-31) ~(Z-38), (Z-40), (Z-
41), (Z-43) ~ (Z-64) and (Z-6
6) to (Z-73).

Additives other than those mentioned above that may be added to the color developing solution include anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like.

The color developing solution of the present invention has a pH of 9 or higher, particularly a pH of 9 to 13.
It is preferably used in

In addition, the processing temperature of the color developer is preferably 38°C or higher, particularly preferably in the range of 40°C to 70°C, and most preferably 43°C. It is in the range of C to 60°C.

In addition to the above, there are no particular limitations on the processing method for the photographic material of the present invention, and any processing method can be applied.

When carrying out the present invention, a process of treating with a treatment liquid having bleaching ability can be used. Processing with a processing solution having bleaching ability means processing with a bleaching solution or a single-bath bleach-fix solution, but for better bleaching,
- This is the case when bath bleach-fixing treatment is performed.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. The following are representative examples of the above aminopolycarboxylic acids.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetraprobionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleach solution and bleach-fix solution used in the present invention can be used at a pH of 0.2 to 9.5, preferably at a pH of 4.0 or higher, more preferably at a pH of 5.0 or higher. Processing temperature is 20℃ ~
It is used at 80°C, preferably at 40°C or higher.

The bleaching solution used in the present invention can contain various additives together with the bleaching agent (preferably an organic acid ferric complex salt) as described above.

Furthermore, substances known to be added to normal bleaching solutions, such as pH buffers, can be added as appropriate.

The silver halide fixing agent contained in the bleach-fixing solution used in the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in ordinary fixing processing.

These fixing agents are 5g/1 or more, preferably 50g/1
It can be used in an amount that can dissolve the above, more preferably 70 g/1 or more.

Incidentally, the bleach-fix solution used in the present invention may contain a pH buffer agent alone or in combination of two or more, as in the case of the bleach solution. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Further, preservatives, stabilizers, solubilizers, anti-staining agents, other additives, and organic solvents can be included as appropriate.

In the processing method using a color developing solution in the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. A fixing treatment may be performed, or a processing solution prior to bleaching or bleach-fixing may be used in a prebath containing a bleach accelerator.

Processing temperatures for various processing steps other than color development of the silver halide color photographic light-sensitive material to which the present invention is applied, such as bleach-fixing (or bleaching, fixing), and further washing with water or stabilization as an alternative to washing as necessary. For about 20℃～8
The temperature is preferably 0°C, more preferably 40°C or higher.

In the present invention, JP-A-58-14834, JP-A-58-14834;
-105145, 58-134634 and 58
-18631 and Japanese Patent Application No. 58-2709 and No. 5
It is preferable to carry out a stabilization treatment as an alternative to water washing as shown in No. 9-89288.

Couplers other than the above-mentioned yellow couplers used in carrying out the present invention are preferably cyan couplers such as phenolic compounds and naphthol compounds, such as U.S. Pat. Nos. 2.369.929 and 2.434.
．． No. 272, No. 2,474.293, No. 2.89
No. 5.826, No. 3.253,924, No. 3.0
No. 34,892, No. 3.311.476, No. 3.
386.301, 3,419.390, 3
, No. 458.315, No. 3.476.563, No. 3.531.383, etc., and the methods described in the same publications may be applied to the synthesis of these compounds. I can do it.

Examples of magenta couplers include pyrazolone,
Compounds such as pyrazolotriazole, pyrazolinobenzimidazole, and indacylon are used. As a pyrazolone magenta coupler, U.S. Patent No. 2.6
No. 00,788, No. 3.062゜653, No. 3.
No. 127.269, No. 3.311.476, No. 3
．． 419.391, 3.519.429, 3,558, 318, 3.684.514, 3.888.680, JP-A-49-29639,
No. 49-111631, No. 49-129538, No. 50-13041, Special Publication No. 53-47167, No. 5
The compounds described in US Pat. , No. 801, 171, No. 2゜983, 6
No. 08, No. 3.005,712, No. 3,684.
No. 514, British Patent No. 937.621, JP-A-49-
Examples include compounds described in No. 123625 and No. 49-31448.

Furthermore, a colored magenta coupler of the type in which the dye flows out into the processing solution by the reaction of the oxidized product of the developing agent as described in US Pat. No. 3,419,391 can also be used.

Yellow couplers that can be used in combination with the yellow coupler of the present invention include conventionally used open-chain ketomethylene compounds, benzoylacetanilide type yellow couplers, and pivaloylacetanilide type yellow couplers, which are generally widely used. Furthermore, a two-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction is preferably used. Examples of these compounds include, for example, U.S. Pat. No. 2,875.057 and U.S. Pat.
No. 3,664.841, No. 3.408.19
No. 4, No. 3,277.155, No. 3,447.9
No. 28, No. 3.415.652, Special Publication No. 49-13
No. 576, JP-A-48-29432, JP-A No. 4B-688
No. 34, No. 49-10736, No. 49-122335
No. 50-28834, No. 50-132926, etc., and can be synthesized according to these publications.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.0 per mole of silver in the light-sensitive silver halide emulsion layer.
It is 5 to 2.0 moles.

Couplers such as colored magenta or cyan dye-forming couplers, polymer couplers, etc. may be used in combination in the silver halide emulsion layer and other photographic constituent layers. Regarding polymer couplers, please refer to Japanese Patent Application No. 1987-193611 filed by the present applicant.
172151 can be referred to.

The method of adding the above coupler to the photographic constituent layers of the silver halide color photographic light-sensitive material used in the present invention is the same as before, and the amount of the above coupler added is not limited; ~5 mol is preferred, and more preferably 1X10-'' to 5X1O-'.

The silver halide color photographic material applicable to the present invention may contain various other photographic additives.
For example, antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure Magazine No. 17643,
Color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

Examples of the support for the silver halide color photographic material to which the present invention is applied include glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. The support is appropriately selected depending on the intended use of the photosensitive material.

In the photosensitive material to which the present invention is applied, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, an anti-halation layer, etc. They can be used in appropriate combinations as layers. Hydrophilic colloids that can be used to form the emulsion layer as described above can be similarly used as binders in these constituent layers, and hydrophilic colloids that can be contained in the emulsion layers as described above can also be used as binders. Various photographic additives can be included.

The processing method of the present invention can be applied to any silver halide color photographic material, such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, and color reversal film for TV.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Furthermore, in all the examples below, the amount added in the silver halide color photographic light-sensitive material is shown per 1 y, and the amounts of silver halide and colloidal silver are shown in terms of silver.

Example 1 A silver halide emulsion shown in Table 1 was produced as a spherical emulsion by a conventional double jet method.

The following layers were sequentially coated on a cellulose triacetate support to prepare a multilayer color photographic material sample.

1st layer: Haley anti-silon layer (HC layer) Haley anti-cilon layer consisting of 0.15 g of black colloidal silver and 1.2 g of gelatin.

2nd layer: Undercoat layer (10 layers) Subbing layer consisting of 1.9 g of gelatin.

3rd layer: Red-sensitive silver halide emulsion layer (R layer) Each of the silver halide emulsions shown in Table 1 was color-sensitized to red sensitivity, and the following cyan coupler (0.21 mol 1 mol Ag) ( C
-1) and 0.007 mol 1 mol Ag of the following colored cyan coupler (CC-1) were dissolved in tricresyl phosphate (hereinafter referred to as TCP), and an inhibitor was dissolved in methanol to prepare gelatin. A red-sensitive silver halide emulsion layer containing a dispersion emulsified and dispersed in an aqueous solution.

4th N: Intermediate layer (2G layer) 0.14 g of 2.5-di-t-butylhydroquinone,
0.07 dibutyl phthalate (hereinafter referred to as DBP).

5th layer: Green-sensitive silver halide emulsion layer (G layer) Each of the silver halide emulsions shown in Table 1 was color-sensitized to green sensitivity, and the following magenta coupler (0.15 mol 1 mol Ag) (
A green-sensitive silver halide containing a dispersion obtained by emulsifying and dispersing M-1) and TCP in which 0.016 mol 1 mol Ag of the following colored magenta coupler (CM=1) is dissolved in an aqueous solution containing gelatin. Emulsion layer.

Layer 6: Yellow filter layer containing 0.3 g yellow colloidal silver, 0.12 g DBP in which 0.2 g antifouling agent (2,5-di-tert-octylhydroquinone) and 2.1 g gelatin are dissolved. .

7th layer: Low-speed blue-sensitive silver halide emulsion layer (B layer) Each of the silver halide emulsions shown in Table 1 was color-sensitized to blue sensitivity, and the following table contains 0.28 mol 1 mol Ag. A blue-sensitive silver halide emulsion layer containing a dispersion in which various exemplary yellow couplers or comparative yellow couplers shown in -1 are dissolved in TCP and emulsified and dispersed in an aqueous solution containing gelatin.

8th layer: High-speed blue-sensitive silver halide emulsion (B layer) Same as the 7th layer, except that the silver halide grain size was slightly larger.

9th layer: Protective layer (3Gji) Protective layer containing 0.6 g of gelatin.

In addition to the above, each layer contained a gelatin hardening agent (1,2-bisvinylsulfonylethane and 2,4-dichloro-6-hydroxy-5-)riazine sodium salt) and a surfactant.

The amount of silver coated was 50 .mu./100 d.

The couplers used in each layer are as shown below.

Cyan coupler (C-1 2-(α, α, β, β, γ, γ, δ, δ-octafluorohexanamide)-5-(2-(2゜4-di-t-amylphenoxy)hexanamide ] Phenol colored cyan coupler (cc-1) 1-hydroxy-4-[4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-(δ-(2,4 -di-t-amylphenoxy)butyl)-2-naphthamide disodium salt magenta coupler (M-1) 1-(2,4,6-drichlorophenyl)-4-(l
-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone yellow coupler Comparative coupler In the above formulation, silver halide having the composition shown in Table 1 was used. Samples Nα1 to Nα19 were prepared by varying the coating amounts of the third layer, fifth layer, seventh layer, and eighth layer, and by varying the amount of gelatin hardener in the ninth layer. Next, the film thickness was measured and recorded in Table-1.

Each sample was exposed to light (16 CMS) through a separate wedge and processed through the processing steps described below to obtain a dye image.

Processing process Color development Time and temperature source shown in Table 2 White
4 minutes (38°C) Fixation 3 minutes
(30-38°C) Wash with water 1 minute
(20-33℃) Stabilization 1 minute (20-33℃)
°C) Drying The composition of the treatment liquid used in each treatment step is as follows.

<Color developer> Sulfate of the above-mentioned exemplary compound (E-2) Listed in Table 1 Anhydrous sodium sulfite 3.0 g Hydroxylamine/2 sulfate 1.0 g Anhydrous potassium carbonate 30.0 g Sodium bromide
1.2g nitrilotriacetic acid 3
Sodium salt (l hydrate) 2.0 g Potassium hydroxide 1.0 g Inhibitor (Z-2) 0.5 g Add water to make 12, pH = 10 with 50% KOH and HzsOa
．． Prepare to 1.

<Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt 50g Ammonium bromide 150.0g Glacial acetic acid 10. Omj! Add water to make up to 1 liter, and adjust to pH=6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate 180g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 12,
Adjust pH=7.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5m
J2 Conidax (manufactured by Konishiroku Photo Industry) 7.5m
f Add water to make 11.

Table 2 shows the graininess (RMS) of the obtained magenta dye.

Immediately after the treatment, the minimum density of the unexposed area of the sample was measured using an optical densitometer PDA-65A (manufactured by Konishi Roku Photo Industry ■) with blue light, and after storing it at 60°C and 60RH% for one week, it was measured again. The difference in concentration that increased due to storage was measured, and the rate of increase in yellow stain was determined. The results are shown in Table-3.

Furthermore, Table 4 shows the results of measuring the minimum yellow density on the same day for each sample similarly exposed to blue light.

Furthermore, the RMS value representing graininess is based on this book, as can be understood from Table 29 Table 3, which shows the variation in density value that occurs when the minimum density + 1.0 density is scanned with a microdensitometer with an aperture scanning area of 250 μM. When the invention is used, favorable results can be obtained in both graininess and yellow stain.

Furthermore, as is clear from Table 4, when the present invention is used,
The problem of yellow layer fogging is also solved.

That is, the minimum yellow density of the sample using the present invention is 0°80
On the other hand, many of the other samples had a value of 0.80 or less, which clearly shows the effect of the present invention.

Therefore, the effects of the present invention can be achieved only when the iodine content of the silver halide, the dry film thickness of the light-sensitive material, the concentration of the color developing agent, and the yellow dye-forming coupler are all within the scope of the present invention. All of the graininess, yellow stain during storage over time, and yellow tint in unexposed areas are improved, and the above improvements will not occur even if any of the above conditions are absent.

Example 2 Silver iodobromide emulsions shown in Table 5 were produced by the following production method. That is, A-C was manufactured by the usual double jet method. For D-, a core/shell type monodispersed emulsion was produced by the functional addition method. L produced a tabular silver halide emulsion by the double gent method while controlling pHlpAg.

Next, photosensitive material samples Nα20 to Nα43 having film thicknesses shown in Table 5 were prepared using the emulsions A-L above and using the same photosensitive material preparation method as in Example 1.

The same experiment as in Example 1 was conducted for each sample, and the obtained data on graininess (RMS value) and minimum yellow density value yellow stain are shown in Table 6.

As is clear from Table 6, the present invention is preferable in both graininess and yellow stain.

Example 3 Yellow coupler (Y-2), which is an example of the yellow coupler added to the sample for 3B in Example 2, (
Y-10), (Y-12), (Y-16), (Y-
20).

When (Y-23) and (Y-26) were replaced with the same tests as in Example 2, almost the same results as in Example 2 were obtained, and sample Nα38 had better results than sample Nα22. Met. From these facts, it can be seen that the effects of the present invention can be effectively achieved by using the yellow coupler according to the present invention.

Example 4 The amount of exemplified compound (E-2) used as a color developing agent in Example 1 was changed as shown in Table-7, and
Processing was carried out at a development temperature of 7. The rest was the same as in the example. However, the photosensitive material sample Na22 used as a sample,
3B was produced in Example 2. (See Table-6).

In Table 7, it can be seen that the products of the present invention surrounded by thick lines give preferable results. Also, the concentration of the developing agent is 1.5×10
-"Mole of 72 or more shows preferable results.

Similarly, the color developing agent was added to Exemplary Compound (E-1).
, (E-4), (E-5), (E-7) and the following (D-
1) and (D-2) were similarly carried out in place of the sulfates, and as a result, color developing agents (E-1) and (E-4) according to the present invention were obtained.
, (E-5) and (E-7), please refer to Table 7 below.
Almost the same result is obtained, but (D-1) and (D-2)
The yellow minimum density increased by 0.03 to 0.05, respectively. Furthermore, when we put these color developing solutions into an automatic processor and experimented, we found that in the case of the color developers using (D-1) and (D-2), (D-1) and (D-
Although crystals of 2) were precipitated, almost no crystal precipitation was observed in the case of using the color developing agent according to the present invention.

Table 7 Developing time 60 seconds (D-1) (D-2) Example 5 Samples were prepared using the emulsion G of Example 2 and using the preparation method of Example 1 with the amount of coated silver changed as follows. did.

That is, samples were prepared in which the amount of silver coated was changed by changing the amount of silver coated in the 3rd, 5th, 7th and 8th layers. Furthermore, as shown in Table 8, the film thickness and the amount of coated silver were adjusted.

For each, use a color developing solution with a solution temperature of 45°C.
After processing for seconds, the RMS value and minimum yellow density of each sample after development were measured, and the results are shown in Table 8. From the results in Table 8, the amount of coated silver is preferably 30 d/100 d or more;
It can be seen that the range is more preferably 35 to 150 .mu./100 cd, and even more preferably 40 to 100 .mu./100 cd.

Table 8 Example 6 For photosensitive material sample Nα38 of Example 2, the RMS value and minimum yellow density value were measured in the same manner as in the previous example using the color developing solution of Example 1 to which an inhibitor was added. Using a color developing agent (E-2), the concentration was 2, OXl0-”mol/
The following samples were processed at a temperature of 50° C. and a color development time of 60 seconds. That is, in the production of sample 22.38 of the photosensitive material used in Example 1, samples were prepared by changing the inhibitor (Z-2) to the inhibitor shown in Table 9. Table-9
From the results shown in , it can be seen that addition of the organic inhibitor according to the present invention is more effective.

Table 9 [Effects of the Invention] As described above, the present invention has excellent rapid processing properties and can obtain dye images with excellent graininess even under rapid processing, as well as improve other photographic properties, especially yellow fog. It can be said that this is a method for processing silver halide color photographic materials that has been improved in these points.

Claims (1)

[Claims] 1. In a method of color development processing of a silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support, the dry film thickness of the silver halide light-sensitive material is 25 μm or less; At least one of the silver halide emulsion layers contains silver halide grains containing 0.5 mol % or more of silver iodide, and further has a relative coupling rate of 0.5 mol % or more.
A silver halide photographic light-sensitive material containing 5 or more fast-reactive yellow couplers in at least one layer of the silver halide emulsion layer is prepared by using an aromatic primary amine color developing agent of 1.5 x 10 per liter. A method for processing a silver halide color photographic light-sensitive material, characterized in that it is processed in a processing time of 180 seconds or less with a color developing solution containing ^-^2 mol or more.