JPS62157030A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a graininess of the titled material by incorporating a compd. capable of releasing an inhibitor to the titled material, and by processing a development for a prescribed development processing period so as to obtain the prescribed amount of a developed silver. CONSTITUTION:The titled method lies in incorporating the compd. capable of releasing the inhibitor to the titled material comprising a core/shell type silver halide particle contg. >=3.0mol% silver iodide, and has <=120sec the color development processing periods, and lies in effecting a color development processing of the titled material so as to be <=0.5, preferably 0.1-0.3 a value of ratio of a silver amount of the developing silver in the max. concn. part a total amount of silver. The color development is effected for <=120sec, preferably <=120sec at >=43 deg.C, further preferably <=90sec at >=43 deg.C. As the compd. capable of releasing the inhibitor, the compd. capable of releasing or dissolving the inhibitor which forms a silver salt having <=1X10<9> solubility product of the silver ion and the prescribed compd. in the development process may be preferable.

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, to a method for processing a silver halide color photographic light-sensitive material in which graininess is improved. This relates to a processing method.

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. For example.

Silver halide photographic light-sensitive materials for color negatives are generally coated in the order of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the exposed side. A bleachable yellow filter layer is provided between the sensitive silver halide emulsion layer and the green sensitive silver halide emulsion layer to absorb blue light transmitted through the blue sensitive silver halide emulsion layer. Furthermore, each emulsion layer is provided with another intermediate layer for various special purposes, and a protective layer is provided as the outermost layer. It is also known that each of these light-sensitive silver halide emulsion layers may be provided in a different arrangement than the above, and each silver halide emulsion layer may be provided in a substantially rotating wavelength range for each color of light. It is also known to use a photosensitive silver halide emulsion layer consisting of two or more layers having photosensitivity and having different sensitivities. In these silver halide color photographic materials, exposed silver halide grains are developed using an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocoupler couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocouplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl magenta coupler and an acylacetamide yellow coupler are used.

These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. The present invention is suitable as a method for processing a silver halide color photographic light-sensitive material in which a coupler is previously non-diffused and contained in a silver halide emulsion layer.

[Background of the Invention] In recent years, in order to downsize cameras and increase their portability, the image size of film has been reduced, and it is well known that doing so causes deterioration of printed images. That is, as the screen size of the color photosensitive material v1 becomes smaller, the enlargement magnification increases to produce prints of the same size, and the graininess and sharpness of the printed images deteriorate accordingly. Therefore, in order to obtain good prints even when cameras are downsized, it is necessary to improve the graininess, resolution, and sharpness of the film.

Among these, as a technique for improving graininess, JP-A-55
Method using fast-reacting couplers described in No.-62454, T, tl, I,)mes "The Theory
of the PboLographic Process
ss" 4th Ed-P620-621, and the method of increasing the number of silver halide grains by reacting with the oxidation product of a color developing agent as described in British Patent No. 2,080,640A. A method using a non-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. -191
No. 036, No. 60-3628, No. 60-128440
As described in No. 1, etc., improvement techniques based mostly on photosensitive materials have been known in the past.

On the other hand, core-shell emulsions have recently been developed as silver halide emulsions that are highly sensitive, have fine grains, and utilize silver effectively to meet the requirements for resource conservation. One of them is a monodisperse core-shell emulsion which is produced by using a preceding silver halide emulsion as a crystal nucleus, successively layering subsequent precipitates thereon, and intentionally controlling the composition or environment of each precipitate.

These core-shell emulsions, including core-shell type high-sensitivity emulsions whose cores contain silver iodide, have been found to have extremely favorable high sensitivity and other photographic properties.

In particular, as a result of studies conducted by the present inventors, the graininess of color photosensitive materials containing core-shell silver halide grains containing 3.0 mol% or more of silver iodide is not sufficient. This is a technical issue that should be greatly improved.

JP-A-58-113930 and JP-A-58-1139 also have high sensitivity as emulsions for improving the conventional drawbacks.
No. 34, No. 5B-127921 and No. 5B-1085
Techniques using tabular silver halide grains such as those described in No. 32 have been developed.

With this tabular grain technology, even if the number of photons captured by silver halide grains increases, the amount of silver used does not increase and image quality does not deteriorate. However, because of these tabular grains, color photosensitive materials containing tabular silver halide grains containing 3.0 mol% or more of silver iodide do not have sufficient graininess, and in particular, small format The graininess of silver halide color photographic materials is a performance that should be improved, especially in extremely small-format silver halide color photographic materials such as so-called disk films, which is a bottleneck to their widespread use.

The technique for improving graininess is disclosed in Japanese Patent Publication No. 15495/1983,
This is done by devising the layer structure of silver halide color photographic light-sensitive materials as described in JP-A-53-7230 and JP-A-57-155539. There are no known techniques to improve sex.

A technical object of the present invention is to provide a processing method for improving the graininess of a high-sensitivity fine-grain type high-sensitivity silver halide color photographic light-sensitive material that can achieve both silver resource protection and high sensitivity.

[Means for Solving the Problem] As a result of intensive research, the present inventors have found that core-shell silver halide grains containing 3.0 mol% or more of silver iodide (hereinafter referred to as core-shell silver halide grains of the present invention) and/or Tabular silver halide grains containing 3.0 mol% or more of silver iodide (hereinafter referred to as
A compound (hereinafter referred to as tabular silver halide grains of the present invention) that releases an inhibitor or inhibitor breaker during development processing that forms a silver salt having a solubility product with silver ions of I x 1G-' or less After imagewise exposure of a silver halide color photographic light-sensitive material containing a silver halide color photographic material (referred to as the inhibitor-releasing compound of the present invention), it is processed for 120 seconds or less using a color developing solution containing an aromatic primary amine color developing agent. In addition, by carrying out color development processing so that the value of [Developed silver amount in the maximum density area 1/[Total silver amount] is 0.5 or less, the above-mentioned technical section 8 (
purpose) was found to be solved.

A preferred embodiment of the present invention is that (1) the inhibitor-releasing compound of the present invention is a DIR compound, (2) the color development processing temperature is 4.
3°C or higher; ■The core-shell emulsion used in the present invention has a core consisting essentially of silver halide containing silver iodide, and silver bromide, silver chloride, silver chlorobromide, or silver iodobromide. or a mixture thereof and has a thickness of 0. O
It contains silver halide grains consisting of a shell of 1 to 0.5 g+a.

As a result of our study on processing methods to solve the above technical problems, we found that the core-shell silver halide grains and/or
Alternatively, in the method of processing a silver halide color photographic material containing tabular silver halide grains of the present invention, the silver halide color photographic material contains an inhibitor-releasing compound and the color development processing time is 120 or more. The value of [developed silver amount in maximum density area]/[total silver amount] is 0.
It has been found that the graininess of a silver halide color photographic light-sensitive material can be improved by color development treatment to give an O of 0.5 or less, more preferably O11 to 0.3. It is particularly advantageous for use in small format color photosensitive materials such as disk films.

The amount of developed silver in the maximum density area is the cornerstone of photographic engineering.
16CMS (Candela Meter,
This is the amount of developed silver when color development is performed by applying an exposure amount of 2 seconds).

dxSxT Note that CMS = □ Cd: Light intensity of light bulb (candela) S: M light time (seconds) T: Transmittance of filter M: Distance! (m) At least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention contains core-shell silver halide grains of the present invention and/or tabular silver halide grains of the present invention. do it.

The color development process is carried out for 120 seconds or less, preferably at 43° C. or more, for 120 seconds or less, most preferably at 43° C.
It may be processed for 90 seconds or more at a temperature of 120°C or higher.
When the treatment is carried out for more than a second, no improvement in graininess is observed, and in particular, the treatment time is more important than the temperature.

The light-sensitive material used in the processing of the present invention contains core-shell silver halide grains and/or tabular silver halide grains in at least one light-sensitive emulsion layer. There are no particular restrictions on the core-shell silver halide grains used, but in the case of high-sensitivity color negative light-sensitive materials, the following are particularly preferably used.

That is, 1. A photosensitive material to which the present invention is advantageously applied contains 3 silver iodides.
．． This is a photosensitive material having an emulsion layer containing core-shell type grains containing 0 mol % or more and having a halogen composition consisting essentially of silver iodobromide.

The core-shell emulsion preferably used in the present invention is described in detail in, for example, JP-A-57-154232, and the preferred core-shell silver halide grains have a core silver halide composition of -0.1 to 40% silver iodide. mole%,
More preferably 5 to 40 mol%, most preferably 8 to 3
The shell is composed of silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or a mixture thereof.

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

Further, in the present invention, preferable effects can be obtained by forming the core as a monodisperse silver halide grain and setting the shell thickness to 0.01 to 2.0 mm.

The silver halide color photographic light-sensitive material preferably used in the processing of the present invention contains silver iodide in a total amount of 3.0 mol% or more, preferably 3 to 40 mol%, more preferably 4 to 15 mol%. , more preferably 5 to 10 mol%
Silver halide grains containing silver bromide, silver chloride, silver chlorobromide, silver iodobromide, or a mixture thereof, in particular using silver halide grains containing silver iodide as a core. By hiding the core using a shell having the specific thickness, the ability of silver halide grains containing silver iodide to increase sensitivity can be utilized, and the disadvantageous qualities of the grains can be hidden. . More specifically, the core is made of silver halide containing silver iodide, and the thickness range necessary to effectively exhibit only the desirable properties of this core and to shield undesirable behavior is strictly regulated. The purpose is to provide a shell to the core. The method of covering the core with a shell that has the minimum necessary absolute thickness to effectively utilize its qualities has changed the purpose of covering the core,
It is extremely advantageous that by changing the material of the shell, it can be used for purposes such as improving storage stability or adsorbing sensitizing dyes inside cars.

Preferably, the silver iodide content in the silver halide grains (core) serving as the host is in the range from 0.1 to 20 mol% solid solution to mixed crystal, more preferably 0.5 to 10 mol%.
It is mole%. The silver iodide content may be distributed unevenly or uniformly in the core, and preferably, low silver iodide is unevenly distributed in the center.

The silver halide emulsion having core-shell silver halide grains of the present invention can be produced by coating a core of silver halide grains contained in a monodisperse emulsion with a shell. In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 10 mol % or less.

In order to form the core into monodisperse silver halide grains, grains of a desired size can be obtained by the tuplechet method while keeping the pAg constant. Furthermore, the production of highly monodisperse silver halide emulsions is described in JP-A-54-48521.
You can apply the method described. A preferred embodiment of the method is a method in which an aqueous potassium-gelatin solution and an aqueous ammonium silver nitrate solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. It is to manufacture. At this time, the time function of the addition rate, pll, I
) By appropriately selecting Ag, temperature, etc., a highly monodisperse silver halide emulsion can be obtained.

Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From this, if we define the relational expression x too = width of distribution (%) by the average particle size, the width of IIj that can meaningfully control the absolute thickness of the coating is 20%.
It is preferable to have the following monodispersity, more preferably 10% or less.

Next, the thickness of the shell that covers the core is such that it does not hide the desirable qualities of the core, and on the contrary, it is thick enough to hide the unfavorable qualities of the core. That is, it is preferable that the thickness be within a narrow range defined by such upper and lower limits. Such a shell can be formed by depositing a soluble halide solution and a soluble silver solution onto a monodisperse core by a double jet method.

On the other hand, if the thickness of the shell is too thin, some parts of the core containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the chemical sensitization effect, rapid development, fixing properties, etc. will be lost. . Preferably, the thickness limit is 0.01 gm.

Further confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0. O1~0.4gm
, and the most preferred thickness is o,ot -0,2lI
It is.

It is the highly monodisperse core that develops enough silver filaments to improve the optical density, the ability of the core to increase sensitivity to be utilized to produce a sensitizing effect, and the rapid development and regularity to occur. This is due to the synergistic effect between the shell whose thickness is regulated as described above and the silver halide composition of the core and shell. Silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used as the silveride. Among them, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of compatibility with the core, performance stability, and storage stability.

The light-sensitive material of the present invention comprises the light-sensitive material described below. That is, at least one of the light-sensitive silver halide emulsion layers contains an inner core consisting essentially of silver bromide and/or silver iodobromide; Contains negative-working silver halide grains having a plurality of outer shells provided outside an inner core and consisting essentially of silver bromide and/or silver iodobromide, and the outermost shell of the silver halide grains. The iodine content of the shell is 10 mol% or less, and the iodine plateau shell (hereinafter referred to as a high iodine shell) has an iodine content of 6 mol% or more higher than that of the outermost shell, and is located inside the outermost shell. An intermediate shell is provided between the outermost shell and the high iodine shell, and has an iodine content between these two levels, and the iodine content of the intermediate shell is 3 times higher than that of the outermost shell. The iodine content of the high iodine shell is 3 mol% or more higher than that of the intermediate shell.

The above "consisting essentially of" means that it may contain silver halides other than silver iodobromide, such as silver chloride; specifically, in the case of silver chloride, the ratio is 1 mol. % or less.

The features of this photosensitive material are the following (1) to (4).

(1) An emulsion containing core/shell type silver halide grains having a high iodine shell inside is used.

(2) An intermediate shell having an intermediate iodine content is provided between the high iodine shell and the surface low iodine shell (outermost shell layer).

(3) The iodine content of the high iodine shell is 6 to 40 mol%, which is 6 mol% or more higher than that of the outermost shell layer.

(4) The difference in iodine content between the intermediate shell and the outermost shell or high iodine shell is 3 mol% or more.

Note that the three-layer core-shell emulsion described in JP-A-60-35726 can also be used in the present invention.

Also, JP-A-59-177535 and JP-A No. 60-86659
The core-shell emulsion described in No. 60-138538 can also be used in the present invention.

The photosensitive silver halide emulsion used in the present invention may be doped with various metal salts or metal complex salts during the formation of silver halide precipitates of the core and shell, during grain growth, or after the completion of growth. For example, metal salts or complex salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, and combinations thereof can be applied.

In addition, excess halogen compounds or by-products or unnecessary salts and compounds such as nitrates and ammonium may be removed during the preparation of the emulsion of the present invention. ,
A dialysis method, a coagulation precipitation method, etc. can be used as appropriate.

Further, the emulsion of the present invention can be subjected to various chemical sensitization methods that are applied to ordinary emulsions. That is, activated gelatin: a sensitizer such as a water-soluble gold salt, a water-soluble platinum salt, a water-soluble palladium salt, a water-soluble rhodium salt, a water-soluble iridium salt, etc.:
Sulfur sensitizer: Chemical sensitizers such as selenium sensitizers, polyamines, and reduction sensitizers such as stannous chloride can be used alone or in combination for chemical sensitization. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the method for optically sensitizing the emulsion of the present invention.1 For example, an optical sensitizer such as a cyan dye such as a zeromethine dye, a monomethine dye, or a trimethine dye or a merocyan dye may be used alone or in combination (for example, supersensitization). It can be optically sensitized. These technologies are described in US Patent 2,
No. 688,545, 2.9+, 2. : No. 129, No. 3
, No. 197,050, No. 1, No. 615.635, No. 3
, No. 628,964, British Patent No. 1,195,102,
No. 1,242,588, No. 1,293,862, West German Patent (OL S) 2,0:10) No. 26, No. 2
, No. 121,780, Special Publication No. 43-4936, No. 44
-14030 etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, the sensitivity ring, the purpose of the photosensitive material, and the use.

In forming the silver halide grains contained in the silver halide emulsion used in the present invention, a silver halide emulsion that is a core grain or a monodisperse silver halide grain is used, and the core grain is surrounded by a shell. By coating the shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained, but such a monodisperse silver halide emulsion cannot be used with its grain size distribution unchanged. Alternatively, two or more types of monodisperse emulsions having different average grain sizes may be blended at any time after grain formation to obtain a predetermined gradation for use.

The silver halide emulsion used in the present invention has a distribution width of 20% or less, and the total halogen content in the emulsion is equal to or higher than that of an emulsion obtained by coating a monodisperse core with a shell of 20% or less. It is preferable that the silver grains contain the silver halide grains of the present invention, but silver halide grains other than the present invention may also be included as long as the effects of the present invention are not impaired. The silver halide other than the one according to the present invention may be a core-shell type other than the one according to the present invention, or may be a type other than a core-shell type, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, it is preferable that at least 65% of the silver halide grains contained in the emulsion are core-shell silver halide grains of the present invention, and almost all of them are core-shell silver halide grains of the present invention. It is desirable that the particles be silver oxide particles.

The present invention includes the case where at least one photosensitive layer is a silver halide emulsion or an emulsion containing the tabular silver halide grains of the present invention. That is, in the emulsion of the present invention used in the silver halide emulsion layer of the present invention, the silver halide grains thereof are (1) core-shell silver halide grains of the present invention as described above; (The tabular silver halide grains of the present invention may be of a core-shell type or of other types.); () being a mixture of (2) and (2) above; Any embodiment is included in the present invention.

The tabular silver halide grains of the present invention will be explained below.

The tabular silver halide grains of the present invention preferably have a grain size or grain thickness of 5 times or more. The tabular silver halide grains are disclosed in JP-A Nos. 58-113930 and 58-113934.
No. 58-127921 and No. 58-108532
In the present invention, from the viewpoint of effects on color staining and image quality, the particle diameter or particle thickness is 5 times or more, preferably 5 to 5 times the particle thickness.
It may be used that is 100 times larger, particularly preferably 7 to 30 times larger. Furthermore, the particle size is 0. : 1 gm or more is preferable, and 0.5 to 6 gm is particularly preferably used. When these tabular silver halide grains are contained in at least 50% by weight of at least one layer of silver halide emulsion, the desired effect of the present invention is more preferably exhibited, and almost all of the tabular silver halide grains are contained in at least 50% by weight of the silver halide emulsion layer. When this is the case, particularly favorable effects are produced.

It is particularly useful when the tabular silver halide grains of the present invention are core-shell grains. In the case of core-shell particles, it is preferable that the requirements described above for the core-shell are also satisfied.

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 planes that make up the tabular silver halide grains. .

The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide.

In particular, silver iodobromide having a silver iodide content of 3 to 10 mol% is preferred.

Next, a method for producing tabular silver halide grains of the present invention will be described.

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

For example, seed crystals containing 40% or more of tabular silver halide grains by weight are formed in an atmosphere with a relatively high 9Ag value of par 1.3 or less, and a silver and halogen solution is grown while maintaining the par value at the same level. It can be obtained by growing seed crystals while simultaneously adding them.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the ffi salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of the silver halide solvent to be used is preferably 1.times.10-' to 1.0% by weight, particularly 1.times.10-2 to 1.0.times.10-'% by weight of the reaction solution.

For example, as the amount of silver halide solvent used increases, the silver halide grain size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of silver halide grains to increase with the amount of silver halide solvent used.

Examples of the silver halide solvent used include ammonia, thioethers, and thioureas. Regarding thioethers, reference may be made to US Pat. No. 3,271.157, US Pat. No. 790,387, US Pat.

During the production of tabular silver halide grains of the present invention.

Added to speed up particle growth. ffl salt solution (e.g. HegNOz aqueous solution) and halide solution (e.g. KB
A method of increasing the addition rate, amount, and concentration of the aqueous solution (r) is preferably used.

These methods are described, for example, in British Patent No. 1. :+35.
No. 925, U.S. Pat. No. 3,672,900, ibid.: l, 6
No. 50,757, No. 4,242,445, Japanese Unexamined Patent Publication No. 1983
Reference may be made to the descriptions in No. 142329, No. 55-158124, and the like.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. Regarding the chemical sensitization method, the description of the sensitization method explained for the core shell can be referred to, but from the viewpoint of silver saving in particular, the tabular silver halide grains of the present invention may be gold sensitized, sulfur sensitized, or sensitized with gold or sulfur. Combination use is preferred.

In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular silver halide grains are present in an amount of 40% or more, particularly 60% or more, based on the fff amount of all the silver halide grains in the layer.

The thickness of the layer containing tabular silver halide grains is 0.5p.
m ~5.0JLa+, especially 1.0J1. m ~1.
It is preferable that the person is OBm.

Also, the coating amount of tabular silver halide grains (for one side)
is 0.5g/rn' to 6g/rn', especially 1g/rr
It is preferable that it is 1' to 4 g/m'.

Other components of the layer containing tabular silver halide grains of the present invention 1 For example, a binder, a hardening agent, an antifoggant, a silver halide stabilizer, a surfactant, a spectral sensitizing dye, a dye, and an ultraviolet absorber. There are no particular restrictions on 1. For example,
nesearch Disclosure Volume 176, 2
Reference may be made to the description on pages 2-28 (December 1978).

Next, a silver halide emulsion layer (
The structure of the upper silver halide emulsion layer (hereinafter referred to as the upper silver halide emulsion layer) will be described below.

The silver halide grains used in the upper silver halide emulsion layer are preferably high-sensitivity silver halide grains used in ordinary direct X-ray films.

The shape of the silver halide grains is preferably spherical, polyhedral, or a mixture of these two. In particular, it is preferable that spherical particles and/or polyhedral particles with a diameter/thickness ratio of 5 or less account for 60% or more (weight ratio) of the total.

The W average particle size is preferably 0.5 pl to 3 gm, and if necessary, ammonia, thioether,
It can be grown using a solvent such as thiourea.

Halogenated ff1 particles can be produced by gold sensitization, other total sensitization methods, binary sensitization, sulfur sensitization, or two of these methods.
It is preferable that the sensitivity is increased by a sensitization method using a combination of two or more methods.

As with the layer containing tabular silver halide grains, there are no particular restrictions on the other compositions of the upper emulsion layer, and the above-mentioned Re
5earch Disclosure 17 [You can refer to No. 13/1.

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

For example, JP-A-58-113930 discloses a multilayer color photographic material having a two-layer dye-forming unit having an emulsion layer containing tabular silver halide grains with an aspect ratio of 8:1 or more in the L layer. , 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 8:1 or more in the green-sensitive layer and the red-sensitive layer. Or again! IIF 1978
No. 113927 discloses a multilayer color photographic material having tabular silver halide grains having a silver iodide content, a lower aspect ratio, or a lower aspect ratio than the central region or the annular region. JP-A No. 59-55426 has an aspect ratio of 3:
A silver halide photographic light-sensitive material containing one or more tabular silver halide grains and a specific sensitizing dye, which can also be applied to a color photosensitive material, is further disclosed in Japanese Patent Application No. 111696/1983, having an aspect ratio of 3=1. There have been disclosed silver halide color photographic materials containing tabular silver halide grains mainly consisting of (111) planes, and these silver halide color photographic materials are also covered by the present invention. A processing method can be applied.

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

Next, the inhibitor-releasing compound of the present invention will be explained.

The inhibitor-releasing compound of the present invention may be any compound that releases or elutes an inhibitor that forms a silver salt having a solubility product with silver ions of I x 10-' or less during development, especially DIR. Compounds, tetrazaindene derivatives, and 6-aminopurine derivatives are preferably used. Among these, DIR compounds are particularly preferably used in order to achieve good results in achieving the object of the present invention. Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as U.S. Pat. Nos. 3,297,445 and 3,37
No. 9.529, West German Patent Application (OLS) 2,4
No. 17,914, JP-A-52-15271, JP-A No. 53-
No. 9116, No. 59-123838, No. 59-127
Examples include those described in No. 038 and the like.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler.For example, British Patent No. 9: No. 15,454, U.S. Patent No. 1.227,554, U.S. Patent No. 4.095.984
No. 4,149,885, etc.

The DIR coupler described above has the property of forming a dye while releasing a development inhibitor when the DIR coupler undergoes a Kabrin reaction with an oxidized color developing agent. Moreover, in the present invention, US Pat. No. 1,652,345 and US Pat.
No. 1, No. 3,958,99: No. 1, No. 3,961,95
No. 9, No. 4,052,213, JP-A-53-1105
No. 29, No. 54-13333, No. 55-161237
It also includes compounds that release a development inhibitor but do not form a dye when they react with an oxidized form of a color developing agent, such as those described in No.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a color patch or a colorless compound, while the released timing group undergoes intramolecular nucleophilic substitution. The so-called Timing D is a compound that releases a development inhibitor through reaction or elimination reaction.
IR compounds are also included in the invention.

Also, JP-A No. 58-160954, No. 58-16294
Timing D, which has a timing group such as 1; bonded to the coupler mother nucleus which produces a completely diffusible dye when reacted with an oxidized form of a color developing agent described in No. 9.
It also includes IR compounds.

According to the present invention, more preferred DIR compounds can be represented by the following general formula (I) and/or (rl), and among these, the most preferred DIR compound is a compound represented by the following general formula (■).

General formula (I) A, -Z.

In the formula, AI is a coupler component (compound) capable of coupling with an oxidized form of an N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent, such as open-chain ketomethylene compounds such as acylacetanilides and acylacetate esters, pyrazolone, etc. , pyrazolotriazoles, pyrazolinobenzimidazoles, indasilones,
These include dye-forming couplers such as phenols and naphthols, and coupling components that do not substantially form dyes such as acetophenones, indanones, and oxacilones.

In addition, zI in the above formula is N-hydroxyalkyl-substituted-
p-phenylenediamine derivative A component (compound) that is released by reaction with a color developing agent and inhibits silver halide development. Preferred compounds include benztriazole, 3-octylthio-1,2,4-triazole, etc. There are heterocyclic compounds and heterocyclic mercapto compounds (heterocyclic mercapto groups include i-phenyltetrazolylthio groups, etc.).

Examples of the above-mentioned heterocyclic group include a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxasilyl group, imidazolyl group, triazolyl group, and the like. in particular.

l-7enyltetrazolyl group, l-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, ■, co, 4-thiazolyl group, 5-methyl-1,3,4
-oxadiazolyl group, benzthiazolyl group, benzoxacylyl group, benzimidazolyl group, 411-1.
2.4-triazolyl group, etc.

In addition, in the above general formula (I), Zl is bonded to the active point 8.

General formula (■) A2-TIME-Z2 In the formula, Z2 is Z defined in the above general formula (1),
is the same as A2 also includes a coupler component which forms a completely diffusible dye as defined in general formula (I). TIME reacts with the oxidized product of A2 or a color developing agent to form the general formula (I) together with Z2.
Represents a timing group capable of separating from the compound represented by I) and subsequently releasing z2, and TIME represents the following general formula (m)
, (rV), (V), (71) and (VI[), but are not limited to these.

General Formula (III) In the formula, X represents an atomic group necessary to complete a benzene ring or a naphthalene ring. Y is 10-1-8-, -N
- (here, R3 represents a hydrogen atom, an alkyl group, or an aryl group), and is bonded to the coupling position. In addition, R1 and R2 each represent a group having the same meaning as R3 above, or the group -C- is substituted at the ortho position or the vous position with respect to Y, and is bonded to the petero atom contained in the inhibitor z2. ing.

General formula (IV) In the formula, W is a group having the same meaning as Y in the general formula (m), and R4 and R6 are also each R in the general formula (m).
It is a group having the same meaning as 1 and R2.

R6 is a hydrogen atom, an alkyl group, an aryl group, an acyl group,
Sulfo group, alkoxycarbonyl group, (, heterocyclic residue, R7 is a hydrogen atom, alkyl group, aryl group, heterocyclic residue, alkoxy group, aminos (, acylamido group,
Represents a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyan group. This timing group is then bound by W to the coupling position of A2.

- attached to the heteroatom of inhibitor Z2 by C-.

Next, an example of a timing group that releases the inhibitor Z2 by an intramolecular nucleophilic substitution reaction is shown by general formula (V).

General formula (V) Nu -E In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is bonded to the coupling position of A2. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, phosphinyl, or thiophosphinyl group and is bonded to the heteroatom of the inhibitor z2.

V has a steric relationship between Nu and E, and after Nu is released from 82, it undergoes an intramolecular nucleophilic substitution reaction with the formation of a 3- to 7-membered ring, and thereby becomes an inhibitor. It is a bonding group that can release Z2.

In the general formula (VI) 0-CH, R represents a hydrogen atom, an alkyl group, or an aryl group, the oxygen atom is bonded to the coupling position of the coupler A2, and the carbon atom is bonded to the nitrogen atom of the inhibitor Z2.

General formula [■] In the formula, Y' is a group having the same meaning as Y in the general formula (m), R9 represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and Y' represents the group of coupler A2. It is attached to the coupling position and is attached with a carbon atom to the heteroatom of the inhibitor Z2.

Typical examples of DIR compounds according to the present invention will be described below, but the present invention is not limited thereto.

[Exemplary compounds]

(D-1) ρ1 (D-2) t ■ CH.

(D-3) 2H5 (D-4) H (D-5) H N=N (D-6) L (D-7) t (D=10) H (D-11) H 03Hz (ts□) h″′, N♂ (D-12) (D-13) H (D-14) M Nsu2 (D-15) (D-16) (D-17) H (D-18) Lo q- of

ζノC1 (D-27) (D-28) 0.2H2,0OOOHOOOO12H2゜t (D-30) (D-31) H (D-34) OH (D-35) (D-36) (D- 37) (D-38) 0.2) 1250COOHCOOO, □) I25 (D-
39) (D-40) (D-41) OH (D-42) (D-43) (D-44) OH (D-46) (D-48) (D-49) (D-50) 1 Just low - low (D-56) (D-57) z- at (D-58) at (n-so) (D-61) H (D-62) (D-+33) (D-64) OH (D-65) OH 2H5 (D-66) OH OH (D-67) OH (D-68) (D-69) (D-70) 02H.

2H5 (D-72) (D-73) nτJ (D-74) H (D-75) nth C2H6 (D-76) H (D-77) H (D-78) H (D-79) H (D-82) n#J (D-83) (D-84) H (D-85) H -N (D-86) (D-87) t H3 The DIR compound of the present invention is a photosensitive halogenated Although it can be added to a silver emulsion layer and/or a non-photosensitive photographic constituent layer, it is preferably added to a light-sensitive silver halide emulsion layer.

Two or more types of DIR compounds of the present invention may be contained in the same layer, or the same DIR compound may be contained in two or more different layers.

These DIR compounds are generally used in an amount of 2 x 10-' to 5 x 10-' moles of silver in the emulsion layer, more preferably l x to-' to l x 10-' moles.

In order to incorporate these DIR compounds into the silver halide emulsion or other photographic composition coating solution according to the present invention,
If the DIR compound is alkali-soluble, it may be added as an alkaline solution; if it is oil-soluble, it may be added as described in US Pat. No. 2,322. (No. 127, same No. 2
．． 1101.17 (No. 1, No. 2.1301.171, No. 2,272,191 and No. 2.:104.
It is preferable to dissolve the DIR compound in a high-temperature solvent and, if necessary, in combination with a low-boiling-point solvent according to the method described in each specification of No. 940, disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, two or more types of DIR compounds may be mixed and used if necessary.Moreover, to explain in detail the preferred method of adding DIR compounds in the uninvented state, one or more types of DIR compounds may be used in combination. Organic acid amides.

Carbamates, esters, ketones, urine + 1/1 bodies, ethers, 1-culture hydrogens, etc., especially sea n-phthalate, 1-leak resyl phosphate.

1-Riphenyl phosphate, C-isooctyl azelate, C-n-phthyl sehacate, tri-hexyl phosphate, N,N-C-ethyl-cabusolamitophthyl, N,N-ethyl lausolamit, n-pentadecyl Phenyl ether, di-octyl phthalate, n
- high boiling point solvents such as nonylphenol, 3-pentadecyl phenylethyl ether, 2.5-C5eC-amylphenyl phthyl ether, monophenyl-di-0-chlorophenyl phosphate or fluorohalaffin, and/or methyl acetate, ethyl acetate, acetic acid propyl,
Alkylbenzene sulfone can be dissolved in a low point solvent such as phtyl acetate, phtyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. acid and an aqueous solution containing an anionic surfactant such as an alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as sorbitan sesquiolein, sorbitan monolaurate, and/or a woody binder such as seratin. , emulsify and disperse using a high-speed rotating mixer, colloid mill or ultrasonic dispersion device, etc.
Added to silver halide emulsions.

In addition, the above DIR compound may be dispersed using a latex dispersion method.The latex dispersion method and its effects are as follows:
JP-A No. 49-74538, No. 51-59943, No. 54-32552, Research Disclosure August 1976, N.

, 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxobentyl)) acrylamide, 2-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

The above DIR compounds are described in U.S. Pat. No. 1, 227,554
No. 615,506, No. 3,617,291, No. 3,5:12.145, No. 3,928,041, No. 3,913,500, No. 3.938,996 issue,
Same: l, No. 958,993, No. 3,961,959, No. 4.045574, No. 4. t152.21'1, 4,053,950, 4.095,984,
No. 4449.886, No. 4,234.678, British Patent No. 2,072. :16:1 No. 2,070,266
No., Research Disclosure No. 21228 (19
1981), JP-A No. 50-81144, JP-A No. 50-811
No. 45, No. 51-13239, No. 51-64927, No. 51-104825, No. 51-105819,
No. 52-65433, No. 52-82423, No. 52
-117627, 52-130327, 52-
No. 154631, No. 53-7232, No. 53-911
No. 6, No. 53-29717, No. 53-70821,
No. 53-103472, No. 53-110529, No. 53-135333, No. 53-143223, No. 5
No. 4-13333, No. 54-49138, No. 54-1
No. 14241, No. 57-35858, No. 54-145
No. 135, No. 55-161237, No. 56-1149
No. 46, No. 57-154234, No. 57-56837
No. and patent application No. 57-44831, No. 57-45809
It can be synthesized by the method described in No.

The IR compound (I) of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer as described above, or is preferably added to at least one of the silver halide emulsion layers. For example, when applied to a normal multilayer color photographic material having a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a red-sensitive silver halide emulsion, one layer of these may be incorporated. Alternatively, it may be contained in two or more layers.

The tetrazaindene derivatives used in the present invention are known as stabilizers for silver halide emulsions in photographic light-sensitive materials, and those represented by the following general formula (■) exhibit particularly favorable effects.

General formula [■] In the formula, m and n are the g number of 1.2 or 3, and R6, R
9 is each a hydrogen atom, and 1 carbon number that may have a substituent
Represents an alkenyl group of ~4, an alkyl group, or an aryl group which may have 8 substituents.

The tetrazaindene derivatives represented by the above general formula (■) are particularly effective, and specific examples of tetrazaindene derivatives that are more effectively used in the present invention are shown below or are limited to these. There isn't.

[Exemplary compound el] A-14-hydroxy-1,lja, 7-tetrazaindene A-24-hydroxy-6-methyl-1,co, :]a,
7-Chitrazaindene A-34-hydroxy-6-hydroxyl 1,1. :I
a.

7-tetrazaindene A-44-hydroxy-6-butyl 1. :l, :Ia
, 7-tetrazaindene A-54-hydroxy-5,6-cymethyl-1,3.3
a.

7-tetrazaindene A-62-ethyl-4-hydroxy-6-broby-1
．． :t,3a,7-tetrazaindene A-72-allyl-4-hydroxy-L,3,3a,7-tetrazaindene A-84-hydroxy-6-phenyl-1,:l,:I
a, 7-tetrazaindene These compounds are described in Japanese Patent Publication No. 46-18102, No. 44-
It can be synthesized by referring to the description in No. 2533 and the like. Among these compounds, those having a hydroxyl group at the 4th position are preferred, and those having a hydroxyl group at the 4th position and an alkyl group or an aryl group at the 6th position are more preferred.

The 6-aminopurine derivatives used in the present invention include those known as stabilizers for silver halide emulsions in photographic light-sensitive materials, and particularly those represented by the following general formula (IX) exhibit preferable effects.

General formula (IX) In the formula, RIO is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent, R11 is a hydrogen atom,
It represents an alkyl group having 1 to 4 carbon atoms which may have a substituent or an aryl group which may have a substituent.

As the 6-aminopurine derivative in the present invention, those represented by the general formula (IX) are particularly effective, but specific examples of 6-aminopurine derivatives that can be used more effectively are shown below, but the invention is not limited thereto. isn't it.

[Exemplary Compounds] B-15-aminopurine B-22-hydroxy-6-aminopurine B-32-methyl-6-aminopurine B-46-amino-8-methylpurine B-56-amino-8-phenylpurine B-62-Hydroxy-6-amino-8-phenylpurine B-72-Hydroxymethyl-6-aminopurine These tetrazaindene and 6-aminopurine derivatives preferably contain from Smg to 1 per mole of silver halide.
When used in an amount of 8 g, good effects are achieved for the purpose of the present invention.

Furthermore, among these compounds which form silver salts with solubility of silver ions of Jxl0-9 or less, compounds with solubility of Ixl0-■ or less are more preferable to exhibit uninvented effects.

However, DIR compounds, tetrazaindene derivatives and 6
- Aminopurine derivatives are known to be added to ordinary silver halide emulsions to improve image quality and to suppress ripening and frizz that occur in emulsion production. It was completely unknown that when used in combination with M1, the effect of improving graininess could be obtained.

The aromatic primary amine color developing agent used in the color developing solution of the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives.

Since these compounds are more stable than the M-state, they are generally in the form of salts, such as 11! Used in acid or sulfate form. These compounds are also used in concentrations of from about 0.1 g to about 10 g per color developer, more preferably from about tg to about 15 g per IIL.

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, Z-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful aromatic primary amine color developer n1 has an amino group having at least 51 water-soluble groups? Among the aromatic primary amine color developing agents, compounds represented by the following general formula (X) are particularly preferred.

General formula (X) In the formula, R1ff represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group represents a straight-chain or branched alkyl group having 5 to 5 carbon atoms, and may have a substituent. . R+4 and R15 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. At least one of R14 and RIS is a hydroxyl group, a carboxylic acid group, a sulfonic acid group,
It is an alkyl group substituted with a water-soluble group such as an amino group or a cissulfonamide group, or a ctt2-0-+-RIB. This p alkyl group may further have a substituent group.

In addition, Li+ represents a rice atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent integers of 1 to 5.

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

The following margins [exemplary compounds] (FJ-1) H2 (E-2) H2 (E-3) H2 (E-4) (E-5) r11'H2 (E-6) H2 (E-7) H2 ( B-8) H2 (B-9) H2 (E-ro) H2 (E-11) H2 (E-12) (E-13) H2 (B-14) H2 ('FJ-ts) H2 (E- 16) H2 These p-phenylenediamine derivatives represented by the general formula (X) can be used as salts of organic acids and inorganic acids, such as hydrochlorides, sulfates, and phosphates.

p-) Luenesulfonate, sulfite, oxalate, benzenedisulfonate, etc. can be used.

In the present invention, among these p-phenylenediamine derivatives represented by the general formula (X), R14 and/or Fits is -F(CH2-y, rho]-pR16(p
.

q and l1ta have the same meanings as above), the effects of the present invention are particularly well achieved.

Preferred compounds for use in the color developer of the present invention include sulfites, hydroxylamines, and development inhibitors.

Sulfites include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc.
It is preferable to use it in a range of 0.1 to 40 g/l, more preferably in a range of 0.5 to 10 g/l.

H) - N-dylamine is used as a crucible for 112-acid salts, sulfuric acid m, etc., and it is preferably used in the range of 0.1 to 40 g/l, and more preferably 0.5 to 40 g/l. lo
Use within the range of g/cross.

Examples of inhibitors include halides such as sodium bromide, potassium bromide, helium iodide, and potassium iodide; , H are in the range of 0.005 to 20 g/cross, preferably in the range of 0.01 to 5 j:/day.

;P-1 extra-1 In the present invention, the beating machine inhibitor means a nitrogen-containing polycyclic compound,
Compounds containing a mercapto group (Y, heteroaromatic compounds, onium compounds, and compounds having Kyoko iodine as substituted J15, preferably the following general formula Cn-1), [:R
-II: A compound represented by l and CR-[1').

The compound represented by the general formula CR-+3 is more preferably a compound represented by the general formula [R-1'V) or (R-V:l, and most preferably the compound represented by the general formula [- Vl
] to [Il-kari].

On the other hand, the compound represented by the general formula (R-II) is most preferably the general formula [R-■] or [R-X[I
) is a compound represented by

General formula [:R-1) (Xt No KN, alkyl group, aryl group, or double viscosity to form a ring, Z is a carbon atom, oxygen atom, nitrogen atom necessary to form a ring,
Liver consisting of sulfur atoms, n and m represent 0, l or 2.

General formula (R-11'1) In the formula, yyy, y, Y3 represents a hydrogen atom, a halogen atom, an alkyl group, an amino group, a hydroxyl group, a nitro group, a calhoquinol group, or a sulunyl group.

General formula [R-■] 1・9 YsT’Xt X.

In the formula, T is a nitrogen atom or a phosphorus atom, X: l is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, Y4,
Y represents an alkyl group or an aryl group, and Y4 and Y,
may be ring-closed to form a heterocycle.

General formula [R-VI] General formula [R-■] General formula [R-■] General formula (RIX) General formula CR-X) General formula [R-■] General formula (R-XIII) 1 for each formula Medium, R, R,, RtSY+, Y, have the same taste as above.

General formula [R-IV] Compounds in which 2 to 5 of 1 to 9 carbon atoms are substituted with nitrogen atoms and derivatives thereof General formula [-V] Compounds in which 2 to 5 of 1 to 9 carbon atoms are substituted with nitrogen atoms Substituted compounds and derivatives thereof [Examples of finite inhibitors] COOC, +1? il l 1 Zl3 C,11゜Zl ・I N11211 lf3 COOI( ” 25C1l, C00I+ 7, 26 Z゛27 (n=35~45) Z34 +1 COOI+ 0JNa R 113c11.cll, -CItCO O) 1COOC
411o(t) ll H Jll Z59 7, 60 II Z6. Alkaline agents such as sodium oxide and sodium carbonate, alkali metal thiocyanates, alkali total halides, pencil alcohol, water softeners and thickeners, development accelerators, and the like may optionally be included.

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

The color developing solution of the present invention is suitable for p119 and above, especially p119.
It is preferable to use .about.13.

In addition to the method described in L, there are no particular limitations on the processing method for the photographic light-sensitive material of the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development and, if necessary, further washing with water or stabilization treatment as an alternative to water washing; How to perform water washing or water washing alternative stabilization treatment:
Alternatively, pre-hardening, neutralization, color development, stop-fixing, water washing (or water-washing alternative stable treatment), bleaching, fixing, water-washing (or water-washing alternative stable treatment), post-hardening, water washing (or water-washing alternative stable treatment)
Color development, water washing (or water washing alternative stabilization treatment), supplementary color development, stopping, bleaching, standardization, water washing (or water washing alternative stabilization treatment), stabilization in this order, development resulting from color development Any method may be used for processing, such as a development method in which the silver is subjected to halogenation bleaching and then color development is performed again to increase the amount of dye produced.

In the uninvention, processing with a processing solution having bleaching ability means
This means processing with a bleaching solution or a -bath bleaching solution, but the effects of the present invention are best achieved when -bath bleaching and fixing stone treatment is performed.

Bleaching agents used in the bleaching solution or bleaching stone solution in the bleaching process are generally known as aminopolycarboxylic acids or hexaacids, organic acids such as citric acid, or those coordinated with total ion such as iron, cobalt, copper, etc. It is being The following are representative examples of the above aminopolycarboxylic acids.

Ethylenecyaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ethercyaminetetraacetic acidethylenediaminetetrabrobionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotributyric acid sodium saltBleaching solution of the present invention and The bleaching solution may be used at a plI O of 2 to 9.5, preferably 4.0 or higher, more preferably 5.0 or higher. Processing temperature is 20°C
It is used at ~80°C, preferably at 40°C or higher.

The bleaching solution of the present invention can contain various additives in addition to the above-mentioned bleaching agent (preferably an organic acid ferric complex salt). As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. Also m-acid, oxalate, acetate, carbonate,
Regular bleaching of pH buffers such as phosphates, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. You can add things that are known to be added to the liquid as appropriate.

The bleach fixing solution of the present invention has a composition in which a small amount of a halogen compound such as potassium bromide is added, or a white fixing solution has a composition in which a large amount of a halogen compound such as potassium bromide or ammonium bromide is added. It is also possible to use a bleach-fix solution, as well as a special bleach-fix solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, kawaram iodide, sodium iodide,
Ammonium iodide and the like may also be used.

The silver halide fixing agent to be included in the bleaching fixing stone solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount that can dissolve at least 5 g/i, preferably at least 50 g/i, more preferably at least 70 g/i.

Note that the bleach-fix solution of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and hydroxide. It is possible to contain pl+buffer consisting of various salts such as ammonium alone or in combination of two or more. Furthermore,
Various optical brighteners, antifoaming agents, surfactants, and antifungal agents can also be contained. Also hydroxyamines, hydrazine, sulfites, isomeric bisulfites, aldehydes)
Preservatives such as binitrous acid adducts of heyaketone compounds, organic chelates such as acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids Stabilizers such as 2-hroal: ]-ru, Kozue P & T4B, solubilizers such as alkanolamines, anti-stain agents such as organic amines, other additives, methanol, dimethylformamide, dimethyl An appropriate amount of organic solvent such as sulfoxide can be included.

In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or '17H white fixing immediately after color development, or after performing processing such as washing or rinsing and stopping other than color development. It may be used for bleaching or liN white fixing treatment, or it may be used as a prebath t7z white containing a bleach accelerator or as a processing solution prior to bleach fixing.

Processing other than color development of the silver halide color photographic light-sensitive material of the present invention 1 For example, bleach-fixing, 27 (or bleaching, fixing), and various processing steps such as washing with water or stabilization as an alternative to washing as necessary. The temperature is preferably 20°C to 80°C, more preferably 40°C or higher.

In the present invention, JP-A-58-14834.

It is preferable to carry out a stabilization treatment as an alternative to washing as shown in Japanese Patent Application No. 58-105145, No. 58-134634, No. 58-18631, and Japanese Patent Application No. 58-2709 and No. 59-89288.

Each of the silver halide emulsion layers according to the invention may contain a coupler, that is, a compound capable of reacting with an oxidized product of a single color developing agent to form a dye.

Various yellow couplers, magenta couplers and cyan couplers can be used as the above-mentioned couplers that can be used without any particular limitations. These couplers may be so-called 2-mer type couplers or 4-9-mer type couplers, and it is also possible to use diffusible dye-releasing type couplers or the like in combination with these couplers.

The yellow coupler may be a closed ketomethylene compound or a so-called two-dose coupler.
〇-aryl m-substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound replacement coupler and active point succinimide compound substituted coupler, active point fluorine-substituted coupler, active point chlorine-substituted coupler Odor No. 1 ↓ Substitution coupler, active point -
〇-sulfonyl substituted couplers can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent No. 2,875.057;
Same: l, No. 255,506 5 times: l, 408.19
No. 4, No. 3,551,155, No. 3,582,3
No. 22, No. 3,725,072, No. 1, 891,
445, West German Patent No. 1,547,868, West German Patent Application No. 2,219,917, West German Patent Application No. 2,261,151, West German Patent No. 2,414.006, British Patent No. 4. 1.425,02
No. 0, Special Publication No. 1978-10783, Japanese Patent Publication No. 47-261
No. 33, No. 48-73147, No. 51-102636
No. 50-6341, No. 50-123342, No. 50-130442, No. 51-21827, No. 50
-87650, 52-82424, 52-11
Examples include those described in No. 5219 and No. 58-95346.

Examples of magenta couplers used in the present invention include pyrazolone-based, pyrazolo l-lyazole-based, pyrasolinobenzimitazole-based, and intasolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers like the yellow couplers but also 2-equivalent type couplers. Specific examples of magenta couplers include US Pat.
8 Co., No. S08, Same: l, 052, 65: No. 1, Same 3,
127.26! No. 1, 3, 31. l, No. 476, same, 419. : No. 191, No. 1,519,429, No. 3.558. : No. 119, No. 3,582,322, No. 1,615,506, No. 1,834,908, No. 1,891,445, West German Patent No. 1,810.46
No. 4, West German Patent Application (OLS) 2,408,6
No. 65, No. 2,417,945, No. 2,418,95
No. 9, No. 2,424,467, Special Publication No. 40-6031
No. 51-20826, No. 52-58922, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49
-74028, 50-60233, 51-26
No. 541, No. 53-55122, patent application No. 55-110
Examples include those described in No. 943 and the like.

Furthermore, useful cyan couplers used in the present invention include, for example, phenolic couplers, naphthol couplers, and the like. Similar to the yellow couplers, these cyan couplers are not 4-equivalent type couplers, but may also be 2-equivalent type couplers. Specific examples of cyan couplers include US Pat. No. 2,369.929 and US Pat. No. 2,4:14,272.

No. 2,474,293, No. 2,521,908, No. 2,895,826, No. 3,0:14,892, No. 111,476, No. 1, 458. 315, 3,476.56:1, 583,971
No. 3,591,183, No. 3,757,411, No. 1,772,002.

No. 3,933,494, No. 4,004,929, West German Patent Application (OL'S) No. 2,414, 8:10,
2,454. : 129, JP 48-59838, JP 51-26034, JP 48-5055, JP 51
-146827, 52-69624, 52-9
No. 0932, No. 58-95346, Special Publication No. 1973-11
572, etc. may be mentioned.

Couplers such as colored magenta or cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding the colored magenta or cyan coupler, a patent application filed in 1973 by the applicant
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 1987-172151 filed by the present applicant.

The method of adding the coupler used in the present invention to the photographic constituent layer of the present invention is conventional, and the amount of the coupler added is not limited to l x t per mole of silver.
o-' to 5 mol, preferably 1 x 1
0-'' to 5 x 10-'.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, Color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, humectants, and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Included are cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, bobbinylimidazole, synthetic hydrophilic polymers of copolymers such as polyacrylamide, and the like.

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

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

In these constituent layers, wood-philic colloids that can be used in the emulsion layers as described above can be similarly used as binders, and they may also be incorporated in the emulsion layers as described above. Various photographic additives can be included.

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

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Note that graininess (RMS) is defined as the color image density (+tj
This was done by comparing the 1000 times value of the standard deviation of the variation.

Furthermore, in all the embodiments below, the halogenated shikara photoj'j! ,! Addition 1j in Hikari material Ning-1 is 1 m'
The correct value is shown, and silver halide and colloid [~Silver is shown in terms of silver.

Example 1 Silver iodobromide emulsions shown in Table 1 were prepared by the following manufacturing method. A was produced using a conventional table sieve 1-. B-D
produced a core/shell type 4i dispersion emulsion by the function addition method.
! ! A crushed. In E, a plate-like silver halide emulsion was prepared by Tuffleciet while controlling the pH and PAg.

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

First layer, antihalation layer (HC layer) Antihalation layer consisting of 0.18g black colloidal silver and 1.5g gelatin.

: fS 2 layers, undercoat layer (10 layers) Subbing layer consisting of 2.0 g of gelatin.

Third layer, red-sensitive silver halide emulsion layer (R layer) Each of the silver iodobromide emulsions shown in Table 1 was color sensitized to /Z red sensitivity, and 0.08 mol 1 Mol AX cyan coupler (C-1), 0.006 mol 1 mol Ag colored cyan coupler (CC-1) and DIR compounds shown in Table 2 are dissolved in 0.5 g tricresyl phosphate (referred to as TCP). and also dissolve the inhibitor in methanol, 1
．． A red-sensitive silver halide emulsion layer containing a dispersion emulsified in an aqueous solution containing 80 g of gelatin.

4th layer, middle layer (2G layer) 0.14g of 2.5-di-butylhydroquinone, 0
．． An intermediate layer consisting of 0.7 g of dibuty rifthalate (referred to as DBP).

Fifth layer, green-sensitive silver halide emulsion layer (G layer) Each of the silver iodobromide emulsions shown in Table 1 above was color sensitized to green sensitivity.
．． 0 g, 0.07 mol 1 mol Ag of magenta coupler (M-1), 0.015 mol 1 mol Ag of colored magenta coupler (CM-1), and 0.64 g of TCP in which the DIR compounds shown in Table 2 were dissolved. A green-sensitive silver halide emulsion layer containing a dispersion emulsified and dispersed in an aqueous solution containing 1.4 g of gelatin.

6th layer, protective layer (3G layer) t' protective layer containing 0.8 g of gelatin.

In addition to the above, each layer contains a gelatin hardening agent (1,2-bisvinylsulfonylethane) and a surfactant, and the halogenated emulsion shown in Table 1 is used in the third R layer and the fifth G layer. Samples were prepared by adding the DIR compounds or inhibitors shown in Table 2 so that the ratio of the amount of developed silver to the amount of coated silver was within the range of the present invention.

Cyan coupler (C-1) 2-(α, α, β, β, γ, γ, δ, δ-octafluorohexanamide)-5-[2-(2,4-di-t-amylphenoxy)hexane Amide l Phenol colored cyan coupler (CC-1> 1-Hydroxy-444-0-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-disulfo) monoamylphenoxy)butyl 1-2-naphthamide disodium salt magenta coupler (M-1) 1-(2,4,5-trichlorophenyl)-3-([α
-(2゜4-amylphenoxy)-acetamide lbenzamide)-3-pyrazolone and 1-(2,
4,6-1-lichlorophenyl)-3-([α-(2,
4-C~amylphenoxy)-acetamide lbenzamide l-4-(4-methoxyphenylazo)-5
-Pyrazolone colored magenta coupler (CM-1)]-(2,4,
5-Trichlorophenyl)-4-(1-naphthylazo)
-3-(2-Chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone Green light, red light, green light + red light (100 MS) was applied to each sample through a wedge, and the following treatment was performed. After processing, a Buddhist calligraphy image was obtained.

Processing steps Color development Bleaching at times and temperatures shown in Table 2
6 minutes 30 seconds (38°C) Joseki 6 minutes 30
2 seconds (30-38℃) Wash with water 3 minutes 15 seconds (20
~33°C) stabilization 3 minutes 15 seconds (20~33°C)
°C) Drying The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2. 0g anhydrous potassium carbonate 30.0g sodium bromide
Add 1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g water to make one sentence.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Hydroacetic acid
Add 10.0 mm of ice water to make one sentence, and adjust the pH to 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0g Solid sulfite ~ Sodium 8.5g Sodium metasulfite 2.3g Add water to 141
and adjust the pH to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5aJ
L Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7. Srm
Add 1 water to make 1 sentence.

The resulting graininess (RM S ) is shown in Table 2. The amount of DIR compound added to each color-sensitive layer was controlled so that the desensitization and density reduction of the white layer were approximately equal. In addition, when the amount of developed silver in the maximum density area after each treatment was measured,
In all experiments 1 to 15, the amount was between 15 and 25% based on the amount of silver coated.

As is clear from Margin Table 2 below, graininess (RMS) was smaller in Experiments 7 to 15 of the present invention compared to Comparative Experiments 1 to 6.
It can be seen that the graininess has been improved even by visual inspection, and it can be seen that this is very preferable.

Example 2 Produced in the same manner as the core/shell type silver iodobromide emulsions B to D used in Example 1, with a shell thickness of 0.05 JL 11 and a silver iodobromide content as shown in Table 3. Separately, tabular silver iodobromide emulsion E was prepared in the same manner as the silver iodide content shown in Table 3. Samples Nos. 16 to 029 were prepared using the core/shell type emulsion in the green-sensitive layer and the tabular emulsion in the red-sensitive layer, and the amount of coated silver was varied as shown in Table 3 by the method described in Example 1. Created. In addition, 1 mol Ag of Exemplified Compound D-110,2x 10-' mol and 1 mol Ag of Exemplified Compound A-11,OX 10-2 mol were added to the green-sensitive layer, and Exemplified Compound D-140 was added to the red-sensitive layer. ,2
xlO-2 mol 1 mol Ag and exemplified compound B -10,0
2 x 10-'' moles of 1 mole Ag were added.

After exposing samples No. 16 to No. 29, color development was carried out using the same processing solution and processing steps as in Example 1 for 3 minutes and 30 seconds at 38° C.
and 55°C.

In addition, the temperature at which the sensitivity obtained by each treatment is almost the same is 38°C for 3 minutes and 30 seconds, while it is 55°C for 1 minute.
It was ℃.

The graininess (RMS) of the processed sample was measured.

The RMS improvement ratio was calculated using the following formula and is shown in Table 3.

As is clear from Table 3, in the present invention, the silver iodide content
It can be seen that a value of [Developed silver amount of maximum C area]/[Total silver amount] of 0.5 or less at mole % or more improves graininess and is very preferable.

Example 3 Using sample No. 26 of Example 2, the effect of adding an inhibitor to the color developer was investigated. Color development was carried out for 1 minute at 55°C using the processing solution of Example 1, and the inhibitor shown in Table 4 was added to the color development solution, and development was carried out to determine graininess (RMS value).
was measured.

Table 4 As is clear from Table 4, it is preferable to add an organic inhibitor to the color developing solution in the present invention.

Example 4 In the method for producing the light-sensitive material of Example 1, the sample amount, silver iodobromide content, and coated silver amount were the same as in Example 2, and the fifth layer and above, that is, the sixth layer and above, were recorded. A photosensitive material coated with each emulsion layer was prepared as shown below.

6th layer...0.3g? 11j color coloi I-translation, 0
．． 2g of contaminated disease [2,5-di-L-octylhydroquinone] dissolved in 0.11g of DBP and 2,1
One layer of yellow filter containing g of gelatin.

7th layer: -1.02g low-sensitivity blue-sensitive silver iodobromide emulsion layer (
Agl; 4 mol%), 1.9 g of gelatin and 1.
84 g of α-14-(1-benzyl-2-phenyl-3
,5-dioxo-1,2,4-t-riazolysinyl)
1-α-pivaloyl-2-chloro-5-[γ-(2,4
C1.-C1. ! Low speed blue sensitive silver halide emulsion layer containing 13g DBP.

8th layer: 1.6g of high-sensitivity dispersion, 9-sensitive silver iodobromide emulsion layer (AgI, 4 mol%), 2-0g of gelatin and 46g of yellow coupler (y-i) dissolved. A highly sensitive blue-sensitive silver halide emulsion layer containing 0.23 g of DBP.

Ninth layer... - protective layer made of gelatin (sixth layer in Example 1)
layer).

When the same experiment as in Example 2 was conducted on the above light-sensitive material sample, it was found that the sample amount of Example 2, [Developed silver amount of 11λ large C area]/[Total silver amount] (%) and RMS improvement of 26 ratio(
%) results were almost the same.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent attorney Nobuaki Sakaguchi (and 1 other person)

Claims (2)

[Claims] (1) Contains core-shell silver halide grains containing 3.0 mol% or more of silver iodide and/or tabular silver halide grains containing 3.0 mol% or more of silver iodide, and has a solubility product with silver ions. After imagewise exposure of a silver halide color photographic light-sensitive material containing a compound that releases an inhibitor or inhibitor breaker that forms a silver salt having a silver salt of 1×10^-^9 or less during development processing, an aromatic primary amine is used. Using a color developing solution containing a color developing agent, color development processing is performed for 120 seconds or less and in such a way that the value of [Developed silver amount in maximum density area]/[Total silver amount] is 0.5 or less. A method for processing a silver halide color photographic material, characterized by: (2) The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color development processing temperature is 43° C. or higher.