JP2684437B2 - Silver halide color photographic light-sensitive material and color image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method using the same. More particularly, the present invention relates to a silver halide color photographic light-sensitive material suitable for ultra-fast processing capable of providing an excellent image with little color turbidity even in a short-time rapid development processing, and a color image forming method thereof.

(Prior Art) A method of developing a silver halide grain exposed with an aromatic primary amine compound as a developing agent, and forming a color image by coupling of an oxidized form of the developing agent and a color coupler formed thereby. Is a well-known technique and widely used as so-called silver halide photography.

In the photographic industry, it has always been one of important tasks to develop a photographic light-sensitive material as quickly as possible because it is necessary to improve productivity of a photofinishing laboratory and shorten customer waiting time.

The easiest method for rapidly developing a photographic light-sensitive material is to activate the reaction by increasing the processing temperature, and this method has already been used to greatly reduce the time required for the development processing.

On the other hand, in recent years, a large number of techniques for rapidly performing development processing using high silver chloride silver halide grains have been disclosed (for example, JP-A-58-95345, 59-232342 and 60-19140).
issue). By using the high silver chloride silver halide grains, the color development processing time which was conventionally required for 3 minutes or more was shortened to 1 minute or less.

A technique for realizing a shorter processing time by using a silver halide emulsion having a high silver chloride content has also been disclosed (Japanese Patent Laid-Open Nos. 196044, 2-28642 and 2-5).
No. 4261). These techniques disclose methods for improving the minimum density of the unexposed area, the storage stability of the dye image, and the mechanical strength of the surface of the photosensitive material, which are easily damaged by rapid processing.

(Problems to be solved by the invention) However, as a result of various studies, the color development processing time
It has been found that there is a problem that color turbidity occurs in the obtained image as a big problem when performing ultra-quick processing for a short time such as 45 seconds or less. Moreover, although the problem of color turbidity, which tends to accelerate the color developing process, also becomes large, the above-mentioned prior art has not shown any solution to this problem.

On the other hand, in JP-B-36-21592, by interposing an intermediate layer containing a diffusion-resistant color forming coupler between silver halide emulsion layers having different color sensitivities, color mixing between emulsion layers is prevented, and rather, color mixing is performed to some extent. The method of adjusting the apparent hue of the coloring dye by doing so is disclosed. However, even if a specific color can be preferably changed by such a method, it is not preferable because it causes an increase in color turbidity in the whole of various colors.

Further, among the above-mentioned prior arts, a technique for intentionally causing color turbidity to realize apparent hue improvement and tone reproducibility improvement is disclosed in JP-B-54-41896, JP-A-56-109345, and JP-A-56-109345. It is disclosed in JP-A-61-191657 and JP-A-2-100046. However, these techniques are basically based on intentionally causing color mixing between the silver halide emulsion layers, and are therefore not preferable from the viewpoint of increasing color turbidity when viewed in various colors as a whole.

On the other hand, an object of the present invention is to provide a method for obtaining a high color density while eliminating color mixing between silver halide emulsion layers.

Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining a good color image with little color turbidity, particularly suitable for rapid color development, and a color image forming method using the same. To do.

The second object of the present invention is to increase the utilization efficiency of the oxidized color developer as the main component of the color developing solution produced by the development of a silver halide emulsion, thereby obtaining a high-density dye image with a smaller amount of silver halide. A silver color photographic light-sensitive material and a color image forming method using the same.

(Means for Solving the Problems) As a result of repeated studies to achieve the above object, the present invention has led to the invention of the following silver halide color photographic light-sensitive material and a color image forming method using the same.

(1) In a color photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivities on a reflective support, the color photographic light-sensitive material comprises a diffusion-resistant cyan coupler-containing layer and a diffusion-resistant magenta coupler. A silver halide having at least one containing layer and at least one diffusion-resistant yellow coupler containing layer, and at least one coupler containing layer capable of supplying an oxidized product of a developing agent to this coupler containing layer during color development. Monodispersed chlorobromide wherein the emulsion layers are constructed so as to be substantially adjacent to each other and the silver halide emulsion is substantially free of silver iodide and contains 95 mol% or more of silver chloride. A silver halide color photographic light-sensitive material comprising silver or silver chloride grains.

(2) At least 1 is provided between the coupler layers having different hues.
The silver halide color photographic light-sensitive material as described in (1) above, which has a color-mixing preventing layer capable of substantially preventing migration of an oxidized product of a developing agent.

(3) In at least one silver halide emulsion layer,
The layer containing a coupler that forms a dye having a high absorption coefficient for light having spectral sensitivity to the silver halide is adjacent to at least one of the emulsion layers as a substantially separate layer. 2) A silver halide color photographic light-sensitive material described in the above.

(4) In a color image forming method for obtaining a dye image by developing a silver halide color photographic light-sensitive material after exposure with a developer containing an aromatic primary amine color developing agent, the color photographic light-sensitive material is The photosensitive material according to (1) above, and the time required for the color development step is 5 seconds or more 45.
A method for forming a color image, which is less than a second.

(5) The color image forming method as described in (4) above, wherein the color developing solution contains at least one N-hydroxyalkyl-substituted paraphenylenediamine color developing agent.

As a result of various investigations by the inventor, the problem of color turbidity associated with the above-mentioned ultra-acceleration is that a large amount of color is developed in a short time in the silver halide emulsion layer when the color development time is set to 45 seconds or less. The present invention as described above is based on the assumption that an oxidized product of a developing agent is generated, and this is diffused into another layer to form an unnecessary dye, which tends to cause color turbidity.

The silver halide color photographic light-sensitive material of the present invention comprises at least three silver halide emulsion layers having different spectral sensitivities (for example, red-sensitive, green-sensitive and blue-sensitive emulsion layers, and further three types in the region including infrared). Emulsion layers having different spectral sensitivities)
And the cyan coupler-containing layer, the magenta coupler-containing layer and the yellow coupler-containing layer may be the same layer or different layers, and at least any one of the coupler-containing layers may have a halogen corresponding to the coupler. The silver halide emulsion layer (which may or may not contain the coupler separately in the emulsion layer) is substantially adjacent to the emulsion layer.

That is, according to the present invention, as described above, an oxidized color developing agent capable of forming a large amount of dye in an emulsion layer, particularly in a short time, and diffusing into other layers to form unnecessary dyes, It was found that the coupler in another layer provided adjacently suppresses the generation of color turbidity and further the coupler which captures the oxidant contributes effectively to dye image formation.

Therefore, it has been found that the color density can be increased by adopting the constitution of the present invention even in the case of a mode in which a large amount of the oxidized color developing agent is not generated or diffusion to other layers is difficult to occur. It is presumed that this is because the oxidized developing agent generated near the adjacent layer effectively contributes to the color density. Furthermore, even when a large amount of a color mixing inhibitor is used in the so-called intermediate layer to prevent color turbidity, the constitution of the present invention makes it possible to efficiently prevent a decrease in maximum density.

Here, "substantially different layer" means that the coupler-containing layer is applied as a distinct separate layer, and also as a colloidal solution of coupler and fine solids emulsified and dispersed in gelatin aqueous solution as oil droplets in gelatin oversolution. It also includes the case where the silver halide grains present in the above are coated in a mixed state and then separated to form another layer with an unclear boundary in some cases.

Furthermore, the light-sensitive material of the present invention preferably has at least one color-mixing preventing layer which can substantially prevent the migration of the oxidized product of the developing agent between the coupler layers having different hues in the above structure.

The fact that the migration of the oxidized form of the developing agent can be substantially prevented means that no color mixing is observed between the coupler layers having different coloring hues during color development processing, and the development as described in the above-mentioned prior art. It is clearly distinguished from the layer for controlling the migration of the oxidized form of the main drug to cause proper color mixing.

In order to substantially prevent the migration of the oxidized product of the developing agent, a conventional 0.1 to 1 mmol / m ² so-called color antifoggant is used. In the present invention, a coupler layer is provided separately from the silver halide emulsion layer. The amount of the above color antifoggant used is
It may be 0.1 mmol / m ² or less. That is, since the amount of the color fog inhibitor used depends on the arrangement of the coupler layer, the amount cannot be limited in the present invention.

On the other hand, a technology relating to a silver halide light-sensitive material having a two-layer silver halide emulsion layer of a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer and a non-light-sensitive layer containing a diffusion-resistant coupler has been published. (JP-A-53-58236,
No. 50-155226). These are inventions for the purpose of improving the sensitivity and / or the sharpness of a silver halide light-sensitive material for photography. According to the specification, silver iodobromide is used as the silver halide and the development to be applied is made. The time is several times longer than that of the present invention. Therefore, the effect of improving color turbidity in rapid processing as in the present invention could not be analogized from these prior arts. The reason why these techniques are completely unrelated to the present invention is that the halogen composition of the silver halide that can be used, the development processing time, the composition of the developing solution, and the like are greatly different, and the method of observing or utilizing the dye image is different. It may be due to something completely different. That is, the above-mentioned light-sensitive material of the prior art is one in which a dye image is formed on a transparent support and observed or utilized by transmitted light, whereas the light-sensitive material of the present invention forms a dye image on a reflective support. It is a light-sensitive material that is observed by reflected light. In the latter case, the effect of color turbidity is practically large, whereas in the former case, this effect is much smaller, and it is considered that there was no problem at all.

In the present invention, in particular, the color photographic light-sensitive material according to the present invention wherein the silver halide emulsion is composed of monodispersed silver chlorobromide or silver chloride grains containing substantially no silver iodide and 95 mol% or more of silver chloride. Using, the temperature is 30 degrees or more and 50 degrees C or less, and the required time is 5 seconds or more and 5 seconds or less, especially 5 seconds or more
It is preferable to perform an ultra-rapid color development process for 30 seconds or less.

In particular, when at least one N-hydroxyalkyl-substituted paraphenylenediamine color developing agent is contained as a color developing solution, the effect of the present invention becomes remarkable and rapid processing suitability is increased, which is preferable.

Specific examples of the method for installing the coupler-containing non-photosensitive layer in the present invention are described below, but the embodiments of the present invention are not limited thereto.

(1) Red-sensitive silver halide emulsion layer containing cyan coupler (hereinafter abbreviated as C-R layer), green photosensitive silver halide emulsion layer containing magenta coupler (hereinafter abbreviated as MG) and yellow For a color photographic light-sensitive material having three light-sensitive layers of a blue-sensitive silver halide emulsion layer containing a coupler (hereinafter abbreviated as YB), at least one light-sensitive layer is adjacent to the same coupler as the light-sensitive layer. A non-photosensitive layer containing a photosensitive silver halide (hereinafter, a non-photosensitive layer containing a cyan coupler is a C layer, a non-photosensitive layer containing a magenta coupler is an M layer, and a non-photosensitive layer containing a yellow coupler is a Y layer). Abbreviated as a layer). In addition to the above abbreviations, more specific constitutional examples will be described below with the non-photosensitive intermediate layer containing a color mixing inhibitor and containing no coupler as the I layer and the protective layer as the P layer.

P layer / CR layer / C layer / I layer / MG layer / I layer / YB layer / support P layer / CR layer / I layer / M layer / MG layer / I layer / Y-B layer / support P layer / C-R layer / I layer / MG layer / M layer / I layer / Y-B layer / support P layer / CR layer / I layer / M- G layer / M layer / Y layer / Y-B layer / support (2) A method of providing a non-photosensitive layer containing a coupler on both sides of a corresponding silver halide emulsion layer by the method of (1) above.
That is, a specific configuration example will be described below.

P layer / C layer / CR layer / C layer / I layer / MG layer / I layer / YB layer / support P layer / CR layer / I layer / M layer / MG layer / M layer / I layer / Y-B layer / support P layer / CR layer / I layer / MG layer / I layer / Y layer / Y-B layer / Y layer / support (3) Above The method of (2), wherein the coupler is not contained in the silver halide emulsion layer sandwiched between the coupler-containing non-photosensitive layers. That is, a specific constitutional example will be described below, in which the red-sensitive silver halide emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer containing no coupler are respectively defined as R layer, G layer and B layer.

P layer / C layer / R layer / C layer / I layer / MG layer / I layer / YB layer / support P layer / CR layer / I layer / M layer / G layer / M layer / I layer / Y-B layer / support P layer / C-R layer / I layer / MG layer / I layer / Y layer / B layer / Y layer / support (4) Above (1) to (3) ) Of the combination of ~.

(5) A method in which the positions of the photosensitive silver halide emulsion layers in (1) to (3) above are freely interchanged, and at the same time a corresponding coupler-containing non-photosensitive layer is provided in the same manner as above.

(6) The so-called false color sensitization in which the photosensitive silver halide emulsion layers in (1) to (5) above are not red-sensitive, green-sensitive or blue-sensitive but have three different spectral sensitivities in the region including infrared. (1) ~ except that it is a material
The same method as (5) in which a coupler-containing non-photosensitive layer is provided.

(7) The same method as (1) to (6) except that in the embodiments (1) to (6), at least one non-photosensitive intermediate layer containing no coupler is omitted.

The method (3) has a further advantage that the utilization rate of couplers is increased and a sufficient density can be obtained even if the total amount of couplers used is reduced.

 Hereinafter, the present invention will be described in detail.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the coloring hue of the coupler may not have the above correspondence.

As the silver halide agent used in the present invention, a silver chlorobromide or a silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 0.1 mol% or less, preferably 0.02 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

The high silver chloride emulsion used in the present invention has a silver chloride content of 95 mol% or more, more preferably 98 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is one grown epitaxially at the corners of the grains.

On the other hand, in order to minimize sensitivity deterioration when the light-sensitive material is subjected to pressure, even in a high-silver chloride emulsion having a silver chloride content of 95 mol% or more, it is preferable to use grains of uniform structure with a small distribution of halogen composition in the grains. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is determined by the diameter of the salt equivalent to the projected area of the grain and the number average thereof is taken) is 0.2 to 1.0 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer or to perform multi-layer coating in order to obtain a wide latitude. Thus, when a plurality of silver halide grains having different grain sizes are used in a light-sensitive material, the ratio of the average grain size of the silver halide grains, regardless of whether they coexist in the same light-sensitive layer or in different light-sensitive layers, is used. Is preferably 0.63 or more and 1.6 or less, 0.7
More preferably, it is 7 or more and 1.3 or less.

The shape of silver halide grains contained in a photographic emulsion is regular (regula, tetradecahedral or octahedral).
r) Those having a crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a complex form thereof can be used. Also,
It may be a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, emulsions in which the average tabular grain having an average aspect ratio (diameter / circle in terms of circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds is preferably 10 ^-9 to 10 ^-2 mol per mol of silver halide over a wide range depending on the purpose.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion used in the present invention is usually subjected to spectral sensitization.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds and the spectral sensitization method, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention prevents scales during the manufacturing process, storage or photographic processing of the light-sensitive material.
Alternatively, various compounds or whole bodies thereof can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

The color light-sensitive material used in the present invention includes a yellow coupler which forms yellow, magenta and cyan colors by coupling with an oxidation product of an aromatic amine color developing agent,
Magenta couplers and cyan couplers are commonly used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) General formula (Y) In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group. In the general formula (C-I), when R ₃ and R ₂ do not form a ring, R ₂ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms,
An alkyl group having 2 to 4 carbon atoms is particularly preferable.
Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. In formulas (C-I) and (C-II), preferred Y ₁ and Y ₂ are a hydrogen atom, a halogen atom, and
An alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. The preferred Y ₃ sulfur is of the type that desorbs at either oxygen or carbon atoms, and the sulfur atom desorption type as described, for example, in US Pat. No. 4,351,897 and WO88 / 94795 is particularly preferred.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazoles based on U.S. Pat. No. 4,500,630 are used in view of the small yellow sub-absorption of the coloring dye and the light fastness. Are preferred and are described in US Pat.
Pyrazolo [1,5-b] [1,2,4] triazole described in JP-A-40,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Razoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A No. 226,849 or 294,785 having an alkoxy group or an aryloxy group at the 6-position as described in JP-A No. 294,785. The use of pyrazolotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Where R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
The substituents of R ₁₃ and R ₁₄ are the same as the substituents allowed for R ₁ , and the leaving group Y ₅ is preferably a group which leaves either an oxygen atom or a nitrogen atom. The nitrogen base paper release type is particularly preferable.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

Specific examples of the couplers represented by formulas (CI) and (C-II) are listed below.

Specific examples of the couplers represented by formulas (MI) and (M-II) are listed below.

Specific examples of the coupler represented by formula (Y) are listed below.

The couplers represented by the above general formulas (CI) to (Y) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol, per mol of silver halide.
It is contained in an amount of 1 to 0.5 mol.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound which is immiscible with water and has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, other than the general formulas (A) to (E), and may be a good solvent for the coupler. Can be used. The melting point of the high boiling organic solvent is preferably 80 ° C.
It is as follows. The boiling point of the high-boiling organic solvent is preferably 160
℃ or more, more preferably 170 ℃ or more.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

Further, these couplers are impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a fresh aqueous colloid solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

Various fading inhibitors can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic fading inhibitors for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silinating or alkylating the phenolic hydroxyl groups of these compounds. Can be mentioned. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,41
8,613, 2,700,453, 2,701,197, 2,728,659
No. 2,732,300, 2,735,765, 3,982,944,
No. 4,430,425, UK Patent No. 1,363,921, U.S. Patent No. 2,
710,801 and 2,816,028 include 6-hydroxycyclomans, 5-hydroxycoumarans, and spirochromans as described in U.S. Pat. Nos. 3,432,300, 3,573,050, and 3,574,
No. 627, No. 3,698,909, No. 3,764,337, JP-A-52-152
No. 225, spiroindanes are described in U.S. Pat.
, P-alkoxyphenols are described in US Pat. No. 2,735,
No. 765, British Patent No. 2,066,975, JP-A-59-10539,
Japanese Patent Publication No. 57-19765 and the like, hindered phenols, U.S. Pat.No. 3,700,455, JP-A No. 52-72224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. Benzene and aminophenol are U.S. Pat. Nos. 3,457,079 and 4,332,886, respectively.
In Japanese Examined Patent Publication No. 56-21144, hindered amines include U.S. Pat.Nos. 3,336,135, 4,268,593, and British Patent 1,326,
889, 1,354,313, 1,410,846, Japanese Patent Publication 51-142
No. 0, JP-A-58-114036, 59-53846, 59-7834
No. 4, etc., metal complexes are disclosed in U.S. Pat. Nos. 4,050,938 and 4,24.
1,155, British Patent No. 2,027,731 (A), etc., respectively. These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794, a 4-thiazolidone compound (for example, those described in US Pat. (For example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
5,805, 3,707,395), a butadiene compound (as described in US Pat. No. 4,045,229), or a benzooxide compound (for example, US Pat.
(Items described in No. 070, No. 3,677,672, No. 4,271,307)
Can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer. Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inactive and substantially colorless compound by combining with an aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented. More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) n-X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by the general formulas (FI) and (F II) are described in the specifications such as JP-A Nos. 63-158545, 62-283338, EP 298321, and 277589. Those that have been described are preferable. On the other hand, by chemically bonding with the oxidation product of the aromatic amine-based developing agent remaining after the color development processing,
More preferred compound (G) which is chemically inert and produces a colorless compound can be represented by the following general formula (GI).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968) are the above groups, or groups derived therefrom are preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
No. 229145, Japanese Patent Application No. 63-136724, JP-A-1-57259
And those disclosed in European Patent Publication Nos. 298321 and 277589 are preferable.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material used in the present invention includes a hydroquinone derivative, an aminophenol derivative,
It may contain gallic acid derivatives, ascorbic acid derivatives and the like.

The light-sensitive material used in the present invention may contain a water-soluble dye or a dye which becomes water-soluble by photographic processing in the hydrophilic colloid layer as a filter dye, or for various purposes such as prevention of irradiation or halation. . Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose sulfate, Examples include polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, and the like.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, particularly a thermoplastic resin, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, for example, JP-A-61-210346,
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), GF Duffin, Potograpic Emulsion Chemistry
(Focal Pree, 1966), VL Zelikman et al Ma
king and Coating Photographic Emuldion (Focal Pres
s company, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic medium from the coupler dispersion by a method such as distillation, washing with noodles, or ultrafiltration, it was mixed with a photographic emulsion.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4-amino-N, N-diethyl-3-methylaniline D-3 4-amino-N (β-hydroxyethyl) N-
Methylaniline D-4 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline D-5 4-Amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline D-6 4 -Amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline D-7 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline D-8 4-amino -N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline D-9 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline D-10 4-amino-N -Ethyl-N- (β-methoxyethyl) -3-methyl-aniline D-11 4-amino-N- (β-ethoxyethyl) -N
-Ethyl-3-methylaniline D-12 4-amino-N- (3-carbamoylpropyl-Nn-propyl-3-methylaniline D-13 4-amino-N- (4-carbamoylbutyl-
Nn-propyl-3-methylaniline D-14 N- (4-amino-3-methylphenyl) -3
-Hydroxypyrrolidine D-15 N- (4-amino-3-methylphenyl) -3
-(Hydroxymethyl) pyrrolidine D-16 N- (4-amino-3-methylphenyl) -3
-Pyrrolidinecarboxamide Of the above p-phenylenediamine derivatives, Exemplified Compounds D-3 to D-8 and D-12 are preferable, but particularly preferable are Exemplified Compounds D-3 to D-7 to obtain the effects of the present invention. At least one N-hydroxyalkyl-substituted paraphenylenediamine color developing agent is used.
In addition, these p-phenylenediamine derivatives and sulfates, hydrochlorides, phosphites, naphthalenedisulfonic acid, p-
It may be a salt such as toluenesulfonic acid. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.2 mol, and more preferably 0.005 mol to 0.1 mol, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, the ions are excluded from a very small amount of sulfurous acid used for the oxidation prevention of the kit of the processing agent in which the developing agent is concentrated before preparing the solution for use.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. If desired, the aromatic polyhydroxy compounds described in 3,746,544 and the like may be contained. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and details thereof are described in JP-A-1-9795.
No. 3, No. 1-186939, No. 1-186940, No. 1-187557
No. etc.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939 and JP-A-1-186939. Amines such as those described in US Pat.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
The content is preferably from × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /
It is. When the bromine ion concentration is more than 1 × 10 ^-4 mol / l, the development is delayed, the maximum density and the sensitivity are lowered, and 3.0
If it is less than 10 ⁻⁵ mol / mol, fog tends to occur.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may contain compounds of other known developer components.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonates, phosphates, tetraborate salts, and hydroxybenzoates are soluble and have a pH of 9.0 or above.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantages of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylsulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1 , 2-Diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'- Examples thereof include bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, the amount is about 0.1 g to 10 g per color developer. An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-4329, U.S. Pat. Nos. 1,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Amine compounds described in 546, 2,596,926 and 3,582,346 etc., Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Pat.Nos. 3,128,183, 41-11431, 42-23883
No. 3 and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer applicable to the present invention is 30 ° C.
To 50 ° C, preferably 35 ° C to 50 ° C. Processing time is 5 seconds ~
30 seconds, preferably 5 seconds to 20 seconds. The replenishment amount is preferably small, but ^{20 to} 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, and preferably 30 to 100 ml.

When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, opening ratio = area of contact between processing liquid and air (cm ² ) / volume of processing liquid (cm ³ ). The above opening ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05.

As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. Examples thereof include the slit developing treatment method described in No. 63-216050.

In order to reduce the aperture ratio, it is preferable to apply not only in both the color development and black and white development steps, but also in the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing, stabilizing and the like.

Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used, but in particular, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, complex salts such as phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide, etc. preferable.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, ferric phosphate, etc. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt.
Among the iron complexes, iron aminopolycarboxylate complexes are preferable, and the amount of addition is 0.01 to 1.0 mol /, preferably 0.05 to 1.0 mol / mol.
~ 0.50 mol /.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, compounds having a mercapto group or a disulfide bond described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978). , Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, 53
-32735, U.S. Pat. Nos. 3,706, 561 and the like, thiourea compounds and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. Rehalogenating agents such as halides (eg ammonium iodide) can be included. If necessary, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium sulfate and guanidine can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiosulfates such as sodium thiocyanate; Thiocyanate: a thioether compound such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and a water-soluble silver halide solubilizer such as ureas, and one or more of these may be used. It can be mixed and used.

Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per one is 0.2 ~
2 mol is preferable, and 0.3 to 1.0 mol is more preferable. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 9, and more preferably from 4 to 8.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, quenchers, surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution or fixing solution contains sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. , Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like. It is preferable that these compounds are contained in an amount of about 0.02 to 1.0 mol / mol, and more preferably 0.04 to 0.6 mol / mol, in terms of sulfite ion.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. After desilvering processing such as fixing or bleach-fixing, washing and / or stabilization processing is generally performed.

The amount of rinsing water in the rinsing process can be set within a wide range depending on the characteristics of the photosensitive material (for example, the material used such as couplers) and applications, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment methods such as alternating current, forward flow, and other various conditions. You can Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in Journal of the Society of Motion Picture and Television Engineers (Jounal
of the Society of Motion Picture and Television E
ngineers) 64, p.248-253 (May 1955 issue). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 5.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, Copper Ions and Others by Hiroshi Horiguchi, "The Chemistry of Bactericidal and Antifungal Activities" (1986
Sankyo Idemita, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (1986), The bactericide described in can be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound capable of stabilizing an image is added to the stabilizing solution. For example, an aldehyde compound typified by formalin or a film suitable for stabilizing a dye.
Examples include buffers for preparing ph and ammonium compounds. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

In the present invention, the water washed and / or stabilized may be treated with a reverse osmosis membrane. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether,
Although polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used, a cross-linked polyimide-based composite membrane or a polysulfone-based composite membrane is preferable because the permeated water amount does not easily decrease.

Also, from the viewpoint of reducing the initial cost, running cost, downsizing, and noise reduction of the pump, etc.
A low-pressure reverse osmosis membrane that can be used at a liquid sending pressure as low as 15 kg / cm ² is preferable. Furthermore, the structure of the membrane is preferably a spiral membrane in which a flat membrane is wound into a roll shape, because the amount of permeated water is less likely to decrease.

Although the liquid feeding pressure in the use of these membranes is in the range as described above, the preferable condition is ^{2 to} 10 kg / cm ² , and the particularly preferable condition is 3 to 7 kg / cm ² for the stain prevention effect and the reduction of the permeated water amount. is there.

The washing and / or stabilizing step is preferably performed by connecting in a multi-stage countercurrent system with a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The treatment with the reverse osmosis membrane is preferably performed on the water in the multistage countercurrent washing and / or stabilizing tank after the second tank. Specifically, the water in the second tank in the case of the two-tank configuration, the second or third tank in the case of the three-tank configuration, and the water in the third or fourth tank in the case of the four-tank configuration is treated with a reverse osmosis membrane and permeated. This is carried out by returning the water to the same tank (a tank from which water was collected for reverse osmosis membrane treatment; hereinafter, referred to as a collection tank) or a washing and / or stabilization tank located thereafter. Further, returning the concentrated washing and / or stabilizing solution to the bleach-fix bath upstream of the collection tank is one measure.

The pH of the washing step or the stabilizing step is preferably 4-10, more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 to 50 ° C, preferably 25 to 45 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably
The duration is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 4 times the amount of light-sensitive material and the amount brought in from the previous bath per unit area.
It is 0 times. Further, it is 500 ml or less, preferably 300 ml or less per 1 m ^{2 of the} light-sensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by reducing overflow of washing water by a multi-stage countercurrent system to flow into the bleach-fixing bath of the preceding bath and replenishing the concentrated solution in the bleach-fixing bath.

 The drying step that can be used in the present invention will be described.

A drying time of 5 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention.

As a means for shortening the drying time, a means on the light-sensitive material side can be improved by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after the washing bath. As a means of improvement from the dryer, it goes without saying that it is possible to accelerate the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the irradiation angle of the drying air to the light-sensitive material and the method of removing the discharged air.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indaniline compounds described in U.S. Pat. , JP-A-53
The urethane compound described in No. 135628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547 and JP-A-58-115.
No. 438 and the like.

Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,296,770 or US Pat. No. 3,674,499 may be performed.

In the color image forming method of the invention, more preferable embodiments are shown below.

(1) A color image forming method according to the color image forming method of the present invention, wherein the color developing solution contains substantially no benzyl alcohol.

(2) A color image forming method according to the color image forming method of the present invention, wherein the color developing solution contains substantially no sulfite ion.

(3) A color image forming method according to the color image forming method of the present invention, wherein the color developing solution contains substantially no hydroxylamine.

(4) The color image forming method according to the present invention, wherein the time required for the color developing step is 5 seconds or more and 20 seconds or less.

(5) A color image forming method characterized in that in the color image forming method of the present invention, a color image is obtained by bleach-fixing following the color development step, followed by washing with water and / or stabilizing treatment and drying.

(6) In the color image method (5), the temperature of color development is 30 ° C or more and 50 ° C or less, the required time is 5 seconds 3 or more and 30 seconds or less, and the temperature of the subsequent bleach-fixing is 30 ° C or more and 50 ° C or less, the required time 5 seconds or more and 30 seconds or less, the temperature of the subsequent washing and / or stabilizing treatment is 25 ° C or more and 50 ° C or less, the required time is 15 seconds or more and 40 seconds or less, the temperature of the subsequent drying process is 40 ° C or more and 80 ° C or less, and the draining process is performed. The total processing time from the start of development to the end of drying is 30 seconds or more 130 including the required time of 5 seconds to 30 seconds.
A method for forming a color image, which is less than a second.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

Example 1 Preparation of a support LBKP (hardwood bleached, sulfate pulp) 100 for photographic printing paper
% (Weight: 175 g / m ² , thickness: about 180 μm); a white pigment-containing resin layer made of water-resistant titanium oxide having the following composition was provided on the surface of white base paper to form a support. That is, polyethylene composition (density 0.920 g / cm ³ , Melton index (MI) 5.0 g
/ 10 minutes) 90 parts by weight, 16 parts by weight of a titanium oxide white pigment surface-treated with silicon oxide and aluminum oxide are added, and a bluish dye (ultra-blue) is further added and kneaded, followed by melt extrusion coating to give a thickness of 30 μm. A water resistant resin layer was obtained.
On the other hand, another polyethylene composition (density 0.
950g / cm ^3, MI8.0g / 10 minutes) only coating to 20μm
To obtain a water resistant resin layer.

Preparation of silver halide emulsion layer (A-1) 25 g of lime-processed gelatin was added to 800 ml of distilled water, dissolved at 40 ° C., and the pH was adjusted to 3.8 with sulfuric acid. In this aqueous solution,
Further, an aqueous solution (I) was prepared by dissolving 1.2 g of sodium chloride and 0.02 g of N, N'-dimethylethylenethiourea.
Next, an aqueous solution (II-a) was prepared by dissolving 100 g of silver nitrate in 400 ml of distilled water, and an aqueous solution (III-a) was obtained by dissolving 34.5 g of sodium chloride in 400 ml of distilled water. Then silver nitrate 2
A solution prepared by dissolving 5 g in 100 ml of distilled water was used as an aqueous solution (II-b), and a solution of 8.5 g of sodium chloride, 10 mg of yellow blood salt and 0.015 mg of dipotassium iridium hexachloride in 500 ml of distilled water was used as an aqueous solution (III-b). ). Next, the aqueous solution (II-a) and the aqueous solution (III-
After adding and mixing a) for 40 minutes at the same time, subsequently, the aqueous solution (II-b) and the aqueous solution (III-b) are simultaneously mixed for 10 minutes.
Add and mix over minutes. Excess salts were removed from the dispersion of silver halide grains obtained by the above operation by the coagulation sedimentation method, and 76 g of lime-processed gelatin was added and dispersed again. The following spectral sensitizing dye (V-
1) was spectrally sensitized by adding 4.6 × 10 ^-4 mol per mol of silver halide, and N, N, N was formed while silver bromide was formed on silver chloride grains already formed by the halogen conversion method. ′
-Sulfur sensitized with triethylthiourea.

As above, average particle size 0.54μm, coefficient of variation
A cubic silver chlorobromide emulsion (A-1) having 0.09 and a silver chloride content of 99.6 mol% was prepared.

Preparation of Silver Halide Emulsion (B-1) The following spectral sensitizing dye (V-2) was used instead of the spectral sensitizing dye (V-1) used for preparing the silver halide emulsion (A-1).
And (V-3) per mol of silver halide, respectively.
The same method as for the emulsion (A-1) except that 4.2 × 10 ⁻⁴ mol and 7.2 × 10 ⁻⁵ mol were used, except that the aqueous solutions (I) and (II-a) in the preparation method of the emulsion (A-1) were used. , (II-b),
(III-a) and (III-b) by adding and mixing time, temperature, stirring method by adjusting the average particle size 0.50μm,
A cubic silver halide emulsion (B-1) having a coefficient of variation of 0.08 and a silver chloride content of 99.6 mol was prepared.

Preparation of silver halide emulsion (C-1) In place of the spectral sensitizing dye (V-1) used for preparing the silver halide emulsion (A-1), the following spectral sensitizing dye (V-4)
Is used in the same manner as in Emulsion (A-1) except that 7.4 × 10 ^-5 mol is used per mol of silver halide, except that aqueous solutions (I), (II-a) and (II) in the method for preparing Emulsion A-1 are used. -B),
(III-a) and (III-b) by adding and mixing time, temperature, by adjusting the stirring method, an average particle size 0.49μm,
A cubic silver chlorobromide emulsion (C-1) having a coefficient of variation of 0.07 and a silver chloride content of 99.6 mol% was prepared.

Preparation of Light-Sensitive Materials (101) to (105) A coating solution was applied onto the water-resistant paper support prepared above to prepare a multilayer color photographic paper having the following layer structure. The coating solution was prepared as follows.

Preparation of coating solution for first layer 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g and 0.7 g of the color image stabilizer (Cpd-7), 27.2 ml of ethyl acetate, 5.5 g of solvent (Solv-1) and 5.5 g of solvent (Solv)
-3) 2.7 g was added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% aqueous gelatin solution containing 8 ml of 10% sodium dodecylbenzenesulfonate.

The emulsified dispersion and the emulsion (A-1) were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper prepared above [white dye (containing TiO ₂ and bluish dye (ultraviolet) in polyethylene on the first layer side] First layer (blue sensitive layer) Emulsion (A-1) 0.25 gelatin 0.98 Yellow coupler (ExY) 0.72 Color image stabilizer (Cpd-1) 0.17 Solvent (Solv-1) 0.21 Solvent (Solv-3) 0.10 Color image stabilizer (Cpd-7) 0.05 Second layer (mixing prevention layer) Gelatin 0.75 Mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) The emulsion (B-1) 0.13 Gelatin 0.94 Magenta coupler (ExM) 0.26 Color image stability Agent (Cpd-2) 0.05 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd) 4) 0.02 Color agent stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (UV absorption) Layer) Gelatin 1.13 UV absorber (UV-1) 0.47 Mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer ( Red-sensitive layer) Emulsion (C-1) 0.21 Gelatin 0.80 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.32 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.20 6th layer (UV absorbing layer) Gelatin 0.38 UV absorber (UV-1) 0.16 Mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 7th layer (Protecting layer) Gelatin 1.06 Polyvinyl alcohol acrylic modified copolymer (Modification degree
17%) 0.08 Liquid paraffin 0.02 2: 1 mixture (volume ratio) (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)] ₃ Thus, a photosensitive material (101) was prepared. Next, in the method for producing the light-sensitive material (101), the first layer and the second layer
The following Y-coupler layer (YL-1) or the same (YL-2) between the layers and / or the C coupler layer (CL-2) or the same (CL-2) between the fourth layer and the fifth layer. ) Was installed as shown in Table 1 to prepare photosensitive materials (102) to (105).

Y coupler layer (YL-1) Gelatin 0.25 Yellow coupler (ExY) 0.18 Color image stabilizer (Cpd-1) 0.04 Solvent (Solv-1) 0.05 Solvent (Solv-3) 0.03 Color image stabilizer (Cpd-7) 0.012 Y coupler layer (YL-2) Gelatin 0.50 Yellow coupler (ExY) 0.36 Color image stabilizer (Cpd-1) 0.08 Solvent (Solv-1) 0.11 Solvent (Solv-3) 0.05 Color image stabilizer (Cpd-7) 0.025 C coupler layer (CL-1) Gelatin 0.20 Cyan coupler (ExC) 0.08 Color image stabilizer (Cpd-6) 0.04 Color image stabilizer (Cpd-7) 0.08 Color agent stabilizer (Cpd-8) 0.01 Solvent (Solv- 6) 0.05 C coupler layer (CL-2) Gelatin 0.40 Cyan coupler (ExC) 0.16 Color image stabilizer (Cpd-6) 0.08 Color image stabilizer (Cpd-7) 0.16 Color agent stabilizer (Cpd-8) 0.02 Solvent (Solv-6) 0.10 Evaluation of Photosensitive Material For the above-mentioned photosensitive materials (101) to (105), a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used and passed through an RGB three color division filter for sensitometry. Gradation exposure was given. The exposure at this time was 0.1 seconds, and the exposure amount was 250 CMS in exposure time. The exposed sample was processed according to the procedure of the development processing (I) described below. Processing process Development process (I) Color developer 38 ℃ 20 seconds Bleaching and fixing 38 ℃ 20 seconds Rinse 38 ℃ 5 seconds Rinse 38 ℃ 5 seconds Rinse 38 ℃ 5 seconds Rinse 38 ℃ 5 seconds Rinse 38 ℃ 5 seconds Dry 65 ℃ 15 seconds (A five-tank counter-current system to the rinse was used.) (The above processing time was in the air after the photosensitive material entered one processing solution and then exited from this processing solution to the next processing solution. Say the value including time).

 The composition of each processing solution is as follows.

The replenishment amount of the above replenisher was 30 ml per 1 m ² of the light-sensitive material.

The replenishment amount of the above replenisher was 30 ml per 1 m ² of the light-sensitive material.

Rinse liquid: ion exchange water was used for both the tank liquid and the replenisher, and the replenishment rate was 55 ml / m ² .

The development processing of this embodiment was performed using an automatic developing machine.
The features of the automatic processor in this case are that each processing bath has a liquid circulation mechanism that sprays a tank liquid at a discharge rate of 2 or more per minute toward the photosensitive layer surface of the photosensitive material, and color development. It has a structure such that the ratio of the area of the surface of the bath where the developing solution is in contact with air to the volume of the developing bath layer is 0.05 m ² / ml or less, and the light-sensitive material is used in the color developing bath and the bleach-fixing bath. It has a structure such that the ratio of the air time in each bath to the time in the liquid is 0.7 or less in the process of entering the next bath through the air after entering, and between the final rinse bath and the drying part. A plurality of liquid removing rollers for wiping off the liquid adhering to the surface of the photosensitive material are arranged on the surface of the photosensitive material, and dry air is blown on the photosensitive layer surface of the photosensitive material at a wind speed of 3 m / sec or more through a porous plate or slit. In addition, the so-called return wind containing water is applied to the surface of the photosensitive material. It has a drying section which has a circulation mechanism of such air away in La quickly, and the like. By using the developing machine as described above, processing in an extremely short time becomes possible, and as a result, the effect of the present invention becomes more remarkable.

Regarding the light-sensitive materials (101) to (105) on which the C, M, and Y three-color separation dye images have been formed by the development processing (I), the G filter density when the B filter density of the yellow coloring portion is 2.0 (that is, the yellow color). The magenta turbid component of the image, hereinafter abbreviated as D _{G / Y} ), and the G filter density when the R filter density of the cyan coloring portion is 2.0 (that is, the magenta turbid component of the cyan dye, abbreviated as D _{G / C} ). It was measured. Table 2 shows the results.

From the above results, it is clear that color turbidity can be greatly improved by providing the coupler-containing non-photosensitive layer of the present invention.

Example 2 In the method for producing the light-sensitive material (101) of Example 1, the following M coupler layer (ML-1 was used between the second layer and the third layer and / or between the third layer and the fourth layer. ) Or (ML-2) is installed as shown in Table 3 to obtain a light-sensitive material (20
1) to (204) were created.

M coupler layer (ML-1) Gelatin 0.24 Magenta coupler (ExM) 0.065 Color image stabilizer (Cpd-2) 0.013 Color image stabilizer (Cpd-3) 0.02 Color image stabilizer (Cpd-4) 0.005 Color image stabilizer (Cpd-9) 0.005 Solvent (Solv-2) 0.10 M coupler layer (ML-2) Gelatin 0.47 Magenta coupler (ExM) 0.13 Color image stabilizer (Cpd-2) 0.025 Color image stabilizer (Cpd-3) 0.04 colors Image stabilizer (Cpd-4) 0.01 Color image stabilizer (Cpd-9) 0.01 Solvent (Solv-2) 0.20 Next, the above-mentioned photosensitive materials (101) and (201) to (20)
Color mixture inhibitor (Cpd-5) used in the second layer (color mixture preventing layer) and the fourth layer (ultraviolet absorbing layer) in the method 4)
Photosensitive material (10
Photosensitive materials (205) to (209) shown in Table 4 were prepared in exactly the same manner as 1) and (201) to (204).

Next, the light-sensitive materials (201) to (2
09) and the light-sensitive material (101) of Example 1 were exposed and developed in exactly the same manner as in Example 1. The reflection densities of the resulting C, M, and Y color-separated dye images were measured, and the color turbidity indexes DG _{/ Y} , _{DG / C} and yellow, magenta in the evaluation method of Example 1 were measured. Maximum density of each cyan color ▲ D ^ma _Y ▼ ^X , ▲ D ^ma _M ▼ ^X , ▲ D ^ma _C ▼ ^X
I asked. The values are shown in Table 5.

As is clear from the above results, by installing the M coupler layer (ML-1) or (ML-2) of the present invention, it is possible to first see an increase in the maximum density of a magenta color image (photosensitive material ( 201) ~ (204) results). Next, in order to prevent color mixture and suppress color turbidity, it is possible to efficiently prevent a decrease in the maximum concentration when the amount of the color mixture inhibitor (Cpd-5) in the intermediate layer (second layer and / or fourth layer) is increased. (Comparison between photosensitive material (205) and photosensitive materials (206) to (209)). Therefore, the present invention provides a method for improving color turbidity without reducing the maximum density of a color image.

In the examples of the present invention, since the coating amount of silver in the third layer (green sensitive layer) is much smaller than that in the other photosensitive layers, oxidation of the developing agent to the other layer when development occurs in this third layer. The diffusion of the body (that is, color mixing and color turbidity) is negligibly small, but when the amount of coated silver is large due to the difference in coupler etc., the M-coupler layer itself has an effect of preventing color mixing. I confirmed that there is.

Example 3 In the same manner as in the photosensitive materials (204) and (209) except that the third layer (green sensitive layer) was changed to the following in the method for producing the photosensitive materials (204) and (209) in Example 2. Photosensitive materials (324) and (329) were prepared.

Third Layer The emulsion (B-1) 0.13 gelatin 079 Next, the photosensitive materials (324) and (329) were evaluated in the same manner as in the evaluation of the photosensitive material in Example 2, and the photosensitive material in Example 2 (204) was evaluated. ) And (209), it was confirmed that the method of the present invention provides a color image with low color turbidity and high maximum density.

This result shows that the effect of the present invention can be realized by a mode in which the coupler layer which is a color forming layer and the silver halide emulsion layer which supplies the oxidized product of the developing agent to the coupler layer are separated and adjacent to each other.

Example 4 In place of the exemplary compound (D-6) of the color developing agent used in the color developer of the developing treatment (I) of Example 1, an equivalent compound of the exemplary compound (D-7) was used. Example 1 in exactly the same manner as in Example 1 (this is referred to as development processing (II)).
Photosensitive materials (101) to (105) of Example 2, photosensitive materials (201) to (209) of Example 2 and photosensitive materials (324) of Example 3 of
(329) was evaluated. As a result, as in Examples 1, 2 and 3, the effect of improving color turbidity can be recognized in the light-sensitive material of the present invention.

Example 5 In the same manner as in Example 1, Example 2 and Example 3 except that the following developing treatments (III-1) and (III-2) were performed instead of the developing treatment (I) in Example 1. Example 1
Photosensitive materials (101) to (105), photosensitive materials (201) to (209) of Example 2, and photosensitive material (32) of Example 3.
When 4) and (329) were evaluated, the effect of improving color turbidity could be recognized in the light-sensitive materials of the present invention, as in Examples 1, 2 and 3.

The composition of each processing solution is as follows.

Here, the same bleach-fixing solution and rinsing solution as those used in the developing treatment (I) of Example 1 were used.

Example 6 Example 1 is repeated except that the following developing treatments (IV-1) and (IV-2) are applied instead of the developing treatment (I) in Example 1.
When the light-sensitive materials (101) to (105) were evaluated by the same method as in (1), the results shown in Table 6 were obtained.

The compositions of the processing solutions of the developing treatments (IV-1) and (IV-2) are the same (these are the five-tank countercurrent flow system from rinsing to →) and are as follows.

Color developer Water 800 ml Ethylenediaminotetraacetic acid 2.0 g 5,6-Dihydroxybenzene-1,2,4-tolylfonic acid 0.3 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g Exemplified compound D-8 5.0 g Diethylhydroxyamine 4.2g Fluorescent whitening agent (4,4'-diaminostyreben series) 2.0g Add water 1000ml pH (25 ℃) 10.05 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid (III) Ammonium 75 g Sodium ethylenediamine tetraacetate 5 g Glacial acetic acid 9 g Water was added to 1000 ml pH (25 ° C.) 5.8 Rinse solution Ion-exchanged water (calcium and magnesium were 3 ppm or less each)
And the same.

As is clear from the above results, the effect of the present invention is remarkable when color development is performed for an extremely short time. on the other hand,
It can be understood that the effect is basically the same though the effect is small in the color development processing for a relatively long time.

Example 7 In the method for preparing the silver halide emulsion (A-1) of Example 1, the following spectral sensitizing dyes (V-5) and (V-6) were used instead of using the spectral sensitizing dye (V-1). A silver halide emulsion (A-2) was prepared in the same manner as in (A-1) except that 1.3 x 10 ^-4 mol and 1.0 x 10 ^-4 mol were added per mol of silver halide.

Next, in the method for preparing the silver halide emulsion (B-1) of Example 1, the spectral sensitizing dyes (V-2) and (V-3) were used.
(B) except that the following spectral sensitizing dye (V-7) was added in an amount of 4.5 × 10 ^-5 mol per mol of silver halide (B).
A silver halide emulsion (B-2) was prepared in exactly the same manner as in -1).

Next, in the method for preparing the silver halide emulsion (C-1) of Example 1, instead of using the spectral sensitizing dye (V-4), the following spectral sensitizing dye (V-8) was added per mol of silver halide. A silver halide emulsion (C-2) was prepared in exactly the same manner as (C-1) except that 5 × 10 ^-4 mol was added.

Next, in the method for preparing the light-sensitive material (101) of Example 1, the usage of the silver halide emulsion in the light-sensitive layer was changed as shown in Table 7 below, and the following compound was added to the third layer with silver halide 1. A light-sensitive material (611) was prepared in the same manner as the light-sensitive material (101) except that 2.6 × 10 ⁻³ mol was added per mol.

Furthermore, the first of the photosensitive materials (201) to (209) of Example 2
The light-sensitive material (layer for yellow color development), the third layer (for magenta color development), and the fifth layer (for cyan color development) are the same as the light-sensitive material (611) except that the formulation using the silver halide emulsion in Table 7 above is changed. Light-sensitive material (62)
1) to (629) are created.

These photosensitive materials are infrared-sensitive color photosensitive materials. The function of each photosensitive layer is shown in Table 8 in comparison with the photosensitive layer of the photosensitive material (101).

The other layers are the same for the photosensitive material (101) and the photosensitive material (611).

Evaluation of photosensitive materials For the photosensitive materials (611) and photosensitive materials (621) to (629) prepared as described above, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200 ° K) was used. Then, gradation exposure was applied through three types of color separation filters shown in Table 9 below. Incidentally, interference filters were used for these filters.

The exposure amount at this time was adjusted so as to be 500 erg / cm ² while passing through the above-mentioned color separation filters. The exposure time was 0.1 seconds.

The exposed photosensitive material (611) and photosensitive material (62
1) to (629), the developing treatment (I) in Example 1, the developing treatment (II) in Example 4, the developing treatments (III-1) and (III-2) in Example 5, and further Example 6 As a result of the development treatments (IV-1) and (IV-2) in Example 1, the evaluation was performed, and as a result, the image forming method of the present invention was colored by turbidity as in the case of Example 2, Example 4, Example 5 and Example 6. The improvement effect was recognized.

Example 8 In the evaluation of the light-sensitive material of Example 7, instead of using a sensitometer for exposure, a semiconductor laser (hereinafter referred to as LD) shown in Table 10 below was used for image-wise exposure. The exposure in this case refers to a process in which three light beams obtained from the following three types of LDs are combined into one light beam, and then scanning exposure is performed on a photosensitive material by a rotating polyhedron. At this time, the aperture and the like of each laser beam were adjusted so that the diameter of the bright spot on the photosensitive material was about 0.03 mm, and the intensity and irradiation time were electrically adjusted according to the required image density. The photosensitive material is imagewise exposed while moving at a constant speed in a direction perpendicular to the scanning direction,
The time required for this exposure was about 10 seconds for an image having a size of 420 mm in length and 297 mm in width.

The exposed photosensitive material (611) and photosensitive material (62
1) to (629), the developing treatment (I) in Example 1, the developing treatment (II) in Example 4, the developing treatments (III-1) and (III-2) in Example 5, and further Example 6 As a result of performing the development treatments (IV-1) and (IV-2) in Example 1 and evaluating the results, as in Example 2, Example 4, Example 5 and Example 6, color turbidity in the image forming method of the present invention. The improvement effect was recognized.

In this embodiment, the exposure wavelength and the color hue correspond as shown in Table 8, but this combination is not essential for obtaining the effects of the present invention.

(Effect of the Invention) According to the present invention, a silver halide color photographic light-sensitive material capable of obtaining a good color image with little color turbidity, particularly suitable for rapid color development, and a color image forming method using the same are obtained. be able to.

Further, a silver halide color photographic light-sensitive material and a silver halide color photographic light-sensitive material capable of obtaining a high-density dye image with a smaller amount of silver by increasing the utilization efficiency of an oxidized product of a color developing agent, which is generated by developing a silver halide emulsion. A color image forming method using can be obtained.

Claims (5)

(57) [Claims] 1. A color photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivities on a reflective support, the color photographic light-sensitive material being a diffusion-resistant cyan coupler-containing layer and a diffusion-resistant type. At least one magenta coupler-containing layer and at least one diffusion-resistant yellow coupler-containing layer, and at least one of the coupler-containing layers is a halogen capable of supplying an oxidant of a developing agent to the coupler-containing layer during color development. The silver halide emulsion layers are configured so as to be substantially adjacent to each other,
And the silver halide emulsion contains substantially no silver iodide.
A silver halide color photographic light-sensitive material characterized by comprising monodispersed silver chlorobromide or silver chloride grains having a mol% of at least silver chloride. 2. A halogen according to claim 1, further comprising at least one color-mixing preventing layer capable of substantially preventing migration of an oxidized product of a developing agent between coupler layers having different hues. Silver halide color photographic light-sensitive material. 3. A silver halide emulsion layer comprising at least one silver halide emulsion layer containing a coupler which forms a dye having a high absorption coefficient with respect to light having a spectral sensitivity.
The silver halide color photographic light-sensitive material according to claim 2, which is adjacent to at least one of the emulsion layers as a substantially different layer. 4. A color image forming method for obtaining a dye image by exposing a silver halide color photographic light-sensitive material to light and then developing it with a developing solution containing an aromatic primary amine color developing agent. A color image forming method, wherein the material is the light-sensitive material according to claim (1), and the time required for the color developing step is 5 seconds or more and 45 seconds or less. 5. The color image forming method according to claim 4, wherein the color developing solution contains at least one N-hydroxyalkyl-substituted paraphenylenediamine color developing agent.