JPH0619531B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a halogen which is capable of rapid development processing and has improved processing stability in the rapid development processing. The present invention relates to a silver halide color photographic light-sensitive material.

In general, a silver halide color photographic light-sensitive material has three kinds of photographic silver halide emulsion layers, which are selectively spectrally sensitized to have sensitivity to blue light, green light and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for color negative, a blue light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, and a red light-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. Between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, there is a bleachable yellow filter layer for absorbing blue light transmitted through the blue-sensitive silver halide emulsion layer. It is provided. Further, each emulsion layer is provided with another intermediate layer for various special purposes and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, and a blue light-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. In the same manner as in the silver halide photographic light-sensitive material for color negative, an intermediate layer such as an ultraviolet absorbing layer and a protective layer are provided for each special purpose. It is also known that each of these silver halide emulsion layers is provided in an arrangement different from that described above, and further, as each silver halide emulsion layer, it is photosensitive to each color light in substantially the same wavelength range. Have 2
It is also known to use a photosensitive silver halide emulsion layer consisting of layers. In these silver halide color photographic light-sensitive materials, the exposed silver halide grains are developed by using, for example, an aromatic primary amine type color developing agent as a color developing agent, and the generated color developing agent is oxidized. The reaction of the product with the dye-forming coupler forms a dye image. In this method, usually, in order to form a dye image of cyan, magenta and yellow, a phenol or naphthol type cyan coupler, a 5-pyrazolone type, a pyrazolinobenzimidazole type, a pyrazolotriazole type, an indazolone type or a cyano type, respectively. Acetyl magenta couplers and acylacetamide yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developing solution. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers have been previously contained in a silver halide emulsion layer to make them non-diffusible.

[Prior Art] In recent years, a silver halide color photographic light-sensitive material which is capable of rapid processing, has high image quality, excellent processing stability, and low cost has been demanded in the industry in recent years.
In the laboratory, in particular, a silver halide color photographic light-sensitive material capable of rapid development processing, improved in processing stability in the rapid development processing, and reduced in maintenance during processing is desired.

In other words, silver halide color photographic light-sensitive materials are run by an automatic processor provided in each laboratory. It is now required to return to users and even to return within a few hours from reception, and the development of silver halide color photographic light-sensitive materials that can be processed more rapidly is urgent. Has been. Further, in the running process, there is a problem in that stable photographic performance cannot be obtained because the photographic characteristics greatly change due to the composition change of the processing liquid and the change of conditions even between the laboratories or even in the same laboratories. Changes in the composition of the processing liquid and changes in conditions are
It is considered that this is due to elution / accumulation of the photographic active substance from the light-sensitive material during development processing (running) and other causes. Therefore, in order to cope with fluctuations in processing conditions, it is required that the developing time, the temperature and pH of the developing solution, and the halogen concentration in the developing solution, particularly the bromide concentration, be highly controlled. However, compared with the development time or the temperature and pH of the developing solution, the concentration of bromide ions in the developing solution is difficult to quantify, and it is difficult to control because of poor measurable property. Therefore, in particular, it is necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on the brom concentration and which is highly process-stabilized. Although processing stability is problematic even during normal processing time, processing stability becomes more problematic in rapid processing. With the rise of small-scale laboratories, which process a relatively small amount, resolution of processing stability in such rapid development processing is an important issue that must be solved in order to reduce processing maintenance. Further, it is a matter of course that such a processing-stabilized silver halide color photographic light-sensitive material is required to be provided economically at low cost.

In view of the prior art, a silver halide color photographic light-sensitive material that can be rapidly processed is disclosed in, for example, Japanese Patent Laid-Open No.
Fine graining technique of silver halide as described in JP-A No. 1-77223, JP-A-58-184142 and JP-B-56-1.
A technique for reducing silver bromide of silver halide as described in JP-A-8939, and 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-56-64339 are added to a silver halide color photographic light-sensitive material. Technology, and JP-A-5
7-144547, 58-50534, 58-
50535, 58-50536, 1-
A technique for adding an arylpyrazolidone to a silver halide color photographic light-sensitive material is known, and in addition, an exposed silver halide color photographic light-sensitive material is used by using an aromatic primary amine type color developing agent. A technique of using a color development accelerator when performing development is also known. For example, as such a color development accelerator, U.S. Pat.
No. 0, No. 2,515,147, No. 2,496,903, No. 4,038,075,
4,119,462, British Patents 1,430,998, 1,455,413
JP-A Nos. 53-15831 and 55-62450.
No. 55, No. 55-62451, No. 55-62452, No. 55-62453, No. 51-12422, No. 55-.
No. 62453, Japanese Patent Publication Nos. 51-12422, 55-4
There are compounds described in 9728 and the like.

However, when using one of these conventional techniques,
Although processing time is shortened, processing stability is poor, and there is a problem in processing stability particularly in rapid development processing.

When the fine grain silver halide is used,
There is a defect that the processing stability is poor, and that the finer the particles, the lower the sensitivity.

When the low silver bromide emulsion is used, the amount of brom ions eluted from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion into the processing solution is small, and the concentration of brom ions in the processing solution is low. However, when the silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed using a processing solution having a low bromide concentration, the processing stability is poor. Here, the processing stability is the degree of fluctuation of the processing solution composition, pH, temperature, bromine ion concentration, etc., and the fluctuation of sensitometry due to the incorporation of other compounds other than the processing solution composition.

Looking at another conventional technique for improving the processing stability, there is an improvement in the processing solution as disclosed in, for example, JP-A-59-121036 and 59-120250. As far as is known, there is no example in which the processing stability is substantially improved by the improvement of the silver halide color photographic light-sensitive material.

Therefore, the present inventor previously proposed the technique disclosed in Japanese Patent Application No. 59-158782. The previously proposed technique is a silver halide color photographic light-sensitive material having a blue light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer on a support. The average grain size of silver halide in the silver halide emulsion layer is 0.20 to 0.55 μm, and the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 A silver halide color photographic light-sensitive material having a content of ~ 65 mol%,
It is possible to perform a rapid color development process, have excellent process stability, and obtain a high-quality image.

[Problems to be Solved by the Invention] As a result of continuing research on the above-mentioned prior art, the present inventor has found that there is room for further improvement in processing stability in rapid development processing.

The present invention has been made in view of the above, and it is a technical object to provide a silver halide color photographic light-sensitive material capable of rapid development processing and further improved in processing stability in the rapid development processing. To do.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above technical problems is a blue-sensitive material containing silver chlorobromide or silver chloroiodobromide on a reflective support. In a silver halide color photographic light-sensitive material having one silver halide emulsion layer, one green light-sensitive silver halide emulsion layer and one red light-sensitive silver halide emulsion layer, the silver halide of the blue light-sensitive silver halide emulsion layer Has an average grain size of 0.20 to 0.55 μm, the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol%, and At least one layer of a green photosensitive silver halide emulsion layer and a red photosensitive silver halide emulsion layer is provided between the blue photosensitive silver halide emulsion layer and the reflection support.

A preferred embodiment of the present invention is a green light-sensitive silver halide emulsion in which the silver halide grains of the blue light-sensitive silver halide emulsion layer are provided between the blue light-sensitive silver halide emulsion layer and a reflective support. The average grain size is larger than or substantially the same as the silver halide grains of at least one of the layers, the red-sensitive silver halide emulsion layer.

In the present specification, the "lower side" or "lower layer" means the side closer to the support or the layer thereof, and the "upper side" or "upper layer" means the side further away from the support or the layer thereof. .

Hereinafter, the present invention will be described in more detail.

The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size) of 0.20 to 0.55μ.
m, preferably 0.30 to 0.50 μm. Average particle size is 0.55
When it exceeds μm, the processing stability is poor, and particularly when the amount of potassium bromide varies, the processing stability is significantly deteriorated. on the other hand,
If the fluctuating grain size is less than 0.20 μm, the sensitivity of the blue-sensitive silver halide emulsion layer is insufficient and magenta color turbidity occurs.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's “Particle Size Analysis” ASTM Symposium on Light Microscopy, 1955, pp. 94-122 or “Theory of Photographic Processes” co-authored by Mies and James, 3rd.
Edition, published by Macmillan, Inc. (1966), Chapter 2.

The silver halide used in the present invention may be a polydisperse emulsion having an average grain size distributed in a wide range, but a substantially monodisperse emulsion is preferable.

The above-mentioned substantially monodisperse silver halide grains in the present invention mean that most of the silver halide grains appear to have the same shape when the emulsion is observed by an electron micrograph, and the grain sizes are uniform, and It has a particle size distribution as defined by the following formula. That is, when the standard deviation s of the particle size distribution is divided by the average particle size, the value is 0.15 or less.

The grain size referred to here is the length of one side of a cubic silver halide grain, or the length of one side when converted to a cube having the same volume in the case of a grain having a shape other than a cube. Therefore, when the individual particle size in this sense is ri and the number thereof is ni, is defined by the following formula.

The relationship between particle size distributions is described in "The Empirical Relationship Between Sensitometric and Particle Size Distributions in Photography" in The Photographic Journal, LXXIX (1949), pages 330-338, by Tribel and Smith. This can be determined by

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention may be silver chlorobromide, silver chloroiodobromide or a mixture thereof. The content is 5 to 65 mol%. In the present invention, the silver bromide content means the total odor of all layers contained in the total green photosensitive silver halide emulsion layer and the total red photosensitive silver halide emulsion layer. It means the content rate of silver halide. If the silver bromide content exceeds 65 mol%, the processing stability will deteriorate,
Magenta color turbidity occurs, which causes deterioration of image quality.
On the other hand, when the silver bromide content is less than 5 mol%, the processing stability is significantly deteriorated.

When the silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content thereof does not exceed 2 mol%. Those are preferable.

The preferable silver bromide content of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 20 to 60 mol%, more preferably 30 to 55 mol%.

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is substantially the same as the silver halide contained in the blue light-sensitive silver halide emulsion layer. Monodisperse ones are preferred.

The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer may be either silver chlorobromide or silver chloroiodobromide, or a mixture thereof, preferably silver chlorobromide. And the silver bromide content is 30 to 95 mol%.

The average grain size of silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2.
˜1 μm, particularly preferably 0.25 to 0.8 μm.

The silver halide color photographic light-sensitive material of the present invention comprises three light-sensitive silver halide emulsion layers having substantially different color sensitivities, that is, a blue light-sensitive silver halide emulsion layer and a green light-sensitive silver halide emulsion. Layer and a red-sensitive silver halide emulsion layer. The coating positions of the three light-sensitive silver halide emulsion layers having different color sensitivities are as follows: a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion below the blue light-sensitive silver halide emulsion layer. At least one of the layers is applied.

In this respect, a preferred embodiment of the present invention is that the green photosensitive silver halide emulsion layer is provided below the [A] blue photosensitive silver halide emulsion layer and the red photosensitive silver halide emulsion layer is provided above. Is to be done. In another preferred embodiment, a red light-sensitive silver halide emulsion layer is provided below [B] the blue light-sensitive silver halide emulsion layer, and a green light-sensitive layer is formed below the red light-sensitive silver halide emulsion layer. A silver halide emulsion layer is provided.

The silver halide color photographic light-sensitive material of the present invention is a green light-sensitive material in which the silver halide grains of the blue-sensitive silver halide emulsion layer are provided between the blue-sensitive silver halide emulsion layer and the reflective support. Of at least one silver halide grain of a photosensitive silver halide emulsion layer or a red-sensitive silver halide emulsion layer,
It is preferable that the average particle size is large or has substantially the same structure. If you explain using a specific example,
It is as follows. That is, the green-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer, the
In the case of the above [A] structure having the arrangement of the red-sensitive silver halide emulsion layer, the silver halide grains of the blue-sensitive silver halide emulsion layer are more than the silver halide grains of the green-sensitive silver halide emulsion layer. The average particle size is preferably large or substantially the same. Further, in the case of a constitution having an arrangement of a green light-sensitive silver halide emulsion layer, a red light-sensitive silver halide emulsion layer, and a blue light-sensitive silver halide emulsion layer from the reflective support side, a blue light-sensitive silver halide silver halide The average grain size of the grains is preferably larger or substantially the same as that of the silver halide grains of the green-sensitive silver halide emulsion layer and / or the red-sensitive silver halide emulsion layer.

Explaining the specific example of the above [B] structure, the silver halide grains of the blue-sensitive silver halide emulsion layer have an average grain size smaller than that of the silver halide grains of the red-sensitive silver halide emulsion layer. Are larger or substantially the same, the green light-sensitive silver halide emulsion layer is more than the silver halide grains of the blue light-sensitive silver halide emulsion layer and / or the red light-sensitive silver halide emulsion layer,
The average particle size may be large, substantially the same, or conversely small. On the other hand, when the silver halide grains of the blue-sensitive silver halide emulsion layer have a larger or substantially the same average grain size than the silver halide grains of the green-sensitive silver halide emulsion layer, they are red-sensitive. The silver halide emulsion layer may have an average grain size larger than or substantially the same as the silver halide grains of the blue-sensitive silver halide emulsion layer and / or the green-sensitive silver halide emulsion layer. , Or vice versa. As described above, at least one of the lower photosensitive silver halide emulsion layers having different color sensitivity from the blue photosensitive silver halide emulsion layer has a small average silver halide grain size. Alternatively, it is preferable that they are substantially the same.

Regarding the ratio of the average grain size of the silver halide grains contained in each layer, a specific example of the above [A] and [B] configurations will be described.
In any case, the ratio of the average grain size of the silver halide grains contained in the photosensitive silver halide emulsion layers having different color sensitivities is 1: 1 to 2: 1 to 3 from the reflection support side. It is preferable. Specifically, from the reflective support side (1) 1: 2:
1, (2) 1: 2: 3, (3) 1: 1: 1 and the average grain size ratio of the silver halide grains.

However, another preferred embodiment of the present invention is that the average grain size of the silver halide grains of the photosensitive silver halide emulsion layer is gradually increased from the reflection support side, and the silver halide of each photosensitive silver halide emulsion layer is increased. That is, the ratio of the average particle diameters of the particles is 1: 1 to 2: 1 to 3 from the reflection support side.
That is, the specific example of the above-mentioned [A] will be described as an example. In the case of the green photosensitive silver halide emulsion layer: the blue photosensitive silver halide emulsion layer: the red photosensitive silver halide emulsion layer, for example,
(1) 1: 1: 1, (2) 1: 1: 2, (3) 1: 1: 3, (4)
The average grain size ratio of silver halide grains such as 1: 2: 2, (5) 1: 2: 3, (6) 1: 3: 3, etc. is included as a preferred example of the present invention. Further, in the case of the specific example of the above [B] configuration, (1) 1: 1: 1, (2) 1: 1: 2, (3) 1:
1: 3, (4) 1: 2: 2, (5) 1: 2: 3, (6) 1: 3:
An average particle size ratio such as 3 is included as a preferred example of the present invention.

The silver amount (silver coating amount) of the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not particularly limited, but it is 0.3 to 1 g / m ^{2 in} the whole light-sensitive silver halide emulsion layer.
Is preferred. That is, the silver amount is preferably 1 g / m ² or less in order to obtain excellent image quality, while the silver amount is 0.3 g / m ² or more in order to obtain high maximum density and high sensitivity. Is preferred.

The silver halide composition preferably used in the present invention is silver chlorobromide or silver chloroiodobromide. Furthermore, it may be a mixture of these. That is, when the silver halide emulsion according to the present invention is used for color photographic paper, particularly fast developing property is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and the halogen composition is at least 1%. Particularly preferred is silver chlorobromide or silver chloroiodobromide containing silver chloride.

The crystals of these silver halide grains may be normal crystals, twin crystals or others, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core shell type) in which the inside and the outside are different. Further, even if these silver halides are of a type that mainly forms a latent image on the surface,
It may be of a type formed inside the particles. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

The monodisperse silver halide grains preferably used in the present invention may be those obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing the silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of the silver halide grains as described in, for example, JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929,080, U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 4414030, No. 52
The thing described in No. 24844 etc. can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201 and 2,072,908.
No. 2,739,149, No. 2,945,763, British Patent 505,979
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
9,234, 2,270,378, 2,442,710, 2,454,629
Nos. 2,776,280 and the like, cyanine dyes, merocyanine dyes or complex cyanine dyes can be mentioned as typical ones. Furthermore, U.S. Pat.Nos. 2,213,995, 2,493,748, 2,519,001, and cyanine dyes as described in West German Patent 929,080 and the like,
A merocyanine dye or a complex cyanine dye can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A typical example of a particularly preferable spectral sensitization method is, for example, JP-B-43-49, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 36, No. 43-22884, No. 45-18433
47, 37-443, 48-28293, 49-6209, 53-12375, and JP-A-52-52.
-23931, 52-51932, 54-80
118, 58-153926, 59-1166.
46, 59-116647 and the like.

The combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine is described in, for example, Japanese Patent Publication Nos. 45-25831 and 47-11.
No. 114, No. 47-25379, No. 48-38406.
No. 48-38407, No. 54-34535, No. 55-1569, and JP-A No. 50-33220, No. 50.
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917 and the like.

Further, as a combination of benzoxazolocarbocyanine (oxa-carbocyanine) with other carbocyanine, for example, Japanese Patent Publication Nos.
-11627, JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408.
No. 48-41204, No. 50-40662, No. 56-25728, No. 58-10753, No. 5
8-91445, 59-166645, 50-
No. 33828 and the like can be mentioned.

Further, as a combination of thiacarbocyanine and other carbocyanine, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
6-18107, 47-8741, JP-A-59-
114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, dye solutions such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohols described in JP-B-50-40659 are prepared in advance. It is used by dissolving it in the hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patents 584,609, 1,277,429, JP-A-48-85130, 49-99620 and 49.
-114420, 49-129537, 52-
108115, 59-25845, U.S. Pat.
4,782, 2,533,472, 2,956,879, 3,125,448
No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,540,887, 3,575,704, 3,653,905, 3,7
18,472, 4,071,312 and 4,070,352.

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

In the present invention, conventionally known yellow couplers, magenta couplers and cyan couplers can be used as the above-mentioned couplers. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and it is also possible to use diffusible dye releasing type couplers in combination with these couplers.

As the yellow coupler, a closed ketomethylene compound which has been used conventionally, an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, an active point hydantoin compound-substituted coupler, which is called a so-called 2-equivalent type coupler, Active point urazole compound-substituted couplers, active point succinimide compound-substituted couplers, active point fluorine-substituted couplers, active point chlorine- or bromine-substituted couplers, active point-o-sulfonyl-substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
5,057, 3,265,506, 3,408,194, 3,551,155
No., No. 3,582,322, No. 3,725,072, No. 3,891,445,
West German Patent 1,547,868, West German Published Application 2,219,917, 2,
261,361, 2,414,006, British Patent 1,425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 51-102636, 5
0-6341, 50-123342, 50-1
No. 30442, No. 51-21827, No. 50-876
No. 50, No. 52-82424, No. 52-115219
No. 58-95346 and the like.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds.

These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. As a specific example of the magenta coupler, US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2,418,959, 2,424,467, Japanese Patent Publication No. 40-60
31, JP-A-51-20826, and JP-A-52-5892.
2, No. 49-129538, No. 49-74027.
No. 50-159336, No. 52-42121,
49-74028, 50-60233, 51
No. 26541, No. 53-55122, Japanese Patent Application No. 55-
Examples thereof include those described in No. 110943.

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,41
No. 1, 4,004,929, West German patent application (OLS) 2,414,83
0, 2,454,329, JP-A-48-59838, 5
1-26034, 48-5055, 51-14
No. 6827, No. 52-69624, No. 52-9093.
No. 2, No. 58-95346 and the like can be mentioned.

In the silver halide emulsion layer and other photographic constituent layers of the present invention, so-called DIR compounds, couplers such as non-diffusible couplers and polymer couplers which react with an oxidized product of a developing agent to form a diffusible dye that appropriately bleeds. You may use together. Regarding the non-diffusible DIR compound and the non-diffusible coupler which reacts with the oxidized product of the developing agent to form a diffusible dye which is appropriately bleeding, the description in Japanese Patent Application No. 59-193611 by the present applicant, and regarding the polymer coupler, Japanese Patent Application No. 5 by the applicant
For the DIR compound, the description of Japanese Patent Application No. 59-158782 by the present applicant can be referred to.

In order to incorporate these couplers in the silver halide emulsion according to the present invention, they may be added as an alkaline solution when the couplers are alkali-soluble, and when they are oil-soluble, for example, US Pat. No. 2,322,027,
No.2,801,170, No.2,801,171, No.2,272,191 and No.2,304,940 according to the method described in each of the high boiling point solvent, the coupler is dissolved in combination with a low boiling point solvent, if necessary, in the form of fine particles It is preferable to disperse it into a silver halide emulsion and add it to the silver halide emulsion. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents and the like may be used in combination if necessary. It is also possible to use a mixture of two or more couplers. Further, in detail, a method for adding a coupler which is preferable in the present invention, one or more couplers may be added, if necessary, other couplers,
Organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate together with hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. , Triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N, N-di-ethyl-caprylamidobutyl, N, N-diethyllaurylamide, n-pentadecylphenyl Ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether,
High-boiling solvent such as monophenyl-di-o-chlorophenyl phosphate or fluoroparaffin, and / or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, It is soluble in low boiling point solvents such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and the like, and anionic surfactants such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or sorbitan sesquioleate and sorbitan. An aqueous solution containing a nonionic surfactant such as monolauryl ester and / or a hydrophilic binder such as gelatin Combined, high-speed mixer, and emulsified by a colloid mill or an ultrasonic dispersing device or the like, is added to the silver halide emulsion.

In addition, the coupler may be dispersed by using a latex dispersion method. The latex dispersion method and its effect are described in JP-A-49-74538, JP-A-51-59943, and JP-A-54-9543.
-32552 Publications and Research Disclosures
August 1976, No. 14850, pp. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4) -Oxopentyl)] acrylamide, 2-acrylamido-2-
Homopolymers, copolymers and terpolymers of monomers such as methyl propane sulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643. A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a film hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

The support of the silver halide color photographic light-sensitive material of the present invention comprises
It may be any of so-called reflective supports, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, such as a glass plate, cellulose acetate, cellulose nitrate. Alternatively, there are polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these reflective supports are appropriately selected according to the purpose of use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other constituent layers used in the present invention. Further, a simultaneous coating method of two or more layers by the method described in US Pat. Nos. 2,761,791 and 2,941,898 can also be used.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

The processing method of the photographic light-sensitive material using the silver halide emulsion according to the present invention is not particularly limited, and any processing method can be applied. For example, as a typical one,
After color development, bleach-fixing treatment followed by washing and / or stabilizing treatment if necessary; after color development, bleaching and fixing treatment are carried out separately, and if necessary, further washing and / or stabilizing treatment; or Pre-hardening, neutralization, color development, stop-fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color development, washing, supplemental color development, stopping, bleaching, fixing, washing, stabilizing May be carried out in any order, such as a method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is carried out again to increase the amount of dye formed.

The color developer used in the processing of the silver halide color photographic light-sensitive material of the present invention is an alkaline aqueous solution containing a color developing agent, preferably having a pH of 8 or more, and more preferably 9 to 12. The aromatic primary amine developing agent as the color developing agent is a compound having a primary amino group on the aromatic ring and capable of developing exposed silver halide. A precursor forming such a compound may be added.

Typical examples of the color developing agent include those of p-phenylenediamine type, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-methyl-4
-Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3
-Methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-
Ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N-ethyl-N-β- [β- (β-methoxyethoxy) ethoxy] ethyl-3-methyl- 4-aminoaniline, N-ethyl-N-β- (β-methoxyethoxy) ethyl-3-
Methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like.

Further, for example, JP-A-48-64932 and 50-1.
Nos. 31526, 51-95849 and Bent et al., Journal of the American Chemical Society, Volume 73, pages 3100 to 3125 (1951), are also representative.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but it is preferable to increase the amount of use in order to increase the activity. The amount used is 0.0002 mol / to 0.7 mol /. Further, two or more compounds can be used in an appropriate combination depending on the purpose. For example 3-methyl-4
-Amino-N, N-diethylaniline and 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
A combination of N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline and the like can be freely combined and used according to the purpose.

In the color developer used in the present invention, various components which are usually added, for example, sodium hydroxide, alkali agents such as sodium carbonate, alkali metal nitrites,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above that are added to the color developing solution include potassium bromide, bromide such as ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl. Examples include compounds for rapid processing liquids such as -5-mercaptotetrazole, stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyldiaminediaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives,
For example, a pH buffer, an optical brightener, an antifoaming agent, a surfactant, a preservative, a chelating agent, a stabilizer, an organic solvent and the like may be added and contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of The processing temperature of various processing steps such as color development, bleach-fixing (or bleaching / fixing) of the silver halide color photographic light-sensitive material of the present invention, and optionally washing with water, stabilization, drying, etc. is from the viewpoint of rapid processing. It is preferably carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is described in JP-A-58 / 58.
No. 14834, No. 58-105145, No. 58-1
34634 and 58-18631 and Japanese Patent Application No. 5
You may perform water washing alternative stabilization treatment as shown by 8-2709 and 59-89288 etc.

[Effects of the Invention] According to the silver halide color photographic light-sensitive material of the present invention, a blue-sensitive silver halide emulsion layer and a green light-sensitive layer each containing silver chlorobromide or silver chloroiodobromide on a reflective support. In a silver halide color photographic light-sensitive material having one silver halide emulsion layer and one red light-sensitive silver halide emulsion layer, the average grain size of silver halide in the blue light-sensitive silver halide emulsion layer is 0.20 to
0.55 μm, the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol%, and the blue-sensitive silver halide emulsion described above. Since at least one layer of a green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer is provided between the layer and the reflective support, rapid development processing is possible. It is possible to provide a silver halide color photographic light-sensitive material having further improved processing stability in the rapid development processing.

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

Example 1 A silver halide color photographic light-sensitive material sample No. 1 was prepared by sequentially coating the following layers on a polyethylene-laminated paper support (hereinafter referred to as BS) from the support side.

Layer 1: 1.25 g / m ² gelatin, 0.22 g / m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.30 g / m ² dioctyl A layer containing 0.62 g / m ² of magenta coupler (M-1) dissolved in phthalate (hereinafter referred to as O-2).

Layer 2 ... 0.70 g / m ² gelatin, 20 mg / m ² irradiation dye (AI-1), 10 mg / m ² (AI-
An intermediate layer composed of 2) (hereinafter referred to as IL).

Layer 3 ··· 1.20g / m ² of gelatin, 0.32 g / m ² (in terms of silver, hereinafter the same) blue-sensitive silver chlorobromide emulsion (silver bromide content and an average particle diameter shown in Table 1), A layer containing 0.80 g / m ² of the yellow coupler (Y-1) dissolved in 0.50 g / m ² of dioctyl phthalate (hereinafter referred to as R-1).

Layer 4: an intermediate layer (I of 1.20 g / m ² ) (I
L).

Layer 5: 1.40 g / m ² gelatin, 0.20 g / m ² red-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.20 g / m ² dioctyl A layer containing 0.45 g / m ² of a cyan coupler (C-1) dissolved in phthalate (hereinafter referred to as P-2).

Layer 6 ... Layer containing 0.30 g / m ² of the following UV absorber (UV-1) dissolved in 1.0 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate (hereinafter referred to as UV) .

Layer 7 ... A layer containing 0.50 g / m ² of gelatin (hereinafter referred to as Pro).

Sample Nos. 2 to 6 were prepared by changing the layer structure of the sample No. 1 thus prepared as shown in Table 2 below.
For the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer other than O-2 and P-3, emulsions having the silver bromide content and the average grain size shown in Table 1 were used.

(Y-1) (M-1) (C-1) (AI-1) (AI-2) (UV-1) As a hardening agent, sodium 2,4-dichloro-6-hydroxy-S-triazine was added to layers 2, 4 and 7 so that the amount was 0.017 g per 1 g of gelatin.

Each of the above photosensitive material sample Nos. 1 to 6 was exposed through an optical wedge and then processed in the next step.

Processing step (38 ° C.) Color development 3 minutes Bleach fixing 1 minute Washing with water 1 minute Drying 60 to 80 ° C. 2 minutes The composition of each processing solution is as follows.

[Color developer] Pure water 800 ml Benzyl alcohol 15 ml Hydroxyamine sulfate 2.0 g Potassium bromide 1.5 g Sodium chloride 1.0 g Potassium sulfite 2.0 g Triethanolamine 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-Aminoaniline sulfate 4.5g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) 2ml (Fluorescent brightener, Sumitomo Chemical Co., Ltd.) Add pure water to make 1 and adjust the pH to 10.1 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fixing solution] Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Sodium bromide 10 g Add pure water to 1 and ammonia water Or pH with dilute sulfuric acid
Adjust to 7.0.

Separately, using a color developing solution which is different only in that the potassium bromide of the color developing solution is 0.5, 1.0, 2.0 and 2.5,
Each of the same sample Nos. 1 to 6 as above was developed.

Sensitometry was performed on each of the obtained samples by a conventional method. Table 3 shows the gamma value at each potassium bromide concentration.

As is clear from Table 3, it can be seen that Sample Nos. 1 to 4 of the present invention have little gamma movement when the potassium bromide concentration varies and are excellent in processing stability. That is, from the comparison of Samples Nos. 5 and 6 outside the present invention, the average grain size of the silver halide grains in the blue-sensitive silver halide emulsion layer was 0.20 to 0.55 .mu.m, and the green-sensitive silver halide emulsion layer and the red The processing stability is improved by using the light-sensitive material (Sample No. 5) in which the silver bromide content of silver halide in the light-sensitive silver halide emulsion layer is 5 to 65 mol%, but the sample for comparison is No. 5 and sample No. 3 of the present invention
In comparison with Sample Nos. 3 and 4, Sample Nos. 3 and 4 of the present invention showed further improvement in processing stability, and the average grain size of the silver halide grains in the photosensitive silver halide emulsion layer was from the side of the reflective support. The most preferable sample Nos. 1 and 2 which are gradually increasing
Then, it can be seen that the effect of improving the processing stability is particularly remarkable.

Example 2 Sample No. 1 and sample No. 5 were used to test for rapid processability. That is, each processing solution of Example 1 was used (however, the potassium bromide concentration of the color developing solution was set to 1.0 g /).
The sensitivity (S), gamma (γ) and maximum density (Dm) when the color development time was set to 1 minute 30 seconds, 2 minutes and 2 minutes 30 seconds were examined. The results are shown in Table 4.

From the results shown in Table 4, sufficient photographic performance was obtained for both sample Nos. 1 and 5 with a color development time of 2 minutes, but comparing the photographic performances of sample Nos. 1 and 5 at a development time of 1 minute and 30 seconds, It is apparent that the sample No. 1 of the present invention develops faster. Therefore, it was found that the silver halide car photographic light-sensitive material of the present invention is also excellent in rapid processability.

Front page continued (72) Inventor Shigeto Hirabayashi 1 Sakura-cho, Hino City, Tokyo Konishi Roku Photo Industrial Co., Ltd. (56) Reference JP-A-58-126530 (JP, A) JP-A-50-79333 ( JP, A) JP 51-11445 (JP, A) JP 56-14236 (JP, A)

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer each containing silver chlorobromide or silver chloroiodobromide on a reflective support. In a silver halide color photographic light-sensitive material having one layer of each of the above, the blue-sensitive silver halide emulsion layer has an average silver halide grain size of 0.20 to 0.55 μm, and the green-sensitive silver halide emulsion layer and the red light-sensitive The silver bromide content of silver halide in the light-sensitive silver halide emulsion layer is from 5 to 65 mol%, and a green light-sensitive silver halide emulsion is provided between the blue light-sensitive silver halide emulsion layer and the reflective support. A silver halide color photographic light-sensitive material comprising at least one layer, a red light-sensitive silver halide emulsion layer.