JPH0516581B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is capable of rapid development, has improved processing stability in the rapid development, and can save silver. This invention relates to a silver halide color photographic material that can suppress the occurrence of fog. In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. ing. for example,
In silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb blue light that passes through the blue-sensitive silver halide emulsion layer. ing. Further, each emulsion layer is provided with other intermediate layers 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-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similar to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer and protective layers are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indazolone or cyano couplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl magenta coupler and an acylacetamide yellow coupler are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in a silver halide emulsion layer and rendered non-diffusible. [Prior Art] In recent years, there has been a demand in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have excellent processing stability, and are low cost. A silver halide color photographic material that can be rapidly processed is desired. In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of improving service to users, processing is carried out on the same day of receipt of development. Recently, there has been a demand for the product to be returned to the user within a few hours of receiving the product, and there is an urgent need to develop silver halide color photographic materials that can be processed even more rapidly. It is. Additionally, in running processing, there is a problem in that photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it impossible to obtain stable photographic performance. . These changes in the composition of the processing solution and fluctuations in conditions are caused by the elution and elution of photographically active substances from the light-sensitive material during the development process (running).
This is thought to be due to accumulation or other causes. Therefore, in order to respond to variations in processing conditions, it is necessary to highly control the development time, the temperature and pH of the developer, and the halogen concentration, especially the bromine ion concentration, in the developer. However, compared to the development time or the temperature and pH of the developer, the bromide ion concentration in the developer is difficult to quantify and difficult to control due to its poor measurability. Therefore, it is particularly necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on bromine concentration and is highly process-stabilized.
Processing stability is a problem even in normal processing time, but processing stability becomes more of a problem in rapid processing. Furthermore, it is a matter of course that such processing-stabilized silver halide color photographic materials are required to be economically provided at low cost. Therefore, if we look at the conventional techniques for silver halide color photographic light-sensitive materials that can be rapidly processed, for example, there is a technique for making silver halide fine grains as described in JP-A-51-77223, JP-A-58-184142, A silver halide color photograph of 1-aryl-3-pyrazolidone having a specific structure as described in Japanese Patent Publication No. 56-18939 and a silver halide color photograph as described in Japanese Patent Publication No. 56-18939 Addition technology to photosensitive materials, as well as JP-A-57-144547 and JP-A No. 58-
50534, No. 58-50535, and No. 58-50536, in which 1-arylpyrazolidones are added to silver halide color photographic light-sensitive materials. A technique of using a color development accelerator when developing a silver oxide color photographic light-sensitive material using an aromatic primary amine color developing agent is also known. For example, such color development accelerators include those described in the U.S. Pat.
No. 2950970, No. 2515147, No. 2496903, No.
No. 4038075, No. 4119462, British Patent No. 1430998,
1455413, JP 53-15831, JP 55-62450
No. 55-62451, No. 55-62452, No. 55-
No. 62453, No. 55-62453, Special Publication No. 51-12422,
There are compounds described in No. 55-49728 and the like. However, when these conventional techniques are used, although the processing time is shortened, the processing stability in the rapid development processing is poor, and there is also a problem with fogging in the same-day performance. When the low silver bromide emulsion described above is used, fewer bromide ions are eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the processing solution is set low. However, when a silver halide color photographic material containing a low silver bromide emulsion is processed using a processing solution with a low bromine ion concentration, processing stability is poor. Processing stability here refers to the degree of variation in sensitometry with respect to variations in processing solution composition, pH, temperature, bromide ion concentration, etc., and to contamination of other compounds other than the processing solution composition. Furthermore, when the above-mentioned fine grain silver halide is used, it has the disadvantage of poor processing stability;
In addition, there was a drawback that the sensitivity deteriorated as the particles became finer. On the other hand, if we look at conventional techniques for improving processing stability, for example, as disclosed in JP-A-59-121036 and JP-A-59-120250, there are techniques that involve improving the processing solution. To the best of our knowledge, there is no example in which the processing stability has been substantially improved by improving a silver halide color photographic light-sensitive material, and it is desired to develop a technique for improving the processing stability by improving the light-sensitive material. On the other hand, silver saving is one technical means for providing low-cost silver halide color photographic materials. Various techniques for saving silver are known, and pyrazolotriazole-based magenta couplers are one of the main techniques for saving silver. However, it has been pointed out that a problem with pyrazolotriazole magenta couplers is high fogging during same-day performance. Various improvements have been attempted to solve this problem. For example, there is a technique for suppressing fog by adding an inhibitor as described in a patent application (title of invention: silver halide photographic light-sensitive material) filed on September 11, 1980 by the present applicant. However, suppressing fog using a suppressor is undesirable because it causes a substantial decrease in sensitivity. Therefore, it is desired to develop a silver halide color photographic light-sensitive material that causes less fog. [Problems to be Solved by the Invention] The present invention has been made in view of the above, and is capable of rapid development processing, improved processing stability in the rapid development processing, and silver saving. A technical object of the present invention is to provide a silver halide color photographic material that can suppress the occurrence of fog. [Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above technical problems has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a support. In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, the silver halide in the blue-sensitive silver halide emulsion layer is silver chlorobromide with a silver bromide content of 30 to 95 mol%. , the average grain size of the silver chlorobromide is 0.20 to 0.55 μm, and the silver bromide content of the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol. %
and is characterized in that the green-sensitive silver halide emulsion layer contains at least one compound represented by the following general formula [] (hereinafter referred to as the pyrazolotriazole-based magenta coupler of the present invention). General formula [] In the formula, R ₁ represents a halogen atom or a monovalent organic group that can be separated by a coupling reaction with an oxidized developing agent, and each of the monovalent organic groups may have a substituent. an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group formed by a 5- or 6-membered ring, an alkylthio group, an arylthio group, a heterocyclic thio group formed by a 5- or 6-membered ring, or

[Formula] Group, (However, A ₁ and A ₂ may be the same or different,
Each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and A ₁ and A ₂ are both It is never a hydrogen atom. Alternatively, A ₁ and A ₂ may be bonded to each other to form a 5- or 6-membered ring together with the nitrogen atom. This 5- or 6-membered ring may be further fused with a benzene ring/heterocycle. ) can be mentioned. R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom, an alkyl group (an alkyl group having 1 to 32 carbon atoms, which may have a linear or branched substituent,
Specifically, for example, methyl group, propyl group, t-
Butyl group, hexadecyl group, 3-(3-pentadecylphenoxy)propyl group, 3-(2,4-di-tert-amylphenoxy)propyl group, 3-
(2,4-di-tert-amylphenoxy)ethyl group, 3-(4-di-tert-amylphenoxy)propyl group, 2-[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamidoethyl ), aryl groups (e.g. phenyl group, α
or β-naphthyl group, 4-methylphenyl group,
2,4,6-trichlorophenyl group, 4-[α-
(3-tert-butyl-4-hydroxyphenoxy)
tetradecanamide]-2,6-dichlorophenyl group, etc.), heterocyclic groups (e.g. pyridyl group, thienyl group, quinolyl group, etc.), acylamino group (e.g. acetylamino group, benzamide group, 3-(2,
4-di-tert-amylphenoxy)butyramide group, 3-(3-pentadecylphenoxy)butyramide group, etc.), alkylamino group (e.g. methylamino group, diethylamino group, n-dodecylamino group, etc.), anilino group ( For example, phenylamino group,
2-chloro-5-tetradecanamidophenylamino group, 4-[α-(3-t-butyl-4-hydroxyphenoxy)tetradecanamido]anilino group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, tetra decyloxycarbonyl group, etc.), alkylthio group (e.g. hexylthio group,
dodecylthio group, etc.), and R ₂ and R ₃ are never hydrogen atoms at the same time. The pyrazolotriazole magenta coupler used in the present invention is disclosed in, for example, US Pat. No. 3,705,896;
No. 3725767, No. 3758309, No. 3810761, British Patent No. 1252418, British Patent No. 1334515, Special Publication No. 58-42045
Although it is already known as described in the present invention, when used in combination with a specific silver halide emulsion, the processing stability is improved, especially the processing stability in rapid processing is greatly improved. This was a surprise even to the present inventors, as it was not known that it could be improved at all. Furthermore, it has been pointed out that a problem with pyrazolotriazole magenta couplers is high fog generation during same-day performance. Therefore, the occurrence of fogging could also be suppressed. This fact was completely unexpected even by the present inventor, who has been involved in research for many years. The present invention will be explained in more detail below. The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size).
It is 0.20-0.55 μm, preferably 0.30-0.50 μm.
If the average particle size exceeds 0.55 μm, processing stability will be poor;
In some cases, the processing stability deteriorates significantly due to fluctuations in the amount of potassium bromide. On the other hand, if the average grain size is less than 0.20 μm, the sensitivity of the blue-sensitive silver halide emulsion layer is insufficient, resulting in magenta color turbidity. 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 commonly used in the technical field for the above purpose. A typical method is Loveland's "particle size analysis method"
ASTM Symposium on Light Microscopy, 1955, pp. 94-122, or Chapter 2 of ``The Theory of Photographic Processes'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). There is. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape,
Particle size distribution can be expressed fairly accurately as diameter or projected area. The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred. In the present invention, the above-mentioned monodisperse silver halide grains mean that most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have the following formula: It has a particle size distribution as defined by . That is,
When the standard deviation s of particle size distribution is divided by the average particle size, the value is 0.15 or less. The grain size here has the same meaning as the grain size mentioned above regarding the average grain size, and in the case of cubic silver halide grains, the length of one side, or in the case of grains with a shape other than a cube, the same The length of one side when converted to a cube with volume, the individual grain size in this sense is ri, and the number is
When ni, then is defined by the following formula. = Σni・ri/Σni The relationship between particle size distribution is described in "Empirical relationship between sensitometric distribution and particle size distribution in photography" The Photographic Journal, Volume LXXIX (1949)
This can be determined using the method described in the paper by Tribel and Smith, pp. 330-338. The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention may be silver chlorobromide, silver chloroiodobromide, or a mixture thereof (or silver chloride, silver bromo A mixture containing some silver bromide may be used, and the silver bromide content is 5 to 65 mol%. In the present invention, one or both of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer may be composed of two or more layers. In the present invention, the silver bromide content refers to the total odor of each layer in the total silver halide contained in each of the all-green light-sensitive silver halide emulsion layer and the all-red light-sensitive silver halide emulsion layer. Refers to the content of silver oxide. When the silver bromide content exceeds 65 mol%, processing stability deteriorates, causing magenta color turbidity. On the other hand, when the silver bromide content is less than 5 mol %, processing stability deteriorates significantly. When the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content does not exceed 2 mol%. Preferably. The silver bromide content of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is preferably 20 to 60 mol%, more preferably 30 to 55 mol%. The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue-sensitive silver halide emulsion layer. Preferably. In the present invention, the silver halide contained in the blue-sensitive silver halide emulsion layer is silver chlorobromide having a silver bromide content of 30 to 95 mol %. Furthermore, the blue-sensitive silver halide emulsion layer in the present invention may consist of two or more layers. The average grain size of the 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 to 1 μm, particularly preferably 0.25 to 1 μm
It is 0.8 μm. Next, the pyrazolotriazole magenta coupler of the present invention will be explained. The pyrazolotriazole-based magenta coupler of the present invention is contained in a green-sensitive silver halide emulsion layer, and when the green-sensitive silver halide emulsion layer is composed of two or more layers, at least one green-sensitive silver halide emulsion layer is included. It is sufficient if it is contained in the silver halide emulsion layer. The amount of the pyrazolotriazole magenta coupler of the present invention added is not limited, but is 2×10 ^-3 to 5× per mole of silver in the green-sensitive silver halide emulsion layer.
10 ^-1 mol is preferred, more preferably 1 x 10 ^-2 ~
It is 5×10 ⁻¹ mol. The pyrazolotriazole magenta coupler used in the present invention is disclosed in, for example, US Pat. No. 3,705,896;
No. 3725767, No. 3758309, No. 3810761, British Patent No. 1252418, British Patent No. 1334515, Special Publication No. 58-42045
No. 58-164882, No. 58-167326, No. 58
−206321, No. 58-214853, No. 58-217339,
Examples thereof include compounds described in No. 59-24653 and the like. Specific examples of the pyrazolotriazole magenta coupler of the present invention are listed below, but the invention is not limited thereto. The silver amount (silver deposition amount) in the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not limited, but is set to 0.3 to 1 g/m ² in the entire photosensitive silver halide emulsion layer. is preferable. That is,
In order to obtain excellent image quality, the silver amount is preferably 1 g/m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is preferably 0.3 g/m ²
It is preferable that it is above. In the present invention, the silver content is particularly preferably 0.4 to 0.8 g/m ² . Silver halide compositions preferably used in the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is, when the silver halide emulsion according to the present invention is used in color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1% of the chlorine atoms. Silver chlorobromide or silver chloroiodobromide containing silver chloride is particularly preferred. Further, the crystals of these silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1.0.0] planes to [1.1.1] planes 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 outside are different. In addition, these silver halides are of the type that mainly forms latent images on the surface,
It may also be of a type formed inside the particles. Furthermore, tabular silver halide grains (see Japanese Patent Application No. 59-170070) can also be used. The substantially monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A-54-48521. Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain activated gelatin;
Sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers. Sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Specifically, ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these act as sensitizers or fog suppressants depending on the amount) can be used alone or Chemical sensitization may be carried out by using appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion contains at least one hydroxytetrazaindene and a nitrogen-containing heterozygous compound having a mercapto group. It may contain at least one kind of ring compound. The silver halide used in the present invention contains an appropriate sensitizing dye at a rate of 5 x 10 _-8 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding up to 3×10 ₋₃ mol.
Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080,
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publications No. 43-4936, No. 43-22884, No. 45-4 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 18433, No. 47-37443, No. 48-28293, No. 49
-6209, 53-12375, JP-A-52-23931,
No. 52-51932, No. 54-80118, No. 58-153926
No. 59-116646, No. 59-116647, and the like. In addition, regarding the combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication No. 25831/1983;
No. 47-11114, No. 47-25379, No. 48-38406,
No. 48-38407, No. 54-34535, No. 55-1569,
JP-A-50-33220, JP-A No. 50-38526, JP-A No. 51-
No. 107127, No. 51-115820, No. 51-135528, No.
Examples include No. 52-104916 and No. 52-104917. Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example,
No. 32753, No. 46-11627, JP-A No. 1483-1983, and Japanese Patent Publication No. 1483-1983 regarding merocyanine.
-38408, 48-41204, 50-40662, JP-A-56-25728, 58-10753, 58-91445
No. 59-116645, No. 50-33828, etc. In addition, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43
-4932, 43-4933, 45-26470, 46
-18107, JP-A No. 47-8741, JP-A-59-114533, etc. Furthermore, the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye is advantageous. It can be used for. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone,
Dimethylformamide or Special Publication No. 50-40659
It is used by dissolving it in a hydrophilic organic solvent such as a fluorinated alcohol as described in the above. The additive may be added at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion. In the silver halide color photographic light-sensitive material of the present invention, a filter dye is added to the hydrophilic colloid layer.
Alternatively, a water-soluble dye may be contained for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609;
No. 1277429, Japanese Patent Publication No. 48-85130, No. 49-99620,
No. 49-114420, No. 49-129537, No. 52-108115
No. 59-25845, U.S. Patent No. 2274782, Id.
No. 2533472, No. 2956879, No. 3125448, No.
No. 3148187, No. 3177078, No. 3247127, No. 3148187, No. 3177078, No. 3247127, No.
No. 3540887, No. 3575704, No. 3653905, No.
It is described in No. 3718472, No. 4071312, and No. 4070352. The green-sensitive silver halide emulsion layer according to the present invention contains the pyrazolotriazole-based magenta coupler of the present invention, but the green-sensitive silver halide emulsion layer contains a magenta coupler other than the present invention. Good too. However, it is preferable that the amount of magenta couplers other than the present invention be less than 45 mol % based on the total amount of magenta couplers. Further, the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer according to the present invention may each contain a coupler, that is, a compound capable of reacting with an oxidized form of a color developing agent to form a dye. can. In the present invention, ordinary yellow couplers, magenta couplers and cyan couplers can be used as the couplers. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers. The yellow couplers include closed ketomethylene compounds, active point -o-aryl substituted couplers called so-called two-equivalent couplers, active point -o-acyl substituted couplers, active point hydantoin compound substituted couplers, and active point urazole compound substituted couplers. and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -o-
Sulfonyl-substituted couplers and the like may be used without particular limitation. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds outside the present invention. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patent Nos. 2600788, 2983608,
No. 3062653, No. 3127269, No. 3311476, No.
No. 3419391, No. 3519429, No. 3558319, No.
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No. 2418959,
No. 2424467, Special Publication No. 6031, No. 40-6031, No. 51-
No. 20826, No. 52-58922, No. 49-129538, No. 49
−74027, No. 50-159336, No. 52-42121, No.
No. 49-74028, No. 50-60233, No. 51-26541,
Examples include those described in Japanese Patent Application No. 53-55122 and Japanese Patent Application No. 55-110943. Furthermore, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. 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. Patent Nos. 2,369,929, 2,434,272, and
No. 2474293, No. 2521908, No. 2895826, No.
No. 3034892, No. 3311476, No. 3458315, No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146827,
Examples include those described in No. 52-69624, No. 52-90932, No. 58-95346, and the like. In order to incorporate the pyrazolotriazole magenta coupler of the present invention and other couplers into the silver halide emulsion of the present invention, if the coupler is alkali-soluble, it may be added as an alkaline solution; For example, US Pat. No. 2322027, US Pat. No. 2801170, US Pat.
2801171, 2272191, and 2304940, the coupler is dissolved in a high boiling point solvent and, if necessary, a low boiling point solvent, and dispersed in fine particles to remove the halogen. It is preferable to add it to a silver oxide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di- n-butyl sebacate, tri-n-hexyl phosphate, N,N-
Di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-di-sec - High boiling point solvents such as amyl phenyl butyl ether, monophenyl di-o-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol mono Dissolved in low boiling point solvents such as acetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or Alternatively, it is mixed with an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc. and added to the silver halide emulsion. Alternatively, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538 and JP-A-51-59943.
54-32552 and Research Disclosure, August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methalichloroyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. The silver halide color photographic material of the present invention may contain various other photographic additives. For example, Research Disclosure Magazine
Antifoggants, stabilizers, as described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc. Further, ordinary transparent supports may be used, and these supports may be used depending on the intended use of the photosensitive material. Selected appropriately. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also US patent
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2761791 and No. 2941898. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . In the light-sensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, protective layer, anti-halation layer, etc. may also be provided as constituent layers. They can be used in appropriate combinations. Hydrophilic colloids that can be used in the silver halide emulsion layer as described above can be similarly used as a binder in these constituent layers, and hydrophilic colloids that can be used in the silver halide emulsion layer as described above can also be used in these layers. Various photographic additives can be included. There are no particular restrictions on the method of processing photographic materials using the silver halide emulsion according to the present invention.
Any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water if necessary. and/or a method of stabilizing; or a method of prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development , a method in which stopping, bleaching, fixing, washing, and stabilizing are performed in this order; a developing method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of produced dye, etc. The treatment may be performed using any method. The color developing solution used in the processing of the silver halide emulsion according to the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added. The color developing agent mentioned above is typically 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-
These include 3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. Furthermore, for example, JP-A-48-64932, JP-A No. 50-
No. 131526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples. The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used is 0.0002 mol/
It is used in the range from 0.7 mol/ to 0.7 mol/. Moreover, two or more compounds can be used in 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-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-
Combinations such as ethyl-N-β-hydroxyethylaniline can be freely used depending on the purpose. The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, Alkali metal halides, benzyl alcohol, water softeners,
A thickening agent, a development accelerator, etc. can also be optionally included. Examples of additives other than those mentioned above that are added to the color developing solution include bromides such as potassium bromide and ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-
Methyl-benzotriazole, 1-phenyl-5
- Compounds for rapid processing solutions such as mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyl etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt Bleaching solution contains various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution mentioned above, various other additives such as PH buffers, optical brighteners, antifoaming agents, surfactants,
Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. The processing temperatures for various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc. performed as necessary for the silver halide color photographic light-sensitive material of the present invention are determined from the viewpoint of rapid processing. Preferably, it is carried out at a temperature of 30°C or higher. [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,
In a silver halide color photographic light-sensitive material having a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, the average grain size of the silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm. Yes, 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 green-sensitive silver halide emulsion layer contains the present invention. It is characterized by containing a pyrazolotriazole magenta coupler,
Rapid development processing is possible, processing stability in the rapid development processing is improved, silver can be saved, and fogging can be suppressed. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially applied from the support side to prepare silver halide color photographic light-sensitive material samples Nos. 1 to 4. Layer 1: 1.2 g/m ² gelatin, 0.32 g/m ² (in terms of silver, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1),
0.80 g/m ² yellow coupler (Y-1) dissolved in 0.50 g/m ² dioctyl phthalate
A layer containing. Layer 2...Intermediate layer consisting of 0.70g/ ^m2 gelatin. Layer 3...1.25 g/m ² gelatin, 0.15 g/m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average particle size are shown in Table 1), 0.30 g/m ² dioctyl phthalate A layer containing 0.52 g/m ² of the following pyrazolotriazole magenta coupler exemplified compound (10) dissolved in . Layer 4: Intermediate layer consisting of 1.20 g/m ² of gelatin. Layer 5...1.20 g/m ² gelatin, 0.30 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 phthalate A layer containing 0.45 g/m ² of the following cyan coupler (C-1) dissolved in . Layer 6...0.30 g/m ² dissolved in 1.00 g/m 2 gelatin and 0.20 g/ ^{m 2} dioctyl phthalate
A layer containing the following ultraviolet absorber (UV-1). Layer 7: A layer containing 0.50 g/m ² of gelatin. In addition, as a hardening agent, 2,4-dichloro-6-
layer 2 of sodium hydroxy-S-triazine;
0.017 per gram of gelatin in 4 and 7, respectively.
g.

[Table] Next, for the above samples No. 1 to 4, the magenta coupler in the green-sensitive silver halide emulsion was replaced with the following (MM-1) (amount of coupler applied per 1 ^m2 ).
0.62g), and the only difference was that the amount of silver in the green-sensitive silver chlorobromide emulsion in layer 3 was changed to 0.22g/ ^m2 .
Samples Nos. 5 to 8 corresponding to Samples Nos. 1 to 4 were created. Each of the photosensitive material samples No. 1 to 8 was exposed through an optical wedge and then processed in the following steps. Processing steps (38°C) Color development 3 minutes Bleach-fixing 1 minute 30 seconds Washing 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows. [Color developer] Pure water 800ml Benzyl alcohol 15ml Hydroxyamine sulfate 2.0g Potassium bromide 1.5g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g 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, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to 1 20% potassium hydroxide or
Adjust the pH to 10.1 with 10% dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Iron () ammonium ethylenediaminetetraacetate
65g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetic acid 20g Sodium bromide 10g Add pure water to make 1, and adjust to PH = 7.0 with aqueous ammonia or dilute sulfuric acid. Separately, add 0.5% potassium bromide to the above color developer.
Each of Samples Nos. 1 to 8, which was the same as above, was developed using color developing solutions with the only difference being 1.0, 2.0, and 2.5. Sensitometry was performed on each of the obtained samples by a conventional method. Table 2 shows the gamma values at each potassium bromide concentration.

【table】

[Table] As is clear from the comparison of Samples No. 3 and 7 and Samples No. 4 and 8, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer When a silver halide emulsion other than the present invention is used in combination with the pyrazolotriazole magenta coupler of the present invention, the effect of improving processing stability is small; As is clear from the comparison in No. 6, if the silver halide emulsion of the present invention and the pyrazolotriazole magenta coupler of the present invention are used in combination, a light-sensitive silver halide emulsion layer, especially a green-sensitive silver halide emulsion layer, can be formed. It can be seen that the processing stability is significantly improved. In addition, the silver halide emulsions in the green-sensitive silver halide emulsion layers of Samples No. 1 and 4 are exactly the same,
The only difference is the silver halide emulsion in the blue-sensitive silver halide emulsion layer. However, the processing stability of the green-sensitive silver halide emulsion layer was improved only when the pyrazolotriazole magenta coupler of the present invention and the silver halide emulsion of the present invention were used (Sample No. 1). I understand. Thus, the fact that the developability of the silver halide emulsion in the green-sensitive silver halide emulsion layer differs depending on the silver halide emulsion in the blue-sensitive silver halide emulsion layer is that
This is thought to mean that the developability of the blue-sensitive silver halide emulsion layer influences the developability of the green-sensitive silver halide emulsion layer. This is a completely unknown and surprising fact. Next, in the above example, Sample No. was used except that the average grain size of the blue-sensitive silver chlorobromide emulsion in layer 1 was 0.5 μm, and the silver bromide content was 5 mol%, 20 mol%, and 40 mol%, respectively. Comparative samples A and B and sample C of the present invention were prepared in exactly the same manner as in Example 1, and evaluated in the same manner as in the above example. The results are shown in 2 of Table 2.

[Table] As described above, the silver bromide content of silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is as follows:
It can be seen that the range of 30 to 95 mol% is preferable. Example 2 Using each of the processing solutions of Example 1 using Samples Nos. 1 to 8 (however, the potassium bromide concentration of the color developer was
It was set at 1.0g/. ) Fog of the green-sensitive silver halide emulsion layer was investigated when the color development time was set to 3 minutes and 30 seconds. The results are shown in Table 3.

[Table] As is clear from the results in Table 3, the sample of the present invention
It can be seen that in No. 1 and No. 2, the occurrence of fogging was suppressed even though pyrazolotriazole magenta couplers were used as couplers. Example 3 Sample No. 1 was used to test for rapid processability. That is, using each treatment solution of Example 1 (however,
The potassium bromide concentration of the color developer was set at 1.0 g/. ) The sensitivity (S), gamma (γ), and maximum density (Dm) were investigated when the color development time was set to 2 minutes, 2 minutes 30 seconds, and 3 minutes. Table 4 shows the results.
Shown below.

【table】

[Table] Relative sensitivity when
As is clear from the results in Table 4, the sample of the present invention
It can be seen that No. 1 provides sufficient photographic performance even with a color development time of 2 minutes, and is excellent in rapid processing. Example 4 The same evaluation as in Example 3 was carried out with the only difference that sample No. 5 was used instead of sample No. 1 in Example 1, and the Dm of the green-sensitive silver halide emulsion layer was
The results were similar to those of Sample No. 1 above. As is clear from this, according to the present invention,
It was found that a high Dm could be obtained despite the small amount of silver used. Example 5 A sample was prepared in which the only difference was that exemplified compound (10) was replaced with (3) and (13) in Sample No. 1 in Example 1, and an experiment was conducted in the same manner as in Example 1. , all samples in Example 1
Good results equivalent to No. 1 were obtained.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The silver halide of the silver halide emulsion layer is silver chlorobromide with a silver bromide content of 30 to 95 mol%, and the average grain size of the silver chlorobromide is 0.20 to 95 mol%.
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 green-sensitive silver halide emulsion layer 1. A silver halide color photographic material comprising at least one compound represented by the following general formula []. General formula [] In the formula, R ₁ is a halogen atom or a monovalent organic group that can be separated by a coupling reaction with an oxidized developing agent, R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom or an alkyl atom. group, aryl group,
It represents a heterocyclic group, acylamino group, alkylamino group, anilino group, alkoxycarbonyl group, or alkylthio group, and R ₂ and R ₃ are never hydrogen atoms at the same time.