JPH0219939B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide color photographic light-sensitive material (hereinafter simply a photographic light-sensitive material) using a high chloride silver halide emulsion that has been spectrally sensitized, particularly by a combination of two or more types of sensitizing dyes. (abbreviated as ), more specifically, photographic sensitization using a high chloride silver halide emulsion that is spectrally sensitized in the wavelength range of blue light (approximately 400 to 500 nm) by a combination of two or more sensitizing dyes. Regarding materials. Here, the high chloride silver halide emulsion refers to an emulsion consisting of silver chloride containing 80 mol % or more of silver halide. Until now, silver halide emulsions mainly containing silver bromide have been used in photographic light-sensitive materials because it is easy to obtain relatively high sensitivity. However, it is known that high chloride silver halide emulsions can be processed more quickly than these silver halide emulsions containing mainly silver bromide. There may be several reasons for this, and one of the reasons may be that it is highly soluble. In addition, since silver chloride absorbs almost no visible light, when used in photographic light-sensitive materials, there is a difference between the blue sensitivity of green-sensitive emulsions and red-sensitive emulsions and the blue sensitivity of blue-sensitive emulsions. There is no need for any ingenuity to expand. This makes it possible to remove the yellow filter layer from photographic materials that reduce the blue sensitivity of green- and red-sensitive emulsions due to the yellow filter layer, thereby reducing the risk of fogging in adjacent emulsion layers. It becomes possible to remove colloidal silver, which was the cause of the problem. In addition, in some photographic materials, silver halide grains with large grain sizes are used in the blue-sensitive emulsion layer to improve the blue sensitivity of green- and red-sensitive emulsions and the blue sensitivity of blue-sensitive emulsions. However, since this is no longer necessary, disadvantages such as easy fogging and poor developability due to large particles are alleviated. recent years,
There has been an increasing demand for rapid processing of photographic light-sensitive materials, and there has been a strong desire to realize photographic light-sensitive materials using high chloride silver halide emulsions having these advantages. However, although it has these advantages, silver chloride does not absorb visible light, which is extremely disadvantageous when used as a blue-sensitive emulsion, and its storage stability is also poor, so that it has not been put to practical use. . Since silver chloride does not absorb visible light, it is clear that spectral sensitization is essential even when it is used as a blue-sensitive emulsion layer. However, in the so-called photographic materials used for photographing subjects,
Unless the spectral sensitivity distribution has a good correspondence with human visual characteristics, good color reproduction cannot be expected in the final image. In addition, so-called print sensitive materials, which are used to make images recorded on photosensitive materials into appreciable images, have an appropriate spectral sensitivity distribution that can accurately accept the information recorded on the photosensitive materials. There must be.
Regarding the use of current color negatives and color photographic paper, in this system, if the overlap between the spectral absorption of the yellow pigment in the color negative and the spectral sensitivity distribution of the blue-sensitive emulsion in the color photographic paper is small, the final image will be significantly affected. The resulting image has low contrast and lacks yellowness. If a color correction filter is used as a means to compensate for such defects, dark yellow parts will become reddish or red will become purplish, causing problems in color reproduction. This phenomenon occurs because the effective blue sensitivity of the blue-sensitive emulsion of the color photographic paper is low, so that the sensitivity of the green-sensitive emulsion layer on the short wavelength side becomes relatively negligible. Generally, for printing in a color printing room, a tungsten lamp (recently, halogen lamps filled with halogen gas are increasingly being used) is used as the light source, and looking at the energy distribution of the light, the light source is On the wavelength side,
Its distribution weight is increasing. Furthermore, this tendency is generally strengthened due to the color masks used in color negatives. Therefore, it is theoretically possible to improve this drawback by extending the spectral sensitization region toward longer wavelengths. Although such a method can actually alleviate the above-mentioned drawbacks, this method also causes other problems. This appears as problems in color reproduction, such as green being reproduced with a bluish tint, or yellow not being sufficiently concentrated. This phenomenon occurs because the color mask correction used in color negatives does not work effectively. Even when simply spectral sensitization is performed in this way, the balance of sensitivity within the relevant wavelength region is actually important and has become a serious problem. Many spectral sensitization techniques in the blue light region have been disclosed so far. For example, Japanese Patent Publication No. 45-19034 is characterized in that it has a sulfoalkyl group or a sulfoalkoxyalkyl group. Japanese Patent Publication No. 46-30023 discloses a technique using a simple merocyanine dye or a complex merocyanine dye having either a benzothiazole nucleus or a benzoxazole nucleus and a rhodanine nucleus.
Benzothiazole nucleus, benzoselenazole nucleus, benzoxazole nucleus, α-naphthothiazole nucleus, β-naphthothiazole nucleus, α, characterized by having a sulfoalkyl group, a sulfoaralkyl group
-One of the nuclei such as naphthoxazole nucleus, β-naphthoxazole nucleus, rhodanine nucleus, 2
- Thioxazoline - A technology using a simple merocyanine dye having one of the 2,4-dione nucleus, thiohydantoin nucleus, etc.
No. 48-78930 describes sulfoalkyl group, 2-
A pyrroline nucleus, a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, characterized by having a (2-sulfoethoxy)ethyl group, a 2-(2-hydroxy-3-sulfopropoxy)ethyl group, A technique using a simple cyanine dye having two nuclei selected from a benzoselenazole nucleus, a naphthoselenazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, an imidazole nucleus, a benzoimidazole nucleus, a pyridine nucleus, and a quinoline nucleus is disclosed. ing. However, these conventional techniques relate to silver halide emulsions containing silver bromide as the main component, and either spectral sensitization technology in the blue light region for silver halide emulsions containing silver bromide as the main component or the inherent sensitivity of silver halide is used. If only the spectral sensitivity range of a blue-sensitive emulsion is taken as the spectral sensitivity range of a blue-sensitive emulsion, its spectral absorption is based on the ultraviolet region, so it does not correspond to the spectral characteristics of the yellow dye, and therefore the color reproducibility of the yellow dye is poor. It was intended to improve the For this purpose, David
El Mac Adam (David L. Mac)
"Color Science End Color Photography (Fujitsuk Today Vol. 20, pp. 27-39 (1967)" (color
science and color photography (Physics
Today), blue-sensitive emulsions are spectrally sensitized to impart absorption on the long wavelength side. Therefore, if such a technique is simply applied to a high chloride silver halide emulsion, the spectral characteristics of the yellow dye and the blue-sensitive emulsion will be different in the relatively short wavelength region (wavelength region less than 445 nm). The deviation of the spectral sensitivity distribution became large, giving only unsatisfactory results. Spectral sensitization using two or more types of sensitizing dyes is also commonly carried out by those skilled in the art. Several combinations of blue-sensing dyes in the blue light region have already been disclosed, for example,
Publication No. 14019 describes a thiazole nucleus, (for the purpose of indicating whether a benzene ring is fused or not, a thiazole nucleus is referred to as a fused thiazole nucleus when both a benzothiazole nucleus and a naphthothiazole nucleus are simultaneously expressed). , will be used below. The same applies to selenazole nucleus, oxazole nucleus, etc.), benzothiazole nucleus,
A simple cyanine dye having two nuclei selected from benzoselenazole nuclei, a naphthothiazole nucleus, and one nucleus selected from a condensed or non-condensed thiazole nucleus and a condensed selenazole nucleus. A combination of simple cyanine dyes having a nucleus and
―29128 Publication describes a simple cyanine dye having one nucleus selected from a condensed or non-condensed thiazole nucleus, a condensed or non-condensed selenazole nucleus, and either a naphthothiazole nucleus or a naphthoselenazole nucleus. and a simple cyanine dye having one nucleus selected from a condensed or non-condensed thiazole nucleus, a condensed or non-condensed selenazole nucleus, and one nucleus selected from a condensed or non-condensed imidazole nucleus,
JP-A-51-30724 discloses a simple cyanine having one nucleus selected from a condensed or non-condensed thiazole nucleus, a condensed or non-condensed selenazole nucleus, and one nucleus selected from a condensed or non-condensed imidazole nucleus. A combination of a dye, a simple cyanine dye having either a pyridine nucleus or a quinoline nucleus, and one nucleus selected from a condensed or non-condensed siimidazole nucleus, and a condensed or non-condensed oxazole nucleus is disclosed. There is. However, like the techniques mentioned above, these techniques are related to emulsions mainly containing silver bromide, and even if these techniques are applied to high chloride silver halide emulsions, satisfactory results in terms of spectral sensitivity cannot be obtained. I couldn't get it. In this way, when using a high chloride silver halide emulsion as a blue-sensitive emulsion, it is not enough to simply apply the conventional technology; it is necessary to have sufficient sensitivity even in the short wavelength region of less than 445 nm. Therefore, there has been a strong desire to develop a technique for combining sensitizing dyes that provides a preferable spectral sensitivity distribution when applied to high chloride silver halide emulsions. A first object of the present invention is to provide a photographic material that can be rapidly processed and has improved color reproducibility. Moreover, the second object of the present invention is to
It is an object of the present invention to provide a color photographic paper which can be rapidly processed and has improved color reproducibility. The above-mentioned object was achieved through intensive research by the present inventors in a photographic light-sensitive material having a blue-sensitive silver halide emulsion layer containing at least one negative-working silver halide on a support. At least one sensitizing dye consisting of 80 mol% silver chloride and having a maximum spectral sensitivity in a wavelength range of 445 nm or more and 490 nm or less, and a sensitizing dye having a maximum spectral sensitivity in a wavelength range of 420 nm or more and less than 445 nm. It has become clear that this can be achieved by using a photographic material color-sensitized with at least one type of dye. The present invention has a maximum value of spectral sensitivity of 445 nm or more.
At least one type of sensitizing dye having a wavelength range of 490 nm or less (hereinafter referred to as a long-wave dye), and at least one type of sensitizing dye having a maximum value of spectral sensitivity in a wavelength range of 420 nm or more and less than 445 nm (hereinafter referred to as a long-wave dye) (referred to as a short-wave dye), and an emulsion consisting of at least 80 mol% silver chloride as a negative silver halide emulsion. The long-wave dye according to the present invention has a maximum value of spectral sensitivity.
Any compound having any structure can be preferably used as long as it has a wavelength range of 445 nm or more and 490 nm or less, but the following compounds can be cited as particularly preferable examples of sensitizing dyes. However, the present invention is not limited to these dyes. The short-wave dye according to the present invention has a maximum value of spectral sensitivity.
Any compound having any structure can be preferably used as long as it is a sensitizing dye having a wavelength range of 420 nm or more and less than 445 nm, but examples of particularly preferable sensitizing colors are shown below. However, the present invention is not limited to these dyes. The long-wave dye and short-wave dye according to the present invention are known, for example, as described in The Chemistry of Heterocyclic Compounds by F.M.
Compounds) Volume 18 The Cyanine Soybean
And Related Compounds (The
Cyanice Dyes and Relataed compounds) (A.
Weissberger ed., Interscience New York
It can be easily synthesized according to the method described in (1964). The optimal concentration of sensitizing dye used in the present invention can be determined according to methods known to those skilled in the art. For example, a method is preferably used in which the same emulsion is divided, each divided emulsion is made to contain a different concentration of sensitizing dye, the sensitivity of each is measured, and the optimum density thereof is determined. The amount of sensitizing dye used in the silver halide emulsion according to the present invention is not particularly limited, but the sensitizing dye is used in an amount of 2 x 10 ^-6 mol to 1 x 10 ^-3 mol per 1 mol of silver halide. is advantageous. Particularly advantageous is the range from 1×10 ^-4 mol to 5×10 ^-4 mol. An advantageous proportion of amounts when combining a long-wave dye and a short-wave dye is the molar ratio of (long-wave dye/short-wave dye)
20/1 to 1/20, particularly 10/1 to 1/10 being particularly advantageous. For adding the sensitizing dye according to the invention to the emulsion, methods well known in this field can be used. For example, these sensitizing dyes can be dispersed directly in emulsions or in pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve,
Acetone etc. (or a mixture of such solvents)
It can be dissolved in a water-miscible solvent, in some cases diluted with water, and in some cases dissolved in water, and added to the emulsion in the form of these solutions. Further, ultrasonic vibration can also be used for this dissolution. Furthermore, as described in U.S. Pat. No. 3,469,987, dyes can be prepared using a method in which the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. As described in Japanese Patent No. 24185, a method is also used in which a water-insoluble dye is dispersed in a water-miscible solvent without being dissolved, and this dispersion is added to an emulsion. Further, the dye can be added to the emulsion in the form of a dispersion by an acid dissolution/dispersion method. Other additions to emulsions include U.S. Patent No. 2912345, U.S. Pat.
The method described in the same No. 3425835 etc. can also be used. The sensitizing dyes contained in combination in the present invention are dissolved in the same or different solvents, and these solvents are mixed or added separately prior to addition to the silver halide emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose. The sensitizing dye according to the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but preferably during or after chemical ripening. The emulsion according to the present invention is a negative emulsion, and
It is a so-called surface latent image type emulsion that mainly forms a latent image on the grain surface. This term "surface latent image type emulsion" is a term representing a concept opposite to the term "internal latent image type emulsion" defined in, for example, Japanese Patent Application Laid-Open No. 47-32814. In the case of a negative emulsion, an image used in practical use is formed by increasing the image density as the amount of light irradiated onto the photographic emulsion increases. Of course, even such emulsions can undergo a phenomenon called solarization, where the emulsion is reversed due to excessive exposure, but this is a phenomenon caused by exposure that is higher than that used in practical use, and is not a problem. . The silver halide used in the present invention is 80 mol%
Although the above-mentioned silver halide includes silver chloride, it is preferable that 90 mol % or more is silver chloride, and more preferably pure silver chloride is used. In this case, most of the remaining silver halide other than silver chloride is silver bromide.Of course, it may be all silver bromide, but depending on the use, it may contain several mol% of silver iodide. You can stay there. The silver halide used in the present invention may have a (100) surface, a (111) surface, or both surfaces on its outer surface. can also be preferably used. Further, silver halide having a (110) plane on the outer surface can be similarly preferably used. The size of the silver halide grains used in the present invention may be within the range normally used for photographic light-sensitive materials, but it is preferable that the average grain size is 0.05 μm to 1.0 μm. Although the particle size distribution may be polydisperse or monodisperse, monodisperse emulsions are more preferably used. Silver halide grains used in the present invention can be prepared by methods commonly used by those skilled in the art. These methods are described in, for example, Mies, The Theory of Photographic Process.
The ammonia method, the neutral method, which is generally known and is described in books such as Process (published by Mac Millan),
It can be prepared by various methods such as acid method. A preferred method is to mix a water-soluble silver salt and a water-soluble halide salt in the presence of an appropriate protective colloid, and adjust the temperature, pAg, PH value, etc. appropriately during the precipitation of silver halide. Preferably, the method is one in which the value is controlled. The silver halide emulsion may or may not be physically ripened. Water-soluble salts are usually removed from emulsions after precipitation or physical ripening, and even if the long-known noodle washing method is used for this purpose, inorganic salts containing polyvalent anions ( For example, ammonium sulfate, magnesium sulfate), anionic surfactants,
Precipitation methods utilizing polystyrene sulfonic acid, other anionic polymers, or gelatin derivatives such as aliphatic or aromatic-acylated gelatin may also be used. The silver halide emulsion used in the present invention can be chemically ripened by a method commonly used by those skilled in the art. For example, the method described in books such as The Theory of Photographic Process by Mies mentioned above, or various other known methods can be used. That is, compounds containing sulfur that can react with silver ions,
For example, thiosulfates or US Pat. No. 1,574,944,
Same No. 2278947, Same No. 2410689, Same No. 3189458,
No. 3,501,313, French Patent No. 2,059,245, sulfur sensitization using activated gelatin, and reducing agents, such as those described in U.S. Pat.
2,518,698, US Pat. No. 2,521,925, US Pat. No. 2,521,926,
Amines described in US Pat. No. 2419973, US Pat. No. 2419975, iminoaminomethane sulfuric acid described in US Pat.
2694637, reduction sensitization method such as the method of HWWood described in Journal of Photographic Science, Vol. 1 (1953), p. 163 et seq., or U.S. Patent No.
Gold sensitization method using gold complex salts, gold thiosulfate complexes, etc. described in No. 2399083, or U.S. Patent No. 2448060,
Sensitization methods using salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium described in No. 2540086, No. 2566245, and No. 2566263 can be used alone or in combination. . The selenium sensitization method described in US Pat. No. 3,297,446 can also be used in place of or in conjunction with the sulfur sensitization method. In the emulsion used in the present invention, gelatin is mainly used as a protective colloid, and inert gelatin is particularly useful. In addition, instead of gelatin, photographically inert gelatin derivatives (e.g., phthalated gelatin, etc.), water-soluble synthetic resin polymers (e.g.,
(polyvinyl alcohol, polyvinylpyridone, carboxymethylcellulose, hydroxymethylcellulose, etc.) can also be used. In the photographic emulsion of the present invention, tetracindenes, mercaptotetrazole compounds, etc. are added for the purpose of preventing fog during the manufacturing process, during storage of photographic light-sensitive materials, or during development processing, or to stabilize photographic performance. It may be included. The photographic material of the present invention may be a so-called internal photographic material containing a coupler, or a so-called external photographic material in which a coupler is supplied during development. As the coupler contained in the photographic light-sensitive material according to the present invention, any compound that can undergo a coupling reaction with an oxidized form of a developing agent to form a coupling product having a maximum spectral absorption wavelength in a wavelength range longer than 340 nm may be used. However, particularly representative ones include those shown below. As a coupler that forms a coupling product having a maximum spectral absorption wavelength in the wavelength range from 350 nm to 550 nm, what is known as a so-called yellow coupler is typical among those skilled in the art. No. 2322027, same no.
No. 2728658, No. 2875057, No. 3265506, No. 3277155, No. 3408194, No. 3415652,
Same No. 3447928, Same No. 3664841, Same No. 3770446,
Same No. 3778277, Same No. 3849140, Same No. 3894875,
British Patent No. 778089, British Patent No. 808276, British Patent No. 875476
No. 1402511, No. 1421126 and No.
No. 1513832, Special Publication No. 13576, No. 13576, Japanese Patent Publication No. 1973-
No. 29432, No. 48-66834, No. 49-10736, No. 49
- No. 122335, No. 50-28834, No. 50-132926,
No. 50-138832, No. 51-3631, No. 51-17438,
No. 51-26038, No. 51-26039, No. 51-50734,
No. 51-53825, No. 51-75521, No. 51-89728,
No. 51-102636, No. 51-107137, No. 51-117031
No. 51-122439, No. 51-143319, No. 53-
No. 9529, No. 53-82332, No. 53-135625, No. 53
-No. 145619, No. 54-23528, No. 54-48541, No. 54-48541, No. 54-23528, No. 54-48541, No.
It is described in publications such as No. 54-65035, No. 54-133329, and No. 55-598. Typical couplers that form coupling products having a maximum spectral absorption wavelength in the wavelength range from 500 nm to 600 nm are those known in the art as magenta couplers, for example, U.S. Pat. Nos. 1969479 and 2213986. , No. 2294909,
Same No. 2338677, Same No. 2340763, Same No. 2343703,
Same No. 2359332, Same No. 2411951, Same No. 2435550,
Same No. 2592303, Same No. 2600788, Same No. 2618641,
Same No. 2619419, Same No. 2673801, Same No. 2691659,
Same No. 2803554, Same No. 2829975, Same No. 2866706,
Same No. 2881167, Same No. 2895826, Same No. 3062653,
Same No. 3127269, Same No. 321437, Same No. 3253924,
Same No. 3311476, Same No. 3419391, Same No. 3486894,
Same No. 3519429, Same No. 3558318, Same No. 3617291,
Same No. 3684514, Same No. 3705896, Same No. 3725067,
British Patent No. 3888680, British Patent No. 720284, British Patent No.
No. 737700, No. 813866, No. 892886, No. 892886, No. 892886, No.
No. 918128, No. 1019117, No. 1042832, No. 1042832, No.
No. 1047612, No. 1398828 and No. 1398979,
West German Patent Publication No. 814996, West German Patent No. 1070030, Belgian Patent No. 724427, JP-A-46-60479, 49
-No. 29639, No. 49-111631, No. 49-129538,
No. 50-13041, No. 50-116471, No. 50-159336
No. 51-3232, No. 51-3233, No. 51-10935
No. 51-16924, No. 51-20826, No. 51-
No. 26541, No. 51-30228, No. 51-36938, No. 51
- No. 37230, No. 51-37646, No. 51-39039, No.
No. 51-44927, No. 51-104344, No. 51-105820,
No. 51-108842, No. 112341, No. 51-112342,
No. 51-112343, No. 51-112344, No. 51-117032
No. 51-126831, No. 52-31738, No. 53-
No. 9122, No. 53-55122, No. 53-75930, No. 53-
It is described in the following publications: No. 86214, No. 53-125835, No. 53-123129, and No. 54-56429. A typical coupler that forms a coupling product having a maximum spectral absorption wavelength in the wavelength range from 600 nm to 750 nm is known in the art as a cyan coupler, and is disclosed in U.S. Patent No.
2306410, 2356475, 2362598, 2367531, 2369929, 2423730,
Same No. 2474293, Same No. 2476008, Same No. 2498466,
Same No. 2545687, Same No. 2728660, Same No. 2772162,
Same No. 2895826, Same No. 2976146, Same No. 3002836,
Same No. 3419390, Same No. 3446622, Same No. 3476563,
Same No. 3737316, Same No. 3758308, Same No. 3839044,
British Patent No. 478991, British Patent No. 945542, British Patent No.
Specifications of No. 1084480, No. 1377233, No. 1388024, and No. 1543040, as well as JP-A-1977-
No. 37425, No. 50-10135, No. 50-25228, No. 50
- No. 112038, No. 50-117422, No. 50-130441,
No. 51-6551, No. 51-37647, No. 51-52828,
No. 51-108841, No. 53-109630, No. 54-48237
No. 54-66129, No. 54-131931, No. 55-
It is described in various publications such as No. 32071. Couplers that form coupling products having a maximum spectral absorption wavelength in the wavelength range from 700 nm to 850 nm include JP-B No. 52-24849 and JP-A No. 53-125836.
No. 53-129036, No. 55-21094, No. 55-
It is described in publications such as No. 21095 and No. 55-21096. The negative silver halide photographic emulsion according to the present invention is
It is generally used together with a so-called yellow coupler, and a particularly preferred yellow coupler is an α-pivaloylacetanilide yellow coupler. Furthermore, the silver halide emulsion of the present invention can also be used in combination with a so-called magenta coupler. Among these, preferred magenta couplers are 5-pyrazolone magenta couplers. When these couplers are incorporated into a photographic light-sensitive material, they are incorporated by dispersing them in a hydrophilic colloid by a technically effective method.
Various known methods can be used to disperse these couplers, but a method in which these couplers are dissolved in a substantially water-insoluble high-boiling solvent and dispersed in a hydrophilic colloid is preferably used. Particularly useful high-boiling solvents include Nn-butylacetanilide, diethyl lauramide, dibutyl lauramide, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, N-dodecylpyrrolidone, and the like. A low boiling point solvent or an organic solvent easily soluble in water can be used to aid in the dissolution. Examples of low boiling point solvents include ethyl acetate, methyl acetate, cyclohexanone, acetone, methanol, ethanol, tetrahydrofuran, etc., and organic solvents that are easily soluble in water include 2-methoxyethanol,
Dimethylformamide etc. can be used.
These low boiling point solvents and organic solvents that are easily soluble in water can be removed by washing with water, coating and drying, or the like. Furthermore, this silver halide emulsion may contain various other photographic additives such as known hardeners, spreading agents, ultraviolet absorbers, fluorescent whitening agents, substance modifiers (wetting agents, polymer aqueous dispersions, etc.). ), condensates of phenols and formalin, etc. The silver halide photographic emulsion according to the present invention is generally coated on a suitable support and dried to produce a silver halide photographic light-sensitive material. Supports used at this time include paper, glass, cellulose acetate, Films such as cellulose nitrate, polyester, polyamide, polystyrene, etc., or laminates of paper and polyolefin (polyethylene, polypropylene, etc.), etc.
A laminate of more than one type of substrate is used. In order to improve the adhesion to the silver halide emulsion, this support is generally subjected to various surface improvement treatments, such as surface treatment such as electron impact treatment, or subbing treatment to provide an undercoat layer. The one prepared is used. The silver halide photographic emulsion is coated and dried on this support by a commonly known coating method, such as dip coating, roller coating, bead coating, curtain flow coating, etc., and then dried. The silver halide photographic material according to the present invention is basically constructed as described above, but is further spectrally sensitized to other wavelength regions, that is, green-sensitive and red-sensitive silver halide photographic materials. A color photographic light-sensitive material can be formed by combining various photographic constituent layers selected as necessary from emulsion layers, intermediate layers, protective layers, lid layers, antihalation layers, backing layers, etc. In this case, each photosensitive emulsion layer may have a two-layer structure consisting of emulsions with different sensitivities. After exposing the photographic material of the present invention, various photographic processes can be used. The processing temperature and time are set appropriately, and the temperature is room temperature or lower than room temperature, for example, 18℃ or less, or higher than room temperature 30℃.
The temperature may be higher than 0.degree. C., for example around 40.degree. C., or even over 50.degree. For color development processing, as a color developing agent, for example, N,N-dimethyl-p-phenylenediamine,
N,N-diethyl-p-phenylenediamine, N
-Carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N-carboxymethyl-
2-Methyl-p-phenylenediamine, N-carbamidomethyl-N-ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminophenol, 3- Acetylamino-4-aminodimethylaniline, N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-N-β-
A sodium salt of sulfoethyl-p-phenylenediamine or the like can be used. The photographic light-sensitive material of the present invention can contain these color developing agents in the hydrophilic colloid layer as the color developing agent itself or as its precursor, and can be processed in an alkaline activation bath. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are disclosed in, for example, US Pat. No. 3,342,599;
Same No. 2507114, Same No. 2695234, Same No. 3719492,
British Patent No. 803783, Japanese Unexamined Patent Publication No. 135628, No. 54
- 79035, Research Disclosure Magazine No. 15159, Research Disclosure No. 12146, and Research Disclosure No. 13924. When these aromatic primary amine color developing agents or their precursors are activated,
It is necessary to add enough amount to obtain sufficient color development. The amount varies depending on the type of photographic light-sensitive material, but it is generally advantageously used in the range of 0.1 mol to 5 mol, preferably 0.5 mol to 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photographic light-sensitive material, it can be added by dissolving it in a suitable solvent such as water, methanol, ethanol, acetone, etc. Also, high boiling point organic solvents such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. can be added. It can be added as an emulsified dispersion, or as a latex polymer impregnated as described in Research Disclosure No. 14850. Usually, bleaching and fixing are performed after color development, but bleaching may be performed simultaneously with fixing. Many compounds are used as bleaching agents, including polyvalent metal compounds such as iron (), cobalt (), copper (), and especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. Acetic acid, aminopolycarboxylic acids such as N-hydroxyethylethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferricyanates, dichromates, etc. alone or as appropriate. combinations are used. A preferred embodiment of the present invention is as follows. 1 Silver halide color photographic light-sensitive material as claimed in the claims containing a yellow-forming coupler 2 At least one of the negative-working silver halide emulsion layers is a blue-sensitive silver halide emulsion layer, and a yellow-forming coupler is included in the silver halide color photographic material. Silver halide color photographic light-sensitive material 3 contained in the blue-sensitive emulsion layer as claimed in the claims.A blue-sensitive emulsion layer containing a yellow-forming coupler and a green-sensitive emulsion layer containing a magenta-forming coupler on a support from the side near the support. A silver halide color photographic light-sensitive material according to claim 1, comprising a red-sensitive emulsion layer containing a red-sensitive emulsion layer and a cyan-forming coupler. [Example 1] A silver chloride emulsion with an average grain size of 0.70 μm was prepared and chemically ripened using 8.2×10 ^-6 mol of sodium thiosulfate per 1 mol of silver chloride according to a conventional method. Chemical ripening conditions were set to optimize photographic performance by adjusting the time and temperature. Sensitizing dye (-7) 5 minutes before the end of chemical ripening
Then, (-7) and (-1) were added to the emulsion as shown in Table 1, and a stabilizer (ST-
1) was added in an amount of 1 g per mole of silver halide, and 0.3 mole of yellow coupler (YC-1) was added per mole of silver halide, and 0.15 mole of a color stain inhibitor (AS-1) was added to 1 mole of this coupler. 1) was dispersed in dibutyl phthalate (hereinafter abbreviated as DBP) and added to the emulsion at the same time. The above emulsion was coated on a photographic paper support coated with polyethylene containing anatase titanium oxide, and the amount of silver was set as metallic silver.
0.35 g/m ² and a gelatin amount of 3.0 g/m ² , and a protective layer was further applied thereon so that the gelatin amount was 2.0 g/m ² . The protective layer contained bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a spreading agent. In this way, samples 1 to 6 were created,
Furthermore, these photosensitometer KS-7 type (Konishi Roku Photo Industry)
(a) using a tungsten lamp (color temperature 2854K) as the light source. (b) Light wedge exposure was performed using light separated by an interference filter having a transmission maximum at 430 nm. (c) Light wedge exposure was performed using light separated by an interference filter having a transmission maximum at 470 nm. Each of the samples subjected to the three types of exposure (a) to (c) above was then subjected to the following color development treatment. The reflection density of the dye image formed for each sample was measured using a Sakura color densitometer PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.).
Measure using the included blue filter,
Specific sensitivity and fog were obtained. Specific sensitivity is based on sample 1 being 100 in exposure without an interference filter, and 100 in sensitivity when exposed to 430nm light for each sample in exposure with an interference filter.
The sensitivity when exposed to light at 470 nm is shown. (ST-1) 4-hydroxy-6-methyl-1,
3,3a,7-tetrazaindene (YC-1)α-(1-benzyl-2,4-dioxo-3-imidazolidinyl)α-pivalyl-
2-Chloro-5-[γ-(2,4-di-t-amylphenoxy)butanamide]acetanilide (AS-1) 2,5-di-t-octylhydroquinone treatment process Color development (CD-1) 33℃ 1 Bleach and fix for 33℃ for 1 minute and 30 seconds Wash with water 30-34℃ for 3 minutes Dry Color developer composition (CD-1) Pure water 800ml Ethylene glycol 12ml Penzyl alcohol 12ml Anhydrous potassium carbonate 30g Anhydrous potassium sulfite N-Ethyl-N -(β-methanesulfonamido)ethyl-3-methyl-4
Aminoaniline 2.0g Sulfate 4.5g Adenine 0.03g Sodium chloride 1.0g Adjust the pH to 10.2 with potassium hydroxide or sulfuric acid. Bleach-fix solution composition Pure water 750ml Sodium iron() ethylenediaminetetraacetate
50g Ammonium thiosulfate 85g Potassium bisulfite 10g Sodium metabisulfite 2g Ethylenediaminetetraacetic acid disodium salt 20g Sodium bromide 3.0g Add pure water to make 1, and adjust to PH = 7.0 with aqueous ammonia or sulfuric acid. The results are shown in Table 1.

[Example 2]

A photographic paper support covered with a polyethylene film containing anatase-type titanium oxide is subjected to corona discharge machining, and the following six layers are sequentially coated on top of this,
A photosensitive material for printing was produced. The amount of each substance is expressed per 1 m ² of photographic material, and silver halide is expressed in terms of silver. Layer 1 0.45g of blue-sensitive silver chloride emulsion (6 kinds prepared under the same conditions as in Example 1), 1.47g of gelatin, 0.8g of yellow-forming coupler (YC-1) and 0.015g of color stain inhibitor (AS). -1) Blue-sensitive emulsion layer containing dissolved and dispersed 2. First intermediate layer containing 0.03 g of DBP dispersed in 1.03 g of gelatin with 0.015 g of color stain inhibitor (AS-1) dissolved therein. Layer 3 0.40g green-sensitive silver chloride emulsion (average grain size
0.45 μm), 0.63 g of magenta coupler (MC-1) and 0.015 g of color stain inhibitor (AS-1) were dissolved in 1.85 g of gelatin. Green photosensitive emulsion layer containing 0.34g of tricresyl phosphate (hereinafter referred to as TCP) dispersed) MC-13-[2-chloro-5-(1-octadecenylsuccinimide)anilino]-1-
(2,4,6-Trichlorophenyl)-5-pyrazolone layer 4 1.45g of gelatin, 0.2g of ultraviolet absorber (UV
-1), 0.3g of ultraviolet absorber (UV-2) and
Dissolved 0.05g of color stain prevention agent (AS-1)
Second intermediate layer containing 0.22g of DBP dispersed UV-1:2-(2-hydroxy-3,5-di-t-butylphenyl)-benzotriazole UV-2:2-(2-hydroxy-5-t -butylphenyl)-benzotriazole layer 5 0.30g of red-sensitive silver chloride emulsion (average grain size
0.40μm), 1.6g gelatin and 0.42g cyan coupler (CC-1), 0.005g color stain inhibitor (AS
Red-sensitive emulsion layer CC-12-[2-(2,4-di-t-amylphenoxy)butanamide]-4,6-di-chloro-5- containing 0.3 g of DBP dissolved in -1) dispersed therein. Methylphenol layer 6 Protective layer containing 1.8 g of gelatin The silver halide emulsion used in layer 1 was chemically ripened by the same method as described in Example 1, as described above, and after addition of stabilizers 10 % aqueous gelatin solution was added and stirred, then cooled and set. The silver halide emulsion used in layer 3 was chemically ripened using 1.5 x 10 ^-5 mol of sodium thiosulfate per 1 mol of silver halide, and 3.0 x as a sensitizing dye.
10 ^-4 mol of andhydro-5,5'-difnyl-9
-Ethyl-3,3'-di-(γ-sulfopropyl)
It was prepared in the same manner as the layer 1 emulsion except that oxacarbocyanine hydroxide was used. The silver halide emulsion used in layer 5 contained 3.0×10 ^-4 mol of 3,3'-di-(β-
It was prepared in the same manner as the emulsion in Layer 3 except that hydroxyethyl)thiadicarbocyanine bromide was used as the sensitizing dye. In addition to the above materials, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid were contained. Sample 7 (-1) with sensitizing dye (1-7) alone
Sample 8 was prepared using the above method, and sample 9 was prepared using a combination of (-7) and (-1). In addition, each emulsion layer is a silver chlorobromide emulsion (blue-sensitive emulsion layer) containing 15 mol% of silver chloride with an average grain size of 0.70 μm;
Silver chlorobromide emulsion (green-sensitive emulsion layer) containing 20 mol% silver chloride with an average grain size of 0.45 μm, average grain size of 0.40 μm
Sample 10 was prepared under the same conditions except that each sample was replaced with a silver chlorobromide emulsion (red-sensitive emulsion layer) containing 20 mol % of silver chloride. Table 2 shows the sample summary.
Shown below.

[Table] When these four types of samples were exposed through a color negative and subjected to the processing described in Example 1, sample 10
In this case, almost no image could be obtained, and the yellowish tinge was particularly lacking. For this reason (CD-2) 3.5 with color developer
When the development was changed to one minute, color prints with good color and tone reproduction were obtained.
Samples 7, 8, and 9 all gave almost good images after being developed for 1 minute with the (CD-1) color developing solution, but sample 7 had the drawback that the green was reproduced with a bluish tint. was. Moreover, in sample 8,
This method has the disadvantage that high-density yellow parts are reproduced with a reddish tinge. Photosensitive material sample 9 according to the present invention does not have such defects, and compared to conventional color prints (sample 10), there is no decrease in saturation even in the high density areas of red and green, and silver chloride It will be easily understood that a color photographic paper having both excellent rapid processability and excellent color reproducibility can be obtained by the combination of the sensitizing dyes according to the present invention. (CD-2) Color developer: Among the compositions of the color developer shown in Example 1, CD-2 is the one in which 0.03g of adenine is set to 0g and 0g of potassium bromide is set to 0.5g.
It is called.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer containing at least one negative-working silver halide layer on a support,
The negative-working silver halide consists of at least 80 mol% silver chloride, and has a maximum spectral sensitivity.
At least one sensitizing dye having a wavelength range of 445 nm or more and 490 nm or less, and a maximum value of spectral sensitivity of 420 nm.
A silver halide color photographic light-sensitive material characterized in that it is color sensitized with at least one sensitizing dye having a wavelength range of less than 445 nm.