JPH0682967A - Silver halide color photogrtaphic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in rapid processability and sharpness and small in changes of sensitivity when humidity varies at the time of exposure and a time length from exposure to development processing varies. CONSTITUTION:The silver halide color photographic sensitive material has at least each one of yellow, magenta, and cyan color-developing silver halide emulsion layers on a support, and the silver halide emulsion layer contains silver chloro-bromide emulsion grains having the content of >=95mol% silver chloride or silver chloride emulsion grains alone and substantially not containing silver iodide, and at least one hydrophilic colloidal layer formed between the support and the silver halide emulsion layer nearest to the support contains a white pigment in a filling rate of >=20 weight %, and the pH and the pAg of the film of the photosensitive material are 5.6-6.5 and 6.0-10.0, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, which is excellent in rapid processability and sharpness, has a small sensitivity change when the humidity at the time of exposure is changed, and is further processed up to a post-exposure development process. The present invention relates to a silver halide color photographic light-sensitive material in which sensitivity changes little with time.

[0002]

2. Description of the Related Art There are a wide variety of silver halide color photographic light-sensitive materials and image-forming methods using them which are currently on the market, and their application examples can be found in all fields. The performance required for many of these light-sensitive materials varies widely depending on their respective uses, and one of them is "high density recording property". In order for silver halide color photographic light-sensitive materials to fully exhibit high density recording properties, they must have high sharpness. For this reason, various techniques for increasing the sharpness have been developed and actually applied depending on the required level of the photosensitive material and the usage form thereof. The factors that reduce the sharpness of a light-sensitive material are mainly halation caused by reflection of incident light at the emulsion layer-support interface or support-air interface and irradiation caused by light scattering by the silver halide grains themselves. Two are known. As one of the methods for improving the sharpness, it is known to color the constituent layers of the photographic light-sensitive material with a dye or the like, which is described in, for example, US Pat. No. 3,625,694.
A method for dyeing a specific layer in a light-sensitive material with a solid fine particle dispersion of a dye is also described in, for example, JP-A-2-2822.
No. 44, etc.

However, the method of using a dye for improving the sharpness has a problem that the stain content of the white background after the treatment becomes large, so that the content of the dye cannot be increased until the sharpness is sufficiently improved. . In particular, when the rapid processing was performed, the dye used was likely to remain in the print after the processing, so that the stain on the white background was likely to increase. In a silver halide color photographic light-sensitive material, the white background stain is not preferable because it determines the quality of the white background of the image, increases the color turbidity of the color image, and impairs the visual sharpness. In particular, when a reflective support is used, the reflection density of stain is theoretically emphasized to several times the transmission density, so that even a weak stain significantly impairs the image quality. Therefore, it is an important issue to reduce the stain on the white background. A method for improving the sharpness by coating a layer containing colloidal silver is disclosed in, for example, JP-A-2-8463.
No. 7, etc., this method also had a large amount of silver remaining in the bleach-fixing step when rapid processing was carried out, and was accompanied by an increase in stain on a white background. Further, as an effective method for improving the sharpness, it is known to coat a layer containing a white pigment on a support. For example, JP-A-3-15645
No. 4 and the like disclose a method of improving the sharpness by dispersing titanium oxide particles at high density in a water resistant resin layer.

[0004]

The inventors of the present invention tried a method of dispersing titanium oxide particles in the water-resistant resin layer at a high density, but the stain on a white background was not deteriorated, but it was necessary for improving the sharpness. By the way, it was found that when the density of the white pigment was increased, the strength of the water resistant resin layer was remarkably lowered, and the flatness of the coating layer was remarkably deteriorated. Further, improving the sharpness by dispersing a white pigment in the hydrophilic colloid layer is described in, for example, JP-A-59-177542. When the present inventors tried this method, the density of the white pigment was increased without causing the above problems, and the sharpness could be sufficiently improved. However, when the method of dispersing a white pigment in the hydrophilic colloid layer is used, when a light-sensitive material using a silver halide emulsion having a silver chloride content of 95 mol% or more, which is particularly suitable for rapid processing, is exposed under high humidity. It was found that there is a large decrease in sensitivity, and the sensitivity changes greatly when the time from exposure to development processing changes, which is a major problem in supplying stable quality prints to users. It is an important issue in view of the current market demand for silver halide color photographic light-sensitive materials to provide prints with excellent sharpness to users in a stable quality and quickly. Therefore, the object of the present invention is to improve the rapid processability and sharpness, and to reduce the sensitivity change when the humidity at the time of exposure is changed (that is, the exposure humidity dependency is small). Another object of the present invention is to provide a silver halide color photographic light-sensitive material in which the change in sensitivity upon change is small (that is, latent image stability is good).

[0005]

As a result of earnest research, the present inventors have found that the object of the present invention can be effectively achieved by a silver halide color photographic light-sensitive material having the following characteristics. (1) A silver halide color photographic light-sensitive material comprising a support having at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer. The silver halide emulsion layer contains silver chlorobromide or silver chloride emulsion grains having a silver chloride content of 95 mol% or more substantially containing no silver iodide, and the support and the color forming property closest thereto. It has at least one hydrophilic colloid layer containing a white pigment so that the filling rate of the white pigment is 20% by weight or more between it and the silver halide emulsion layer, and the coating pH of the photosensitive material is 5.
0 to 6.5, and the coating pAg is 6.0 to 10.0.
And a silver halide color photographic light-sensitive material.

(2) In the above silver halide color photographic light-sensitive material, the coating amount of the white pigment contained in the hydrophilic colloid layer is 2 g / m ² or more, and the silver halide color photographic material Photosensitive material. (3) The silver chlorobromide emulsion grains are supported during the grain forming process of forming a portion corresponding to 20% or less of the grain volume in the whole grain forming process and / or from the end of grain formation. By the time it is coated on the body, a total of 0.0005 to 0.05 mol of the bromine ion-releasing compound and / or bromine-releasing compound per mol of silver halide are added to the system containing silver halide grains. The silver halide color photographic light-sensitive material as described in the above item (1) or (2), which is formed.

When a hydrophilic colloid layer containing a white pigment is provided on a support, the coating amount of the white pigment is 0.
5 g / m ² or more is suitable, and 2 g / m ² or more is preferable. It is more preferably 4 g / m ² or more, and particularly preferably 8 g / m ² or more. The upper limit is not particularly limited, but is preferably 40 g / m ² or less. The weight of the white pigment referred to in the present invention is an amount including the weight of the white pigment when it contains various surface treatment agents or dispersion stabilizers for the purpose of improving the dispersibility of the white pigment. . The filling rate of the white pigment in the hydrophilic colloid layer containing the white pigment is preferably 40% by weight or more, and most preferably 70% by weight or more. The upper limit is not particularly limited, but is preferably 99% by weight or less. The thickness of the hydrophilic colloid layer containing the white pigment is determined by the above content and the coating amount, but is preferably in the range of 0.5 to 10 μm.
To 5 μm is more preferable.

Examples of the white pigment used in the present invention include titanium dioxide, barium sulfate, lithopone, alumina white, calcium carbonate, silica white, antimony trioxide, titanium phosphate, zinc oxide, lead white and gypsum. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be of rutile type or anatase type, and may be produced by any of the sulfate method and chloride method. The average particle size of the particles of the white pigment used in the hydrophilic colloid layer is 0.1 to 1.0 μm.
Can be used. It is preferably 0.2 to 0.3 μm. In the present invention, gelatin can be preferably used as the hydrophilic colloid (binder) constituting the hydrophilic colloid layer containing the white pigment, the silver halide emulsion layer, the non-photosensitive intermediate layer and the like. If desired, other hydrophilic colloids may be used in place of gelatin in any proportion.

Examples of these are gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives (such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate), sodium alginate and starch. Examples include sugars such as derivatives, polyvinyl alcohol, partial acetals of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, and other wide range of synthetic polymers. it can. In the present invention, the white pigment-containing hydrophilic colloid layer may contain various materials added to the photographic light-sensitive material, in addition to the white pigment and the binder. For example, a surfactant as a coating aid,
A hardener, a dye, an antifoggant, or the like. Furthermore, a high-boiling point organic solvent dispersed in the form of fine oil droplets can be contained. When the dispersion of the high-boiling point organic solvent is contained, various oil-soluble materials (such as optical brightener) can be dissolved and contained therein.

The light-sensitive material of the present invention comprises a support, at least one light-sensitive emulsion layer coated thereon, a non-light-sensitive layer such as a color mixing prevention layer or a protective layer, and a hydrophilic material containing a white pigment. And a colloidal layer. In the present invention, the hydrophilic colloid layer containing the white pigment is coated between the support and the photosensitive emulsion layer closest to the support. As the support used in the present invention, paper made of natural pulp or synthetic pulp, baryta paper, resin-coated paper coated with polyolefin such as polyethylene and polypropylene, polyester or the like, polyethylene, polypropylene, polystyrene, polycarbonate, hard vinyl chloride Examples thereof include synthetic polymer films such as polyethylene terephthalate, and natural polymer films such as cellulose diacetate, cellulose triacetate, and nitrocellulose. From the viewpoint of accelerating the development processing of the light-sensitive material, the support preferably has water resistance. That is, it is preferable to use water resistant resin coated paper or polymer film.
It is also possible to use a support having a surface of diffuse reflection of the second kind. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second-class diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of the surface irregularities is preferably 0.1 to 2000 cycles / mm for irregularities having a roughness of 0.1 μm or more, and more preferably 50 to 600 cycles / mm. For more information on such supports, see
It is described in JP-A-2-239244.

In the present invention, the white pigment is contained only in the hydrophilic colloid layer containing the white pigment, and the resin constituting the support, for example, the resin coating the paper substrate or the resin film which is the support itself is used. May be not included, or the white pigment may be included in the resin constituting the support in addition to the hydrophilic colloid layer containing the white pigment.

A photosensitive emulsion layer may be provided directly on the hydrophilic colloid layer containing a white pigment, or a photosensitive emulsion may be formed through one or a plurality of non-photosensitive hydrophilic colloid layers. You may install layers. When this non-photosensitive hydrophilic colloid layer is provided, the total thickness of these layers is preferably 5 μm or less. Further, it is preferably 2 μm or less. These non-photosensitive hydrophilic colloid layers can contain various photographically useful substances, if necessary. For example, it is a surfactant as a coating aid, a hardener, a dye, or an antifoggant. Further, a coloring layer capable of being decolorized during development processing can be constituted by containing colloidal silver, a dye dispersed in a solid state, a dye dyed with a cationic polymer or the like. Alternatively, a high-boiling point organic solvent dispersed in the form of fine oil droplets may be contained. In these solvents, a photographically useful substance such as an oil-soluble color mixing inhibitor, a fluorescent whitening agent or an ultraviolet absorber can be dissolved and contained.

The colored layer which can be decolorized by the treatment used in the present invention may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a processing color mixing inhibitor such as gelatin or hydroquinone. May be. This colored layer needs to be provided as a lower layer (on the side of the support) of the emulsion layer having a sensitivity in a region that substantially overlaps with the light wavelength region absorbed by the colored substance. It is possible to individually install all of the colored layers corresponding to the emulsion layers sensitized to have sensitivity in different wavelength regions, or to selectively install some of them. It is also possible to provide a coloring layer having absorption in a wide range of wavelength formula regions so as to correspond to a plurality of emulsion layers having different sensitizing wavelength regions.

The optical reflection density of the colored layer is such that the optical density value is 0.2 or more at a wavelength having the highest optical density in the visible light region of 400 nm to 700 nm as a light wavelength.
It is preferably 0 or less. More preferably 0.5
It is preferably 2.5 or more and 2.5 or less, particularly 0.8 or more and 2.0 or less. A conventionally known method can be applied to form the colored layer. For example, a method of dispersing a fine powder of a dye in a solid state, a method of mordanting an anionic dye on a cationic polymer, a method of adsorbing the dye to fine particles such as silver halide and fixing it in a layer, a method of using colloidal silver. And so on.
As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-308244, pp. 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. Regarding the method of preparing colloidal silver as a light absorber, US Pat. Nos. 2,688,601 and 3,459,
No. 563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The coating pH in the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic constituent layers obtained by coating the coating solution on a support, and does not necessarily coincide with the pH of the coating solution. do not do. The coating pH can be measured by the following method as described in JP-A-61-245153. That is, (1) 0.05 cc of pure water is dropped on the surface of the photosensitive material on the side coated with the silver halide emulsion. Next, (2) after standing for 3 minutes, the coating pH is measured with a coating pH measuring electrode (GS-165F manufactured by Toa Denpa). In the present invention, the coating pH obtained by such a measuring method is 5.0 to
It is 6.5. The pH of the coating film can be adjusted using an acid (eg sulfuric acid, citric acid) or an alkali (eg sodium hydroxide, potassium hydroxide) as necessary.
If the coating pH is less than 5.0, problems such as inhibition of dura mater and deterioration of sensitivity are likely to occur. On the other hand, when the coating pH exceeds 6.5, desensitization when exposed under high humidity and sensitivity change when the time until post-exposure treatment changes are large.

The coating pAg in the silver halide color photographic light-sensitive material of the present invention is the pAg of all photographic constituent layers obtained by coating the coating solution on a support, and does not necessarily coincide with the pAg of the coating solution. do not do. The coating pAg can be measured by the following method. (1) 20 microliters of pure water is dripped on the surface of the light-sensitive material coated with the silver halide emulsion. Next, (2) after standing for 1 minute, the coated pAg measuring electrode (GS-16 manufactured by Toa Denpa Co., Ltd.)
The film pAg is measured at 5F). In order to change the potential obtained here to pAg, the potential of the following solution is measured, a calibration curve is prepared, and the potential is converted to pAg using this calibration curve.

Solution No. pAg Preparation method ――― ――― ―――――――――――――――――――― (1) 2 AgNO ₃ 0.17 g is dissolved in water, Make up to 100 ml. (2) Take 5 ml of 3 solution (1) and make up to 50 ml with water. (3) Take 5 ml of 4 solution (2) and make up to 50 ml with water. (4) Take 5 ml of 5 solution (3) and make up to 50 ml with water. (5) -Dissolve 2.38 g of KBr with water to make 100 ml. (6) -Take 5 ml of solution (5) and make up to 50 ml with water. (7) Take 5 ml of the solution (6) and make up to 50 ml with water. (8) Mix 11.67 solution (4) (5 ml) and solution (5) (5 ml). (9) Mix 5 ml of 10.67 solution (4) and 5 ml of solution (6). (10) Mix 9.67 solution (4) (5 ml) and solution (7) (5 ml). ――― ――― ――――――――――――――――――――

The present invention provides the coating pA thus measured.
g is 6.0 to 10.0. Preferably 7.0-9.
It is 0, and more preferably 7.2 to 8.7. Coating pAg
Can be adjusted using a water-soluble halide (eg sodium chloride, potassium bromide) or a water-soluble silver salt (eg silver nitrate), if necessary. The film p
If Ag exceeds 10.0, problems such as a decrease in sensitivity are likely to occur. On the other hand, if the coating pAg is less than 6.0, desensitization when exposed under high humidity and sensitivity change when the time until post-exposure treatment changes are large.

The silver halide emulsion grains used in the present invention are substantially silver iodide-free silver chlorobromide or silver chloride having a silver chloride content of 95 mol% or more. Further, the silver chlorobromide emulsion grains are formed on the support during the grain formation process forming a portion corresponding to 20% or less of the grain volume in the whole grain formation process and / or from the end of grain formation. 1 silver halide in total before coating
The addition of 0.0005 to 0.05 mol of a bromine ion-releasing compound and / or bromine-releasing compound per mol reduces the exposure humidity dependence and further improves the latent image stability. preferable. When a water-soluble bromide is added to silver chloride or silver chlorobromide grains, silver bromide having a low solubility product is deposited on the grains and a so-called halogen conversion reaction occurs. Therefore, the silver bromide content of the grain is a value obtained by adding the amount of the water-soluble bromide added to the original silver bromide content of the grain.

In the present invention, the silver chloride content of the finally formed emulsion grains must be 95 mol% or more, and the amount of the water-soluble bromide added is 0.0005 to 0 per mol of silver halide. It is preferably in the range of 0.05 mol. For the halogen composition of the emulsion grains before adding the water-soluble bromide, either pure silver chloride or silver chlorobromide is used, but the silver bromide content is 5 mol% even if the addition amount of the water-soluble bromide is added. It should be set so as not to exceed. If the silver bromide content of the silver halide grains exceeds 5 mol%, the rapid processability is impaired. The steps of preparing the silver halide emulsion used in the present invention include a grain forming step by a reaction of a water-soluble silver salt and a water-soluble halide, a physical ripening step of silver halide grains, a water-soluble salt removing step (a desalting and washing step). ), A chemical sensitization process. When spectrally sensitizing the emulsion of the present invention,
The spectral sensitizing dye may be added in any of the above steps. The obtained silver halide emulsion is mixed with a dispersion of a coupler which is a dye forming element, a stabilizer, a coating aid such as a surfactant or a viscosity modifier, gelatin or the like to prepare a coating solution.

When the bromine ion-releasing compound and / or the bromine-releasing compound is added during grain formation, the period for which this is done is preferably the period for forming a portion corresponding to 20% or less of the grain volume. Including the case of adding instantly as the length of. The bromine ion-releasing compound and / or the bromine-releasing compound may be added continuously or discontinuously. However, in the case of discontinuous addition, the total length of the addition period is equal to or less than the period for forming a portion corresponding to any 20% of the particle volume.
If this is continued to be added during the formation of a portion exceeding 20% of the particle volume, it is difficult to obtain the effect described above.
A preferable addition period is a period for forming a portion corresponding to 10% or less of the particle volume, and more preferably a period for forming a portion corresponding to 5% or less of the particle volume. And when to add these compounds,
It is preferably after forming 50% or more of the volume of the silver halide grains, and more preferably after forming 80% or more. In the present invention, the addition of the bromine ion-releasing compound and / or the bromine ion-releasing compound is preferably carried out in the steps from the completion of particle formation to the preparation of the coating solution. More preferably, the steps from the start of chemical sensitization to the preparation of the coating solution are preferable. The addition of the bromide-releasing compound and / or the bromine-releasing compound has the effect of reducing the desensitization caused by exposure under high humidity, which occurs when a hydrophilic colloid layer containing a white pigment is applied as shown in the present invention. Can be suppressed. If the added amount of these compounds is too large, desensitization occurs when pressure is applied, which is a problem. The addition amount of the bromine ion-releasing compound and / or the bromine-releasing compound in the present invention is preferably 0.0005 to 0.05 mol per mol of silver halide. More preferably, it is in the range of 0.001 to 0.02 mol. When the addition of these compounds is divided into a plurality of times and the addition thereof is performed, the total amount may be within the above range. Examples of the bromide ion-releasing compound and / or the bromine ion-releasing compound include water-soluble bromide and its alkali metal salt (N
a, K, Li salt, etc.) and ammonium salt can be preferably used. Furthermore, silver bromide fine particles having a smaller particle size than the host grains or silver chlorobromide fine particles having a high silver bromide content can be preferably used. In addition, the compounds described in JP-A-1-285942 can also be preferably used. Here, the particle size of the silver bromide fine particles or the silver chlorobromide fine particles may be smaller than the particle size of the host particles, and generally, it is preferably about 0.05 μm or less.

The color light-sensitive material of the present invention is constituted by coating at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer on a support. can do. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color forming layers described above, and are also formed on the support in the order described above. It can be constructed by coating. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. It may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

The silver halide grains used in the present invention are substantially silver iodide-free silver chlorobromide or silver chloride consisting of 95 mol% or more of silver chloride, and the preferable silver chloride content is It is 98 mol% or more. Here, "containing substantially no silver iodide" means that the silver iodide content is 1 mol% or less,
It is preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing storage stability of a light-sensitive material, JP-A-3-84
No. 545 on the emulsion surface as described in No. 545
High silver chloride grains containing 3 mol% of silver iodide may be preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform.

Regarding the halogen composition distribution inside the silver halide emulsion grains, the grains having a so-called uniform structure having the same composition in any portion of the silver halide grains, or the core and the inside of the silver halide grains are used. Particles with a so-called laminated structure having different halogen compositions with the shell (single layer or multiple layers) that surrounds, or a structure having a non-layered portion with different halogen compositions inside or on the surface (if present on the particle surface, the particles are Particles having a structure in which different composition portions are joined to the edges, corners or surfaces of the above) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion of the present invention preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content,
More than 100 mol% and more than 100 mol% are more preferable.
The silver bromide content of the silver bromide localized phase can be determined by the X-ray diffraction method (for example,
"Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis" Maruzen,
It is described in. ) Etc. can be used for analysis. And these localized phases can be inside the grain, on the edges of the grain surface, on the corners or on the faces,
As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion has a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% of the particles having the above-mentioned regular crystal form are used in the present invention.
The above content is preferably 70% or more, more preferably 90% or more. In addition to these, tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more, having a projected area of 50% or more of all grains can also be preferably used.

The silver chlorobromide emulsion or silver chloride emulsion used in the present invention is described in P. Glafkides Chimie
et Phisique Photographiqu
e (Paul Montel, 1967), G.E.
F. Duffin Photographic Em
ulsion Chemistry (Focal Pr
ess company, 1966), V.I. L. Zelikman
et al. Making and Coating
g Photographic Emulsion (F
It can be prepared by the method described in Ocal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a form of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains different metal ions or complex ions thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions mainly selected from iridium, rhodium and iron or their complex ions in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of a silver salt or other aqueous solution, or in the form of fine silver halide grains containing metal ions in advance and dissolving the fine grains. It is contained in the localized phase and / or other particle portion (matrix). The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, and tellurium sensitization with a tellurium compound are performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Further European patent 0,447,
5-arylamino-1,2,
A 3,4-thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of the spectral sensitizing dye used for spectral sensitization in the red region include F.I. M. Harmer's Heterocycle
ic compounds-Cyanine dyes
and related compounds (Jo
hn Wiley & Sons [New Yor
k, London], 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red light-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-
The spectral sensitizing dye described in No. 123340 is extremely preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, European patent 0,420,01
No. 1, page 4, line 21 to page 6, line 54, European Patent 0,420,0
No. 12, page 4, line 12 to page 10, line 33, European patent 0,44
The sensitizing dyes described in US Pat. No. 3,466 and US Pat. No. 4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, No. 4427555, No. 57-2208
As described in US Pat. No. 9, etc., an aqueous solution is prepared by coexisting an acid or a base, or US Pat.
An aqueous solution or colloidal dispersion prepared by coexisting with a surfactant as described in 6,025 may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. JP-A-5
As described in JP-A-3-102733 and JP-A-58-105141, it may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928, that spectral sensitization is carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. It can be carried out prior to the chemical sensitization as described above, or it can be added before the completion of silver halide grain precipitation to start the spectral sensitization. Furthermore, the spectral sensitizing dyes may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., a portion prior to chemical sensitization and the balance after chemical sensitization. Additions are also possible and can be at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ^-5 mol to 1 mol of silver halide.
5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol
An amount of 5.0 × 10 ⁻³ mol is used, and 0.1 times to 10000 times, preferably 0.5 times to 5 times per mol of the sensitizing dye.
There is an advantageous usage amount in the range of 000 times.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance exposure. As a preferred exposure method for high illuminance exposure, there is a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, more preferably shorter than 10 ⁻⁶ seconds. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to a conventional color developing treatment, but in the case of the color light-sensitive material of the present invention, it is preferable to carry out bleach-fixing treatment after color development for the purpose of rapid processing. Especially when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fixing solution is about 6.
It is preferably 5 or less, more preferably about 6 or less.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material. As the additives for treatments, those described in the following patent publications, particularly European Patent 0,355,660A2 (JP-A-2-139544) are preferably used.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

The cyan, magenta, or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents described in the table above. It is preferable that the polymer is dissolved or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer to be emulsified and dispersed in a hydrophilic colloid aqueous solution. The water-insoluble and organic solvent-soluble polymers that can be preferably used are the single polymers described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. Examples thereof include a polymer and a copolymer. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent No. 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
A compound chemically bonded to the compound in the above-mentioned patent specification which produces a substantially colorless compound and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment It is possible to use the compounds in the above-mentioned patent specification, which form an inactive and substantially colorless compound, simultaneously or alone, for example, the reaction of the coupler with the residual color developing agent in the film or its oxidant and the coupler during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of the coloring pigment.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole type cyan coupler described in Japanese Patent No. 33144, European Patent No. 0,333,185A2
3-Hydroxypyridine cyan couplers (especially the couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine leaving group to make them 2-equivalent, couplers (6) and (9) Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples), and European Patent 0,456. 226A1 pyrrolopyrazole type cyan couplers, European Patent 0,484,909 pyrroloimidazole type cyan couplers, European Patent 0,
488,248 and European Patent 0,491,197A1
It is preferable to use the pyrrolotriazole type cyan coupler described in No. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent 0,447,969
An acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group described in A1, European Patent 0,
Malondianilide type yellow couplers having a cyclic structure described in US Pat. No. 5,11,482.
The acylacetamide type yellow coupler having a dioxane structure described in No. 8,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination. In addition, JP-A-63-231451 and JP-A-6-231451.
3-123047, 63-241547, JP-A-1-173499, 1-213648, 1-2.
It is also preferable to use a so-called short-wave type yellow coupler described in 50944.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler as described in the publicly known documents in the above table is used.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A.

As the processing method of the color light-sensitive material of the present invention, in addition to the methods described in the above table, JP-A-2-20725 is known.
No. 0, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20 The method is preferred.

[0050]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of large-sized silver halide emulsion B1 for blue-sensitive silver halide emulsion layer) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N, N'-dimethylimidazolidine-2-thione was added. 3.2 ml of (1% aqueous solution) was added. An aqueous solution containing 0.5 mol of silver nitrate and an aqueous solution containing 0.5 mol of sodium chloride were added to and mixed with this aqueous solution at 66 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.45 mol of silver nitrate and an aqueous solution containing 0.45 mol of sodium chloride were added and mixed at 72 ° C. with vigorous stirring. Thereafter, at 40 ° C., a copolymer of isobutene-maleic acid-1-sodium salt was added, and the mixture was washed with water for sedimentation for desalting.
Further, 90.0 g of lime-processed gelatin was added. A silver bromide fine grain emulsion having a grain size of 0.05 μm was added to this emulsion in an amount of 0.0053 mol to form a silver bromide rich layer on the grain surface, and then a blue-sensitive sensitizing dye 2 × 10 ⁻⁴ mol / Mol Ag was added, and optimum chemical sensitization was performed with a sulfur sensitizer (triethylthiourea). Further, 5 × 10 ⁻⁴ mol / mol Ag of 1- (5-methylureidophenyl) -5-mercaptotetrazole was added. The grain shape, grain size and grain size distribution of the obtained emulsion (B1) were determined from electron micrographs. The emulsion grains were cubic, the grain size was 0.88 μm, and the coefficient of variation was 0.10. The grain size is represented by the average value of the diameter of the circle equivalent to the projected area of the grain, and the grain size distribution is the standard deviation of the grain size divided by the mean grain size. Emulsions with different grain sizes were prepared by changing the temperature during the formation of silver halide grains, the addition time of the aqueous silver nitrate and sodium chloride solutions, and the amount of silver bromide fine grain emulsion. A blue-sensitive small-sized emulsion, a red-sensitive emulsion, and a green-sensitive emulsion used below were prepared by adding a dye or a green-sensitive sensitizing dye. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0051]

[Table 5]

[0052]

[Table 6]

[0053]

[Table 7]

After the corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing dodecylbenzene sulfonic acid was provided, and various photographic constituent layers were further coated to form a multi-layer color having the following layer constitution. A printing paper, Sample (1), was prepared. The coating liquid was prepared as follows. Preparation of coating liquid for the first layer (white pigment-containing layer) An average particle size of 0.
400 g of 23 μm rutile type titanium oxide white pigment (Titanium White R780 manufactured by Ishihara Sangyo Co., Ltd.) and 4 liters of water were added, and 5 cc of a 5% aqueous solution of sodium dodecylbenzene sulfonate was added as a dispersant, and ultrasonic dispersion was performed. Preparation of Second Layer Coating Liquid Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-)
2) 7.5 g, color image stabilizer (Cpd-3) 16.0 g, ethyl acetate 180.0 cc and solvent (Solv-1)
And (Solv-2) 25 g each were added and dissolved,
This solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion (cubic, 6: 4 mixture of a large size emulsion B1 having an average grain size of 0.88 μm and a small size emulsion of 0.70 μm (silver molar ratio), grain size distribution, The coefficient of variation was 0.10 and 0.08, respectively, and each size emulsion contained 0.53 mol% of silver bromide localized on the grain surface). The emulsion A and this silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the second layer having the composition shown below. The coating liquid for the other layer was also prepared in the same manner as the second layer coating liquid. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-15 and C in each layer
The total amount of pd-16 was 25.0 mg / m ² and 5 respectively.
The amount added was 0.0 mg / m ² . Also for emulsions for green-sensitive emulsion layers and red-sensitive emulsion layers, 1- (5-
Methylureidophenyl) -5-mercaptotetrazole was added in an amount of 9.7 × 10 ⁻⁴ per mol of silver halide.
Mol, 5.5 × 10 ⁻⁴ mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ^-4
Mol added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0055]

[Chemical 1]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support: Polyethylene laminated paper First layer (white pigment-containing layer) Gelatin 1.13 Titanium oxide white pigment 4.50 (white pigment filling rate 80% by weight) Second layer (blue sensitive emulsion layer) Silver chlorobromide emulsion ( Cubic, 6: 4 mixture (Ag molar ratio) of large size emulsion B1 having an average grain size of 0.88 μm and small size emulsion B2 of 0.70 μm, the coefficient of variation of grain size distribution being 0.10 and 0.08, respectively. , AgBr 0.53 mol% was locally contained in a part of the grain surface in each size emulsion) 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Third Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Fourth Layer ( Green-sensitive emulsion layer: Silver chlorobromide emulsion (cubic, 6: 4 mixture (Ag molar ratio) of large size emulsion G1 having an average grain size of 0.55 μm and small size emulsion G2 having a grain size of 0.39 μm. Coefficients of variation are 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.13 Zetilan 1.45 Magenta coupler (ExM) 0.16 colors Image stabilizer (Cpd-6) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer Agent (Cpd-9) 0.08 Solvent (Solv -3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fifth layer (color mixing prevention layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Sixth layer (red sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion R1 with average grain size 0.50 μm, and small size emulsion R2 with 0.45 μm 7: 3 mixture (Ag molar ratio) Grain size distribution coefficient of variation was 0.08 and 0.11, and AgBr 0.5 mol% was locally contained in a part of the grain surface in each size emulsion) 0.20 Gelatin 0 .85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-10) 0.15 Color image stabilizer ( Cpd-11) 0.15 color image stabilizer (Cpd- 2) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-6) 0.22 Solvent (Solv-1) 0.01 Seven layers (ultraviolet absorbing layer) gelatin 0.55 ultraviolet absorber (UV-1) 0.40 color image stabilizer (Cpd-13) 0.15 color image stabilizer (Cpd-6) 0.02 eighth layer ( Protective layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.15 Liquid paraffin 0.03 Color image stabilizer (Cpd-14) 0.01

The compounds used here are shown below.

[0060]

[Chemical 2]

[0061]

[Chemical 3]

[0062]

[Chemical 4]

[0063]

[Chemical 5]

[0064]

[Chemical 6]

[0065]

[Chemical 7]

[0066]

[Chemical 8]

Samples (2) to (15) were prepared by changing the coating amount of titanium oxide, coating pH, etc. in sample (1) as shown in Table-A. However, the titanium oxide filling rate was set to 80% by weight for Samples (2) to (5) and (11) to (15), and to 15% by weight for Samples (6) to (10), and the coating pH value was set. Was adjusted by adding 1N sulfuric acid or sodium hydroxide aqueous solution to the coating liquid for the protective layer and the color mixing prevention layer. Also the coating pAg
The amount of the aqueous sodium chloride solution added to the second layer coating solution was adjusted to 8.0 for all the light-sensitive materials. Further, in Comparative Samples (16) to (20), the first layer was not coated in Sample (1), and 16% by weight of a white pigment of titanium oxide was added to the polyethylene laminate on the emulsion layer coated side of the support. The titanium was contained so that the coating amount was 4.5 g / m ² .

[0068]

[Table 8]

In order to evaluate the exposure humidity dependency, each sample was stored at a humidity of 35% and 85% (temperature 25 ° C.) for 30 minutes, and then, under each condition, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) was used. , The color temperature of the light source was 3200 ° K), and through the blue, green, and red filters, gradation exposure was given at an exposure amount of 250 CMS with an exposure time of 0.1 seconds for sensitometry, and the sensitivities were compared. . Degree of desensitization under high-humidity exposure according to the value (S _85- S ₃₀ ) obtained by subtracting the sensitivity (S ₃₀ ) when stored at 35% humidity from the sensitivity (S ₈₅ ) when stored at 85% humidity. Was evaluated. The evaluation of the change in sensitivity when the time from the exposure to the development process varied was evaluated by performing the same exposure as above and then storing for 2 hours at a temperature of 25 ° C. and a humidity of 55%. Compared. The sensitivity change due to storage was evaluated by the value obtained by subtracting the "sensitivity before storage" from the "sensitivity after storage". The sensitivity was evaluated by using the logarithm of the reciprocal of the exposure dose required for the processed sample to give a density of 1.0. A value called CTF is used here for the evaluation of the sharpness. CTF represents the attenuation of the amplitude with respect to the spatial frequency as a square waveform. Here, the sharpness is shown at a spatial frequency (lines / mm) that gives a CTF value of 50%. The higher the value, the higher the sharpness.

The exposed samples were treated with a paper processor using the following treatment steps and treatment liquid compositions. Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161 ml 17 liter Bleach fixing 30-35 ℃ 45 seconds 215 ml 17 liter Rinse 35 ℃ 90 seconds 350 ml 10 liter Dry 70-70 ℃ 60 seconds * Replenishment The composition of each processing solution is as follows per 1 m ² of the light-sensitive material.

Color developing solution Tank solution Replenishing solution Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine.1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water added 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Bromide Ammonium 40 g Water is added 1000 ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively)

The results are shown in Table-B. The results showed the change in sensitivity of the blue-sensitive (B) emulsion layer and the value of CTF.

[0074]

[Table 9]

As is clear from the results of Table B, the sharpness is remarkably improved by applying the hydrophilic colloid layer containing the white pigment of the present invention. However, as a result, the samples having a coating pH of 6.0 or more showed a large degree of desensitization when exposed to light under high humidity, and further had a large change in sensitivity when the time until post-exposure treatment changed. .
[Reference: Samples (5), (10), (15)] When the coating pH was adjusted to 4.0 or lower, the sensitivity of each emulsion layer was lowered. [Reference: Sample (4),
(6), (11)] When the coating amount of the white pigment is relatively small, the coating of the white pigment is less likely to occur, although there are few problems such as exposure humidity dependency and latent image stability as the problems of the present invention. If the amount is small, the sharpness is low. [Reference: Samples (7) to (9)] When a white pigment is contained in the polyethylene laminate on the emulsion layer coating side of the support, the sharpness is improved even if the coating amount of the white pigment is relatively large. The effect is low. [Reference: Samples (16) to (20)] Only by adjusting the coating pH of the present invention, the sharpness is excellent, and the desensitization when exposed under high humidity is small, and further, it is possible to perform the post-exposure treatment. A color photographic light-sensitive material having a small change in sensitivity with time was obtained. [Reference: Samples (1) to (3), Samples (12) to (14)]

Example 2 Silver bromide by silver bromide fine particles at the time of preparing the silver halide emulsions B1 and B2 used for preparing the coating solutions for the second layer of the samples (1) and (5) used in Example 1. The formation of the rich layer was stopped, and an aqueous potassium bromide solution was added at the time shown in Table-C to change the halogen composition of the silver halide emulsion to prepare a coating solution for the second layer. Using this coating solution, sample (21)
~ (32) were created. Also in these samples, Example 1
The coating pAg was adjusted to 8.0 by the same method as that shown in. These samples were evaluated in the same manner as in Example 1.
The results are shown in Table-D.

[0077]

[Table 10]

[0078]

[Table 11]

From the results shown in Table D, it is understood that the effect of the present invention becomes remarkable by adding the water-soluble bromide. This effect was also obtained when a gold-sulfur sensitized emulsion was used.

Example 3 By changing the ratio of gelatin to titanium oxide in the first layer of the sample (12) used in Example 1, the filling rate of titanium oxide in the first layer was changed as shown in Table E. Changed sample (3
3) to (37) were prepared. The coating amount of titanium oxide in each sample was 2.5 g / m ² .
The sharpness of these samples was evaluated in the same manner as in Example 1. The results are shown in Table-E.

[0081]

[Table 12]

As can be seen from Table-E, the sharpness was inferior in the sample in which the filling rate of the white pigment in the hydrophilic colloid layer was less than 20% by weight.

Example 4 Samples (1), (2), (4) prepared in Example 1
In (5), (6), (8) and (10), the coating pAg was changed by changing the amount of the sodium chloride aqueous solution added to the second layer coating solution, and the sample (3
8)-(54) were produced.

[0084]

[Table 13]

[0085]

[Table 14]

The same evaluations as in Example 1 were performed on these samples. The results are shown in Table-G.

[0087]

[Table 15]

[0088]

[Table 16]

As can be seen from Table-G, the coating pH of the present invention
However, if the coating pAg is less than 6.0, the sensitivity decreases, and if the coating pAg exceeds 10.0, the desensitization under high humidity exposure is large, and the time until post-exposure treatment is large. It can be seen that the change in sensitivity becomes large when changed. Further, it can be seen that the effect of the present invention is particularly remarkable in a light-sensitive material having high sharpness.

[0090]

According to the present invention, the rapid processability and the sharpness are excellent, and the change in sensitivity when the humidity during exposure is changed is small,
Further, it is possible to obtain a silver halide color photographic light-sensitive material which has a small change in sensitivity when the time from the exposure to the development process is changed.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer on a support. In the material,
The silver halide emulsion layer contains silver chlorobromide or silver chloride emulsion grains having a silver chloride content of 95 mol% or more substantially containing no silver iodide, and the support and the color forming halogen closest to the support. The filling rate of the white pigment between the silver halide emulsion layer and the silver halide emulsion layer is 20% by weight.
As described above, at least one hydrophilic colloid layer containing a white pigment is provided, the coating pH of the photosensitive material is 5.0 to 6.5, and the coating pAg is 6.0 to 1.
A silver halide color photographic light-sensitive material characterized by being 0.0. 2. The halogen according to claim 1, wherein in the silver halide color photographic light-sensitive material, the coating amount of the white pigment contained in the hydrophilic colloid layer is 2 g / m ² or more. Silver halide color photographic light-sensitive material. 3. The silver halide color photographic light-sensitive material as described above, wherein the silver chlorobromide emulsion grains form a part corresponding to 20% or less of the grain volume of all grain forming steps. In the meanwhile, and / or during the period from the completion of grain formation to the coating on the support, 0.0005 to 0.05 mol of a bromide ion-releasing compound and / or bromide-releasing compound are added per mol of silver halide in total. 3. The silver halide color photographic light-sensitive material according to claim 1, which is formed by adding it to a system containing silver halide grains.