JPH0651459A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material excellent in rapid developing property, showing small decrease in color density even when the concn. of bromine compd. and bromine ion is increased in the developer, and showing little change in development density for exposure at high humidity. CONSTITUTION:This silver halide color photosensitive material has at least one color-developing silver halide emulsion layer on a supporting body, and at least one silver halide emulsion layer contains silver chloride/bromide emulsion particles with >=90mol% silver chloride. These silver chloride/bromide emulsion particles contain >=10mol% silver bromide particles having at least two partial structure on the crystal particles. Further, the photosensitive material has a hydrophilic colloid layer with a coating mat. of >=2g/m<2> containing >=20wt.% white pigment between the supporting body and the color developing silver halide emulsion layer nearest to the supporting body.

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 light-sensitive material, and more specifically, it is excellent in rapid development processing property and has a high color development density even if the concentration of bromine compound and bromine ion in the development processing solution is increased. The present invention relates to a silver halide color photographic light-sensitive material which causes less deterioration and has less variation in color density even when exposed to high humidity, and more particularly to color photographic paper.

[0002]

2. Description of the Related Art Among color photographic light-sensitive materials, speeding up of processing is important for products used in a market where a large number of prints are finished in a short delivery time such as a light-sensitive material for photographic paper. Regarding the speeding up of the development processing, as described in International Publication WO87 / 04534, the development processing is dramatically improved by using a silver halide emulsion having a high silver chloride content, and it is widely used in the market. . The process of processing a color photographic light-sensitive material usually consists of developing, bleach-fixing and washing with water. In the developing / bleach-fixing solution, there are various water-soluble compounds washed out from the light-sensitive material as the color photographic light-sensitive material is run. The color photographic light-sensitive material containing the above-described silver halide emulsion having a high silver chloride content is often affected by the presence of the water-soluble compound in the development processing and bleaching steps, and the photographic property is often changed. Among the water-soluble compounds, the change in photographic property is large due to the increase of the bromine compound and bromine ion concentration, and especially in the case of silver halide emulsions with high silver chloride content, the bromine compound and bromine ion concentration in the developing solution increase. Then, there is a problem that the decrease in color density becomes large. The increase in the bromine compound and bromine ion concentrations in the developing solution is also observed in market laboratories, for example, when a part of the bleaching solution having a high bromine compound and bromine ion concentration is mixed in the developing solution or the developing solution replenishment amount is increased. Making mistakes is a real possibility. As a solution to such a problem, it was necessary to establish a technique for suppressing the decrease in the density of the color image area as much as possible even if the concentrations of the bromine compound and the bromine ion in the developing solution were increased.

[0003]

With respect to the above problems, as disclosed in JP-A-1-177028, silver chloride 90
Use of a silver halide emulsion in which at least two mol% of silver halide grains have at least two partial structures differing in silver bromide content by at least 10 mol% in the crystal grains is It is an effective means for suppressing the decrease in color density even when the bromine compound and bromine ion concentrations increase. However, in order to suppress a decrease in color density and a gradation change in a silver halide emulsion having two or more partial structures having different silver bromide contents described above, the silver bromide content in the partial structure is 10 mol. %, But when the difference in the silver bromide content of this partial structure is further widened, when the silver halide color photographic light-sensitive material containing the silver halide emulsion grains is exposed under high humidity, As compared with the case where the exposure is performed under normal humidity, the density of the color image portion is increased unintentionally, which is not preferable in terms of print reproducibility. However, there is no known technique for suppressing an undesired increase (fluctuation) in color density that occurs when a silver halide color photographic light-sensitive material is exposed under high humidity. Therefore, there is a need for a technique that does not cause a decrease in color density even when the concentration of bromine compounds and bromine ions in the developing solution increases, and that suppresses fluctuations in color density even when exposed to high humidity. It was Therefore,
The object of the present invention is excellent in rapid processing, does not cause a decrease in color density even when the bromine compound and bromine ion concentration in the development processing solution increase, and fluctuations in color density even when exposed under high humidity. It is to provide a small amount of silver halide color photographic light-sensitive material.

[0004]

As a result of earnest research by the present inventor, as will be described below, the filling rate of the white pigment between the support and the closest color forming silver halide emulsion layer is 20.
It has been found that by coating a hydrophilic colloid layer having a coating amount of not less than 2% by weight and a coating amount of not less than 2 g / m ^2, it is possible to effectively suppress the variation in color density when exposed under high humidity. It was That is, the above object was effectively achieved by the silver halide color photographic light-sensitive material described below. (1) In a silver halide color light-sensitive material having at least one color forming silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is silver chloride 9
A chlorobromide containing 0 mol% or more of silver chlorobromide emulsion grains, and the silver chlorobromide emulsion grains having at least two partial structures in which the silver bromide content differs by 10 mol% or more in crystal grains. Hydrophilic, which is silver emulsion grains and has a white pigment filling rate of 20% by weight or more between the support and the color forming silver halide emulsion layer closest to the support and the coating amount of 2 g / m ² or more. A silver halide color photographic light-sensitive material, which is coated with a photosensitive colloid layer. (2) The halogen according to the above item (1), further comprising a colored layer which can be decolorized by a development process at any position of the hydrophilic colloid layer group constituting the light-sensitive material on the support. Silver halide color photographic light-sensitive material. (3) At least one of the partial structures is a silver bromide-rich region formed in the vicinity of at least one apex of silver chlorobromide grains, and the average silver bromide on the surface of the silver chlorobromide grains is 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the content is 5 mol% or more and 15 mol% or less. (4) The silver halide color according to the above (3), wherein the silver bromide-rich region is formed by supplying bromine and / or bromine ions to the silver halide host grains a plurality of times. Photographic material.

A useful silver chlorobromide emulsion used in the silver halide color photographic light-sensitive material of the present invention is silver chlorobromide containing substantially no silver iodide. Substantially free of silver iodide means that the silver iodide content is 1 mol% or less, preferably 0.5 mol% or less, and most preferably no silver iodide is contained. is there. In the silver chlorobromide emulsion used in the present invention, the total silver bromide content is preferably 0.1 mol% or more and 10 mol% or less. More preferably, it is 0.3 mol% or more and 2 mol% or less. In the silver chlorobromide emulsion of the present invention, it is necessary that the crystal grains contained therein have at least two partial structures in which the silver bromide content differs by 10 mol% or more. It is preferred that the emulsion forms a cyan color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer and a yellow color forming silver halide emulsion layer. If the content of silver bromide differs from the partial structure described above by 10 mol% or more, the position or form of existence thereof is not particularly limited within the crystal grains. Therefore, the inside and the surface of the crystal grains may have a so-called core-shell type structure in which the halogen composition in the above-mentioned meaning is different, or may have a multilayer core-shell structure. Further, it may have a so-called junction type structure in which guest crystals having different halogen compositions are deposited and bonded to a certain site of a host crystal particle having a certain halogen composition, for example, a corner, an edge or a plane of the crystal particle. Although it is difficult to describe the structure specifically, it is also possible to introduce a partial structure having a halogen composition different from that of the crystal grains before conversion by so-called halogen exchange. Furthermore, by combining these structures, for example, crystal grains having a core-shell structure are used as host crystal grains to deposit a guest crystal having a halogen composition different from the halogen composition on the surface of the grain, or a crystal having a multilayer core-shell structure. It is also possible to add halogen conversion to the particles. The boundary of the partial structure thus formed may be a clear boundary with respect to the composition, or may be a boundary that forms a mixed crystal due to a composition difference and continuously changes. The difference in the content of silver bromide contained in two or more partial structures having different silver bromide contents is the same as that of grains having a uniform structure unless the silver bromide contents in the two or more partial structures are significantly different. If the composition difference does not change so much and the composition difference is too large, on the other hand, performance problems such as pressure desensitization are likely to occur, which is not preferable. A suitable composition difference is preferably 10 mol% or more and 40 mol% or less,
It is more preferably 15 mol% or more and 30 mol% or less.

The shape of silver chlorobromide used in the present invention may be a cube, an octahedron, a tetradecahedra, a rhodohedron or another shape. In particular, in the case of junction type particles, it is not indefinite, but junction crystals are uniformly generated on the corners, edges or planes of the host crystal, and exhibit regular grain shapes. It may also be spherical. In the present invention, octahedral grains, tetradecahedral grains or cubic grains are preferably used, and cubic grains are particularly preferably used. Crystal grains having a junction structure as disclosed in JP-A-62-89949 are also preferably used. Tabular grains are also used, and an emulsion in which tabular grains having a ratio of grain diameter in terms of circle to grain thickness of 5 or more and 8 or less account for 50 mol% or more of the projected area of all grains is excellent in rapid developability and advantageous. Is. Even for such tabular grains, those having two or more partial structural properties having different silver bromide contents as described above are more preferably used.

The average size of grains of the silver halide emulsion used in the present invention (average diameter of spheres equivalent to volume) is 2 μm.
In the following, 0.1 μm or more is preferable. Particularly preferred is 1.4 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but monodisperse emulsions are preferred.
In particular, the above-mentioned cubic, octahedral, junction grain or tabular grain monodisperse emulsions are preferred in the present invention. 85% of all particles within ± 20% of average particle size by number of particles or weight
It is preferable to use a monodisperse emulsion having a content of at least 100%, and further to use two or more kinds of such monodisperse emulsions by mixing or multilayer coating. When two or more kinds of monodisperse emulsions are mixed and used, they are preferably mixed and used at a silver conversion mixing ratio of 5% or more and 95% or less. The average grain size of the mixed emulsions is 1: in terms of volume.
It is preferable that the difference is 1.1 or more and 1: 8 or less,
Further, it is preferable that they are different in the range of 1: 1.2 or more and 1: 6 or less. In the present invention, the "vicinity of the apex" is preferably a length of 1/3 (more preferably 1/5) of the diameter of a circle having the same area as the projected cube or cubic crystal-like regular crystal silver chloride grains. It is within the area of a square with one side being the corner and the apex of the grain (a cube or the intersection of the edges of normal crystal grains regarded as a cube) being one corner. The content of silver chlorobromide grains having a silver bromide-rich region according to the present invention is 70 mol% based on all silver halide grains contained in the same emulsion layer.
The above is preferable. For the preferred method for preparing the silver halide emulsion of the present invention, see JP-A-3-156439, 298-3.
It is described on page 02.

The following method is preferable as the method of supplying bromine and / or bromine ions a plurality of times in the present invention. A method in which an aqueous solution of a water-soluble compound such as potassium bromide is added to and mixed with a silver halide emulsion. A method in which silver halide grains having a smaller average grain size than silver halide host grains and a high silver bromide content (mol%) are added to and mixed with a silver halide emulsion. A method of adding and mixing bromine and / or a bromine ion precursor to a silver halide emulsion as disclosed in JP-A-1-285942. Further, the above methods may be combined in the supply of the bromine and / or bromine ions. Furthermore, the silver bromide content of the silver bromide-rich region formed by supplying bromine and / or bromide ions once in a plurality of times is
Alternatively, it is preferably higher than the silver bromide content in the silver bromide-rich region formed by supplying bromine ions (preferably higher by 5 mol% or more). The bromine and / or bromide ions are supplied once during a plurality of times of supply, after the formation of the silver bromide-rich region by the preceding supply of bromine and / or bromide ions is completed by 80 mol% or more. Is preferred. In the present invention, the silver bromide content of the host grains and the silver bromide content of the silver bromide-rich region need to differ by at least 10 mol% or more. Further, the silver bromide content in the silver bromide rich region is preferably 10 mol% or more and 70 mol% or less (more preferably 30 mol% or more and 60 mol% or less).

The structure of the silver halide grains of the present invention is observed by various analytical methods. First, by observation with an electron microscope, it is observed that a new phase is bonded near the apex of the particle due to the morphological change of the particle. Further, the halogen composition of the host particles and the new phase can be obtained by the X-ray diffraction method. For the average halogen composition of the surface, see X
By PS (X-ray Photoelectron Spectroscopy) method,
For example, it can be measured using an ESCA750 spectroscope manufactured by Shimadzu-du Pont. About this measuring method, please refer to Someno / Yasumorii "Surface Analysis" Kodansha (issued in 1977).
It is described in. By knowing the halogen composition of the host grain and the new phase by the X-ray diffraction method and knowing the average silver halide composition of the surface by the XPS method, how much of the new surface rich in silver bromide than the host grain on the entire surface can be measured. Can be roughly estimated. Further, in order to identify the existence position of a new phase richer in silver bromide than the host grains and to measure how much it occupies in the vicinity of the apex of the grains, the method by observation with the electron microscope is used. other,
It can be measured by an EDX (Energy Dispersive X-ray analysis) method using an EDX spectrometer equipped in a transmission electron microscope. This measuring method is specifically described in "Electron Beam Microanalysis" by Keiyoshi Soejima, Nikkan Kogyo Shimbun (issued in 1987).

The silver chlorobromide emulsion used in the present invention is P. Glafk
By ides Chimie et Phisique Photographique (Paul Mon
tel, 1967), by GF Duffin Photographic Em
ulsion Chemistry (Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be prepared by the method described in Emulsion (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a 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. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A-62-215272 are preferably used. Further European patent publication EP 0,447,647
5-Arylamino-1,2,3,4-
A 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 spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
[York, 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-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-12 is known.
The spectral sensitizing dye described in No. 3340 is very 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 of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, left lower column, or JP-A-3-20730, page 4, lower left column-
Page 15, lower left column, European Patent Publication EP 0,420,011, page 4, line 21 to page 6, line 54, same, 0,420,012, page 4, line 12 to page 10, line 33, 0,443,466, U.S.A. The sensitizing dyes described in Japanese Patent No. 4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in a 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. 3,822,135 and US Pat.
As described in No. 06,025, an aqueous solution or colloidal dispersion in which a surfactant coexists 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. As described in JP-A Nos. 53-102733 and 58-105141, they 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. 3,62.
It is also possible to perform spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-8-9139 and JP-A-5-225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate 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 amount of these spectral sensitizing dyes added is in a wide range 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.

In the present invention, by providing a hydrophilic colloid layer containing a white pigment between the support and the color forming silver halide emulsion layer closest to the support, the silver bromide content of the silver halide emulsion grains can be improved. It is surprising that the undesired fluctuation of the color density when exposed under high humidity, which is caused by providing at least two partial structures different by 10 mol% or more, can be effectively suppressed.
When the hydrophilic colloid layer containing the white pigment in the present invention is provided on the support, the coating amount of the white pigment is 2
It is necessary to make it g / m ² or more. It is preferably 4 g / m ² or more, more 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 (the ratio of the white pigment to the total of the white pigment and the hydrophilic colloid) needs to be 20% by weight or more. It 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 a white pigment is determined from the above filling rate and coating amount, but is preferably in the range of 0.5 to 10 μm,
The range of 5 μm is more preferable.

Examples of the white pigment used in the present invention include titanium dioxide, barium sulfate, lithopone, white alumina, calcium carbonate, white silica, antimony trioxide, titanium phosphate, zinc oxide, white lead 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. As the particle size of the white pigment particles used in the hydrophilic colloid layer, those having an average particle size of 0.1 to 1.0 μm can be used. Preferably 0.2-0.3
μm.

In the present invention, gelatin can be preferably used as the hydrophilic colloid (binder) constituting the hydrophilic colloid layer containing a 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 thereof include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate), sodium alginate and starch derivatives. Saccharides, polyvinyl alcohol, partial acetals of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid,
There may be mentioned a wide range of synthetic polymers such as polymethacrylic acid, polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole. 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, it is a surfactant as a coating aid, a hardener, a dye, or an antifoggant. 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 and 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. A photosensitive emulsion layer may be directly provided on the hydrophilic colloid layer containing a white pigment, or a photosensitive emulsion layer may be provided via one or a plurality of non-photosensitive hydrophilic colloid layers. You may. 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 desired. 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 mixture preventing agent, a fluorescent whitening agent or an ultraviolet absorber can be dissolved and contained. In addition to the white pigment-containing hydrophilic colloid layer, the light-sensitive material of the present invention may contain a white pigment in the water-resistant resin that coats the paper substrate. In this case, it is preferable to include a white pigment in the water resistant resin on the side on which the photosensitive emulsion layer is coated.

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 is arranged 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 is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to install only a part of them arbitrarily.
It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer has an optical density value of 0.2 at a wavelength having the highest optical density in a visible light region of 400 nm to 700 nm as a wavelength of light.
It is preferably not less than 3.0 and not more than 3.0. It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 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 which 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 in Japanese Patent Application Laid-Open No. 2-308244
No. 4-13 of the issue. 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 support used in the present invention may be either a "reflection type support" or a "transmission type support", and preferably a "reflection type support" is used. The "reflective type support" refers to one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear, and such a reflective type support is
The support is coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate, or the hydrophobic resin itself containing a light-reflecting substance is used as the support. It includes what was there. Examples of the support that can be used include polyethylene-coated paper,
Reflective supports such as polypropylene-based synthetic paper, transparent supports such as glass plates, polyethylene terephthalate,
Examples include polyester films of cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, and the like. The support used in the present invention is a paper support whose both surfaces are coated with a waterproof resin layer, and it is preferable that at least one of the waterproof resin layers contains white pigment fine particles. The white pigment particles are preferably contained in a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflecting white pigment particles, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a divalent to tetravalent alcohol. It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles, and the size of the distribution is such that the occupied area ratio (%) (R _i ) of the fine particles projected onto a unit area. Can be measured and obtained. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of R _{i to} the average value (R) of R _i . In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable.

In a preferred embodiment of the color light-sensitive material of the present invention, 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 are coated on a support. It can be installed and configured. 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.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 ppm
It is preferable to use low calcium gelatin of 200 ppm or less, more preferably below. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

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 development process, but in the case of the color light-sensitive material of the present invention, it is preferable to carry out a bleach-fixing process 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 and processings applied for processing this light-sensitive material. As the additive, the following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Laid-Open No. 2-1
Those described in Japanese Patent No. 39544) are preferably used.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[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 listed 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 EP 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, the compound in the aforementioned patent specification which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing It is possible to use the compounds in the above-mentioned patent specification, which are chemically bonded to the oxidized product of the residual aromatic amine color developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, For example, it is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the coupler with the residual color developing agent in the film or the oxidant thereof during storage after processing.

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 EP 0,333,185
3-Hydroxypyridine cyan couplers described in A2 (among others, couplers (42) listed as specific examples)
4 equivalent couplers having a chlorine-releasing group to make them 2 equivalents, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 ( Of these, coupler examples 3, 8, and 34 listed as specific examples are particularly preferable), pyrrolopyrazole-type cyan couplers described in European Patent EP 0,456,226A1, and European Patent EP 0,484,909.
Pyrroleumidazole type cyan couplers described in Japanese Patent Nos. EP 0,488,248 and 0,491,19.
Use of the pyrrolotriazole type cyan coupler described in 7A1 is preferable. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

As the yellow coupler, in addition to the compounds described in the above table, European Patent EP 0,447,9
69A1 acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group, malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0,482,552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 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. Also, JP-A-63-231451
No. 63-123047, No. 63-241547, and JP-A Nos. 1-173499 and 1-213648.
It is also preferable to use a so-called short-wave type yellow coupler described in JP-A 1-250944.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents of the above table are used, and among them, hue is also image stability,
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
Use of a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A is preferable.

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 can be used.
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.

[0037]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of silver chlorobromide emulsion B1) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and the aqueous solution containing 0.5 mol of silver nitrate and 0.5% of sodium chloride.
An aqueous solution containing a mole was added and mixed 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 66 ° C. with vigorous stirring. After that, desalting was performed by washing with sedimentation water at 40 ° C. Furthermore, lime-processed gelatin 9
0.0 g was added. This emulsion has a grain size of 0.05 μm
0.002 mol of silver bromide fine grain emulsion of
After addition at 0 ° C to form a silver bromide rich region on the surface of the silver chloride host grain, a sulfur sensitizer was added and optimum chemical sensitization was performed at 50 ° C. In the silver bromide fine particles, 0.8 mg of potassium hexachlorosiridium (IV) ate was contained per 0.005 mol of the silver bromide fine particles during the grain formation. The grain shape, grain size, and grain size distribution of the obtained large-sized silver chlorobromide emulsion B1 were determined from electron micrographs. The silver halide grains were cubic, the grain size was 0.55 μm, and the coefficient of variation was 0.08.
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.

(Preparation of silver chlorobromide emulsion B2) In the method for preparing silver chlorobromide emulsion B1, 0.004 mol of silver bromide fine grain emulsion having a grain size of 0.05 μm was added in an amount of silver. A modified emulsion was prepared and designated as silver chlorobromide emulsion B2. (Preparation of Silver Chlorobromide Emulsion B3) An emulsion obtained by changing the preparation method of Silver Chlorobromide Emulsion B1 by adding 0.008 mol of silver bromide fine grain emulsion having a grain size of 0.05 μm. To prepare a silver chlorobromide emulsion B3. (Preparation of silver chlorobromide emulsion B4) In the preparation method of silver chlorobromide emulsion B1, silver bromide fine grain emulsion having a grain size of 0.05 μm was added in an amount of 0.004 mol at 50 ° C. to obtain silver chloride. After forming a silver bromide-rich region on the surface of the host grain, a silver bromide fine grain emulsion having a grain size of 0.05 μm was added in an amount of 0.004 mol at 50 ° C. to give an odor on the surface of the silver chloride host grain. An emulsion prepared by changing only the formation of the silver halide-rich region was prepared and designated as silver chlorobromide emulsion B4. (Preparation of silver chlorobromide emulsion B5) A silver chlorobromide fine grain emulsion having a silver bromide content different from that of the silver bromide fine grain emulsion used in silver chlorobromide emulsion B1 (silver bromide content 60 mol%, grains Size 0.0
5 μm) was prepared, and the present silver chlorobromide fine grain emulsion was added in an amount of 0.004 mol at 50 ° C. to form a silver bromide-rich region on the surface of the silver chloride host grains. 0.005 μm silver bromide fine grain emulsion in terms of silver amount of 0.00
A silver chlorobromide emulsion B5 was prepared by adding 4 mol of the silver chloride at 50 ° C. and changing the emulsion except that a silver bromide rich region was formed on the surface of the silver chloride host grain. (Preparation of silver chloride emulsion B6) A silver halide emulsion having no silver bromide-rich layer was prepared by omitting the step of adding a silver bromide fine grain emulsion having a grain size of 0.05 μm in the method for preparing silver chlorobromide emulsion B1. It was prepared and designated as silver chloride emulsion B6. (Preparation of Silver Chlorobromide Emulsion B7) In the method for preparing silver chlorobromide emulsion B3, an aqueous solution containing 0.5 mol of silver nitrate and an aqueous solution containing 0.5 mol of sodium chloride were vigorously stirred to produce 6
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 66 ° C. with vigorous stirring to obtain an aqueous solution containing 0.5 mol of silver nitrate. And 0.4 mol sodium chloride,
An aqueous solution containing 0.1 mol of potassium bromide was added and mixed at 66 ° C. with vigorous stirring, and then an aqueous solution containing 0.45 mol of silver nitrate, 0.36 mol of sodium chloride and 0.09 mol of potassium bromide. Was changed to the addition and mixing at 66 ° C. with vigorous stirring, and an emulsion different only in that host grains were prepared, and silver chlorobromide emulsion B was prepared.
It was set to 7. (Preparation of silver chlorobromide emulsion B8) A silver halide having no silver bromide-rich layer is omitted by omitting the step of adding a silver bromide fine grain emulsion having a grain size of 0.05 μm in the method for preparing silver chlorobromide emulsion B7. An emulsion was prepared and designated as silver chloride emulsion B8. The silver bromide contents of different partial structures of the prepared emulsion were determined by X-ray diffraction method, and the average halogen composition on the surface was determined by XPS method.

[0039]

[Table 5]

Next, after corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic paper (Sample 101) having the layer structure shown was produced. The coating liquid was prepared as follows. Preparation of coating liquid for third layer Magenta coupler (ExM1) 16.0 g, color image stabilizer (Cpd-5) 15.0 g, color image stabilizer (Cpd-2)
3.0 g, color image stabilizer (Cpd-6) 1.0 g, color image stabilizer (Cpd-7) 1.0 g and color image stabilizer (Cpd-)
8) 8.0 g, solvent (Solv-3) 50.0 g, solvent, (Solv-4) 15.0 g, solvent, (Solv-
5) Dissolved in 15.0 g and 45 cc of ethyl acetate, and added this solution to 10% sodium dodecylbenzenesulfonate 4
After being added to 200 cc of 20% gelatin aqueous solution containing 0 cc, it was emulsified and dispersed by a high-speed stirring emulsifying machine to prepare an emulsified dispersion B. On the other hand, the previously prepared silver chlorobromide emulsion B1
(Cube, average grain size 0.55 μm. Coefficient of variation of grain size distribution is 0.08, 0.2 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. The green sensitizing dyes C and D shown below are 4.0 × 10 ⁻⁴ mol and 7.0 mol per mol of silver, respectively.
× 10 ⁻⁵ mol was added. Also, sulfur sensitization was optimally performed on this emulsion. The above emulsified dispersion B and this silver chlorobromide emulsion B1 were mixed and dissolved to prepare a coating solution for the third layer having the composition shown below. The coating solutions for the first to second layers and the fourth to seventh layers were also prepared in the same manner as the third layer coating solution. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Further, the total amount of Cpd-14 and Cpd-15 in each layer, each was added to a 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-mercaptotetrazole was added to each of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, and 1 mol of silver halide.
2.5 × 10 ⁻⁴ mol was added. Further, 4-hydroxy-6-methyl-1, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0045]

[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 [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluing dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion A (cube, average grain size) 0.88 μm
3: 7 mixture of large size emulsion A of (1) and small size emulsion A of 0.70 μm (silver molar ratio). The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. Consists of)
0.27 Gelatin 1.36 Yellow coupler (ExY1) 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 Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0. 03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B1 0.13 Gelatin 1.45 Magenta Coupler (ExM1) 0.16 Color Image Stabilizer (Cpd-5) 0.15 Color Image Stabilizer ( Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0 .50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15 Fourth layer (color mixing prevention layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-7) 0 .02 solvent (Solv-2) 0.18 solvent (Solv-3) 0.18

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cube, average grain size 0.50 μm)
1: 4 mixture of large size Emulsion C and 0.41 μm small size Emulsion C (silver molar ratio). The variation coefficients of the grain size distribution are 0.09 and 0.11, respectively, and in each size emulsion, 0.8 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. Consists of)
0.20 Gelatin 0.85 Cyan coupler (ExC1) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-6) 0.22 Color image stabilizer (Cpd-8) 0.11 Color image stabilizer (Cpd-6) 0.11 Solvent (Solv-1) 0.11 Color image stabilizer (Cpd-1) 0.33 Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorber (UV-1) 0.38 Color image stabilizer (Cpd-12) 0. 15 Color image stabilizer (Cpd-5) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic modification of polyvinyl alcohol Copolymer (Modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01 where The compound use is shown below.

[0049]

[Chemical 2]

[0050]

[Chemical 3]

[0051]

[Chemical 4]

[0052]

[Chemical 5]

[0053]

[Chemical 6]

[0054]

[Chemical 7]

[0055]

[Chemical 8]

Samples 102 to 1 in which the silver halide emulsion B1 contained in the green-sensitive emulsion layer was changed to B2 to B8 with respect to the light-sensitive material (Sample 101) having the above-mentioned layer structure.
08 was produced. The following experiments were conducted to examine the photographic characteristics of the obtained samples 101 to 108. First, a sensitometer for the sample (FWH manufactured by Fuji Photo Film Co., Ltd.
The mold and the light source color temperature of 3200 K) were used to provide gradation exposure for sensitometry through a green filter. The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 1/10 second. Then, color development processing 1 shown below was performed. Color development processing 1 (Processing step) (Temperature) (Time) Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Water wash 28-35 ℃ 95 seconds

Color developer Triethanolamine 8.12 g N, N-diethylhydroxylamine 4.93 g Optical brightener (UVITEX CK manufactured by Ciba-Geigy) 2.80 g 4-Amino-3-methyl-N-ethyl-N- [Β- (Methanesulfonamido) ethyl] -p-phenylenediamine sulfate 4.96 g sodium sulfite 0.13 g potassium carbonate 18.40 g potassium hydrogen carbonate 4.85 g EDTA · 2Na · 2H ₂ O 2.20 g sodium chloride 1.36 g Add water 1000ml pH 10.05

Bleach-fixing solution Ammonium thiosulfate (54 wt%) 103.0 ml NH ₄ [EDTA.Fe] 54.10 mg Sodium sulfite 16.71 g Glacial acetic acid 8.61 g Water was added to 1000 ml pH 5.44

For color development treatment 1, potassium bromide (8.4 × 10 ^-2 mol / liter) was further added to the developer.
A color developing treatment 2 and a color developing treatment 3 were prepared by preparing a developing solution in which 2.6 cc / liter of the aqueous solution was dissolved and 5.2 cc / liter thereof.

Next, samples 109 to 116 were prepared which differed from the samples 101 to 108 only in that a hydrophilic colloid layer containing titanium dioxide as a white pigment was provided between the support and the first layer. . The coating liquid for the titanium dioxide-containing layer was prepared as follows. Calcium-removed 10% gelatin aqueous solution with ion exchange 1,00
Rutile titanium white pigment with an average particle size of 0.23 μm per 0 g (Titanium White R780 manufactured by Ishihara Sangyo Co., Ltd.) 4
00 g of water and 4000 cc of water were added, and 8 cc of a 5% sodium dodecylbenzenesulfonate aqueous solution was added as a dispersant, followed by ultrasonic dispersion. Using the coating liquid thus seen,
The titanium dioxide was applied so that the applied amount was 1 g / m ² . Further, coating materials 117 to 132 which are different from the samples 109 to 116 only in the coating amount of titanium dioxide were prepared.

Exposure and color development processing 1, 2 and 3 were performed on each of the samples 101 to 132, and color development processing 1 was performed.
The optical density (D ₂ ) of magenta in the color development processing ₂ and the optical density (D ₃ ) of magenta in the color development processing 3 were measured with the amount of light giving the optical density of magenta in the color development processing (D ₁ ). difference in concentration between the color developing 2,3 for development processing 1 ( "D ₂ -D _1", "D ₃ -D
₁ ") was measured. Also, 25 ° C 35% RH, 25 ° C 5
Exposure was carried out under the condition of 5% RH, color development processing 1 was carried out, and the density difference was measured. (The concentration at 25 ° C and 35% RH is D _{35% RH.}
And when the concentration at 25 ° C 55% RH is D _{55% RH} ,
The density difference "D _{55% RH-} D _{35% RH} " was measured. According to Table-B, when silver halide emulsions B2 to B5 are used and a hydrophilic colloid layer containing titanium dioxide as a white pigment in an amount of ² g / m ² or more is provided between the support and the first layer (sample) 1
18 to 121 and Samples 126 to 129), even if the concentration of the bromine compound in the developing treatment solution increased, the concentration change of the magenta color development part remained small, and even when exposed under high humidity, the magenta color development part It can be seen that the concentration fluctuation is suppressed.

[0062]

[Table 9]

[0063]

[Table 10]

[0064]

[Table 11]

Example 2 In contrast to the samples 101 to 132 prepared in Example 1, the coloring substance layers A and B and the intermediate layer were formed on the hydrophilic colloid layer containing the white pigment on the support provided in Example 1. Samples 201 to 232 were prepared by producing a multilayer color photographic paper in which the above was coated in this order from the support side. The coloring substance-containing layer A contains colloidal silver prepared by the following method as a coloring substance.
2 g of anhydrous sodium carbonate was added to 1,000 g of a 10% aqueous gelatin solution, and the mixture was kept at 45 ° C. To this, 500 cc of a 10% silver nitrate aqueous solution was added, and 1,000 cc of an aqueous solution containing 35 g of anhydrous sodium carbonate and hydroquinone was added over 10 minutes. After the addition was completed, the mixture was allowed to stand for 10 minutes, and then about 100 cc of 1N sulfuric acid was added to adjust the pH to 5.0.
The obtained colloidal silver sol was poured into a cooling dish, gelled sufficiently, then cut into noodles, washed with cold water for 6 hours, and desalted to obtain a colloidal silver dispersion. The coloring substance-containing layer B contains a solid dispersion of a dye prepared by the following method as a coloring substance. Water 21.7 cc, 3.0 cc of 5% aqueous solution of sodium p-octylphenoxyethoxyethane sulfonate and 0.5 g of p-octylphenoxy poly (polymerization degree 10) oxyethylene ether 700 cc
1.65 g of Dye D-1 and beads of zirconium oxide (diameter: 1 mm, volume: 500 cc) were added, and the mixture was dispersed for 2 hours using a vibrating ball mill BO type manufactured by Central Processing Machine. After dispersion, take out the contents and take 12.5
% Gelatin aqueous solution was added and the beads were removed by filtration to obtain a solid dispersion of the dye.

[0066]

[Chemical 9]

The composition of these layers is as follows: As the color mixing inhibitor and the solvent, those used in Example 1 were used.
The gelatin used in these layers contains 1
The one removed to 0 ppm or less was used. Coloring substance-containing layer A Black colloidal silver (coated amount in terms of silver) 0.10 g / m ² Gelatin 0.99 g / m ² Color mixture inhibitor (Cpd-4) 0.08 g / m ² Solvent (Solv-1) 0.16 g / m ² solvent (Solv-4) 0.08 g / m ² Coloring substance-containing layer B Dye D-1 0.06 g / m ² Gelatin 0.66 g / m ² Intermediate layer Gelatin 0.99 g / m ² Color mixture inhibitor (Cpd-4) 0.08 g / m ² solvent (Solv-1) 0.16 g / m ² solvent (Solv-4) 0.08 g / m ²

Samples 201 and 2 are the same as in Example 1.
32, exposure, color development processing 1, 2 and 3 are performed,
The optical density of the magenta in the color developing processing 2 and the color developing processing 3 is measured with the light amount that gives the optical density of the magenta in the color developing processing 1, and the density of the color developing processing 2 and 3 with respect to the color developing processing 1 is measured. The difference was measured. Also, 2
Exposure under the conditions of 5 ° C. 35% RH, 25 ° C. 55% RH,
Color development processing 1 was performed and the density difference was measured. According to Table-C, when silver halide emulsions B2 to B5 were used and a hydrophilic colloid layer containing titanium dioxide as a white pigment in an amount of ² g / m ² or more was provided between the support and the first layer (Sample 218).
221 and Samples 226 to 229), even if the concentration of the bromine compound in the development processing solution increased, the concentration change of the magenta color development part remained small, and the density of the magenta color development part even when exposed under high humidity. It can be seen that the fluctuation is suppressed. Further, by comparing Example 1 and Example 2, it can be seen that the effect of suppressing the concentration fluctuation is effective even when the colored layer is provided. Moreover, the sharpness is further improved by providing this colored layer.

[0069]

[Table 12]

[0070]

[Table 13]

[0071]

[Table 14]

[0072]

According to the present invention, there is rapid processing suitability,
A silver halide color photographic light-sensitive material that does not cause a decrease in color density even when the bromine compound and bromine ion concentrations in the developing solution increase, and has little undesired fluctuation in color density even when exposed to high humidity. Can be obtained.

Claims (4)

[Claims] 1. A silver halide color light-sensitive material having at least one color-forming silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more. A silver chlorobromide emulsion grain containing emulsion grains, wherein the silver chlorobromide emulsion grains have at least two partial structures in which the silver bromide content differs by at least 10 mol% in the crystal grains, and the support A hydrophilic colloid layer having a white pigment filling rate of 20% by weight or more and a coating amount of 2 g / m ² or more is provided between the above and the closest color forming silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized in that 2. The color layer according to claim 1, further comprising a colored layer which can be decolorized by a developing process at any position of the hydrophilic colloid layer group constituting the light-sensitive material on the support. Silver halide color photographic light-sensitive material. 3. At least one of the partial structures is a silver bromide-rich region formed in the vicinity of at least one apex of the silver chlorobromide grains, and the average odor on the surface of the silver chlorobromide grains. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide content is 5 mol% or more and 15 mol% or less. 4. The silver bromide rich region is formed by supplying bromine and / or bromine ions to a silver halide host grain a plurality of times.
A silver halide color photographic light-sensitive material described in 1.