JPH0728207A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material, especially a printing material, which has a halation preventing layer containing silver particles and is excellent in rapid processing property, desilverizing property, and stability of latent images even if time passed after the photosensitive material is produced. CONSTITUTION:This silver halide color photographic material contains at least one photosensitive silver halide emulsion layer on a paper supporting body. At least one silver halide emulsion layer contains silver chloride particles or silver chloride/bromide particles containing >=90mo1% silver chloride. Moreover, the photosensitive material has a halation preventing layer containing planer silver particles of about <=0.02mum particle size between the base body and the silver halide emulsion layer. Further, the paper base body consists of an base paper of pH>=5 and pH<=9.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photographic technology.

[0002]

2. Description of the Related Art Recently, in silver halide color photographic light-sensitive materials, especially in light-sensitive materials for printing, there has been a strong demand for speeding up of development processing steps, and technological developments have been made one after another in order to shorten the processing steps year by year. It has been introduced to the market. Particularly in silver chlorobromide which does not substantially contain silver iodide, it has recently been known that increasing the silver chloride content or using pure silver chloride is effective, and each company has a high silver chloride content. Practical use of high silver chloride grains has been made. On the other hand, among the historical progress of silver halide color photographic light-sensitive materials, the improvement of quality is remarkable. These "quality" include many factors such as hue, saturation, graininess, fastness, etc., but improvement of image sharpness (image sharpness) is also an important factor. There is no doubt.

In order to improve the sharpness, various techniques for improving the sharpness have been studied, especially in the photographic material system. In recent years, the importance is pointed out also in the print material system having a reflective support. It became so. As a means for improving the sharpness of a print material system having a reflective support, a method of pre-dispersing an anti-irradiation dye in the hydrophilic colloid layer for reducing scattering of incident light in the photosensitive layer at the time of exposure and A method for increasing the white pigment loading of the water resistant layer provided on the surface of the support in order to reduce the scattering of the incident light on the surface of the support during exposure and reduce the image bleeding due to the scattering of the incident light during image observation after processing Is generally known. Regarding the former, an example in which an anti-irradiation dye is improved is disclosed in JP-A-62-2833.
No. 36 specification and the like. Regarding the latter, an improved example of a polyethylene layer containing titanium oxide is described in JP-A-61-259246. In addition, a hydrophilic binder layer is provided on the surface of the support,
There is also a method of improving the sharpness by containing colloidal silver, solid fine particle dye, or white pigment in this layer, and for example, there is a method described in JP-A-3-127058.

Among the above techniques, providing a hydrophilic binder containing colloidal silver, which is called an antihalation layer, on a support is widely used in a photographic material system because the effect of improving sharpness is great. However, when it is applied to a printing material system that requires rapid processing, the hue of yellow is deteriorated due to defective desilvering, and it has not reached a level at which it can be used practically, and its improvement has been desired.

The inventors of the present invention have disclosed a system for printing materials having a paper support carrying a silver halide emulsion layer containing silver chlorobromide grains or pure silver chloride grains having a high silver chloride content, to a system of a printing material. When the antihalation layer containing tabular silver particles having a thickness of 0.02 μm or less described in No. 134358 was applied, it was possible to improve the desilvering defect while maintaining excellent sharpness. However, the provision of this antihalation layer deteriorates the latent image stability (stability of the latent image from the time of exposure to the time of development) with the passage of time after the production of the light-sensitive material, and the exposure It was found that the sensitivity and gradation greatly changed depending on the time from the start to the development. On the other hand, in the major commercial laboratories at present, there is a tendency that the time from exposure to development processing is not always constant due to division of labor in the printing process. That is, after exposure, for example, the paper is not always developed immediately,
The time from exposure to development processing varies from a few seconds to a few hours. Therefore, the deterioration of latent image stability is a serious problem.

As a means for improving the latent image stability of a silver halide color photographic light-sensitive material containing silver chlorobromide grains or silver chloride grains having a high silver chloride content, a technique of using an organic compound having a hydroxyl group is disclosed in Japanese Patent Laid-Open No. No. 5-45779, etc. When the present inventors examined this technique, although there was certainly an improving effect immediately after the production of the light-sensitive material, it was effective against the deterioration of the latent image stability after a lapse of time after the production of the light-sensitive material. Was small and insufficient. Also,
Japanese Patent Application Laid-Open No. 4-125638 discloses a technique of incorporating at least one kind of periodic group VIII metal ion into the particles in order to improve latent image stability. When the improvement of the latent image stability by this technique was examined, there was an improvement effect, but it was not sufficient yet.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present inventor is to have an antihalation layer containing silver particles, to be excellent in rapid processing property and desilvering property, and to elapse the time after the production of the light-sensitive material. It is an object of the present invention to provide a silver halide color photographic light-sensitive material excellent in latent image stability, especially a printing material.
It is another object of the present invention to provide a color image forming method which can quickly and stably obtain a color photograph having excellent image quality.

[0008]

It has been found that the object of the present invention can be achieved by the following method. (1) In a silver halide color photographic light-sensitive material containing at least one light-sensitive silver halide emulsion layer and at least one antihalation layer on a paper support, the silver halide emulsion layer has a silver chloride content of 90 mol. % Or more of silver chlorobromide particles or silver chloride particles, the antihalation layer contains tabular silver particles having a thickness of about 0.02 μm or less, and the paper support has a pH of 5 or more and 9 or less. A silver halide color photographic light-sensitive material,
(2) The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide grains contain at least one kind selected from Group VIII metal ions of the periodic table. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide grains contain iron ions and iridium ions.

The present invention will be described in more detail below. The silver halide color photographic light-sensitive material of the present invention has at least one silver halide emulsion layer and an antihalation layer interposed between the reflective support and the light-sensitive layer. As the antihalation layer, a layer made of a suitable hydrophilic binder such as gelatin is used as a light absorber in an amount of about 0.02 μm.
It contains tabular silver particles having a thickness of m or less, so-called colloidal silver. The content of tabular grains in the silver grains of the antihalation layer is preferably 50 wt% or more, more preferably 70 wt% or more. In a preferred embodiment of the invention the antihalation layer contains colloidal silver grains which are tabular grains having an edge length having an average edge length of at least twice its thickness. Here, the thickness means more specifically the shortest distance between parallel planes. Further, the edge length means more specifically the diameter of a sphere capable of inscribing particles. The edge length and thickness of the colloidal silver particles can be determined by observing an electron micrograph. The colloidal silver particles preferably have an average edge length of 0.04 μm or less and a thickness of 0.005 to 0.02 μm,
Further, it is more preferable that the average edge length is 0.02 to 0.04 μm and the thickness is 0.005 to 0.012 μm for the purpose of obtaining the effect of the present invention. The antihalation layer is preferably provided between the support and the lowermost photosensitive emulsion layer. In the present invention, the presence of the tabular silver particles described above is superior to conventional colloidal silver antihalation layers containing larger and thicker particles at coating amounts up to about 200 mg silver per square meter of antihalation layer. The effect can be obtained. The amount of silver contained in the antihalation layer of the present invention is preferably small from the viewpoint of preventing desilvering failure and image color turbidity. Specifically, about 200 mg per 1 m ^{2 of} antihalation layer
The following is preferable, and a silver amount of 50 to 100 mg is more preferable.

In the light-sensitive material of the present invention, the antihalation layer produces nuclei having a diameter of about 0.02 μm or less dispersed in the hydrophilic colloid layer, and the solution of the nuclei-containing dispersion is mixed with the silver ion-containing solution. It is obtained by mixing, plating the nuclei in the solution with silver, terminating the plating so as to obtain particles of a desired hue, and coating the particles thus obtained on a support to form an antihalation layer. To be Preferably, the plating step is carried out by reducing the silver salt with a reducing agent. In the present invention, the method using a specific reducing agent according to the following specific embodiments is more preferable in that it does not cause other problems. Further, in the present invention, according to the following aspect, the colloidal silver in the antihalation layer is
It is preferred that the halide present in the adjacent photosensitive layer is prevented from converting to a yellow type.

The colloidal silver used in the present invention is previously produced by a chemical amplification method in which nuclei as a starting material are two-dimensionally (planarly) grown on a very small size plate according to the method described in JP-A-5-134358. It can be produced by depositing silver on the formed nuclei. This process can be divided into two types: nuclear production and amplification. Small silver nuclei can be produced by reducing silver nitrate in gelatin with a strong reducing agent. During amplification of the nucleus, the color changes from yellow to orange, reddish orange, red, purple and blue. Any of these colors can be selected by controlling the degree of amplification, that is, the ratio of starting nuclei to the amount of silver in the amplification bath. The higher the ratio, the greater the amount of silver plated and the color changes from orange to blue. In addition, amplification can be terminated by stopping as described below.

The colloidal silver nuclei in the present invention are produced by adding a silver solution, preferably a silver nitrate solution, to a hydrophilic colloid matrix containing a reducing agent (eg, gelatin aqueous solution). The hydrophilic colloid containing nuclei is preferably gelatin, but other hydrophilic polymers or alkali metal salts of fatty acids may be used. Although potassium borohydride is preferred as the reducing agent, other strong reducing agents such as other hydrogenating agents, dimethylamine borane, stannous chloride, and other water-soluble salts that provide stannous ion can be used. Good.

The silver nitrate solution used for nucleation was added to a gelatin aqueous solution containing a reducing agent with vigorous stirring, and then cooled and solidified. At this time, the reduction of silver ions with potassium borohydride or another similar reducing agent gives very small metal nuclei and fine metal platelets. The resulting dispersion is extruded through a screen to produce noodle gelatine particle nuclei. For example, when using 50 mesh stainless steel clean, the average diameter is about 250
Disperse nuclei with a diameter of 5-7 nm in gelatin noodles of ~ 300 μm. To prevent the gelatin noodles from sticking into large agglomerates, the dispersion may be further diluted with water to disperse the nuclei in a solid gelatin matrix different from the aqueous phase.

The dispersion noodles can be produced by using either a subsurface noodle forming method or a terplate noodle forming method. Among these, the method of forming submerged noodles is preferable in that a smooth and uniform noodle can be produced. The nuclei in the dispersion are silver salts and sulfites (K, N
amplification by treatment with a solution of hydroxynone monosulphonate or a similar reducing compound such as hydroxyamine ascorbate, together with a plating solution containing a silver complex salt forming agent such as a, ammonium salt). Preferably, the plating solution is prepared by mixing the silver salt solution with the sulfite / bisulfite solution and then rapidly adding the mixed solution to the dispersion. The sulfite complexing solution may contain reagents that promote the growth of silver platelets, for example calcium salts such as calcium acetate.

The amplification of the nuclei transforms the silver particles into metastable non-spherical particles. The silver particles initially change from yellow to orange, reddish orange, red, purple, and blue due to the progress of the reaction, and the amplification of the silver particles is confirmed by the color change of the resulting particles. Amplification can also be extended to produce a green color. The reaction can be stopped by diluting with water or by eliminating the reactants to stop the reaction in the desired color. The silver-containing noodles are collected by filtration through a nylon mesh pack or similar means and washed. The noodles are then stabilized in water, then melted and purified by filtration. The metastable silver thus obtained can be cooled and stored if storage is required. If the silver particles are not yellow, the agglomerated particles are non-spherical, usually with an average edge length of about 0.02-0.04 μm, and about 0.005-0.02 μm, preferably 0.005-.
It contains a large amount of tabular grains having a thickness of 0.12 μm.
Such tabular grains usually have an average edge length of at least twice the grain thickness. In the present invention, the tabular grains preferably have an average edge length of 2 to 15 of the grain thickness.
Times, more preferably 2 to 8 times.

In the present invention, gelatin can be preferably used as a binder for the hydrophilic colloid layer containing colloidal silver, 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 and casein, cellulose derivatives (eg, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate), sodium alginate and starch derivatives. Examples thereof include a wide range of synthetic polymers such as saccharides, polyvinyl alcohol, partial acetals of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. In the present invention, the colloidal silver-containing hydrophilic colloid layer may contain various materials to be added to the photographic light-sensitive material, in addition to the colloidal silver and the binder. For example, a surfactant as a coating aid, a hardener,
It is a dye or an antifoggant. Furthermore, a high-boiling point organic solvent dispersed on fine oil droplets can be contained. When the dispersion of the high-boiling point organic solvent is contained, it is preferable that various oil-soluble materials are dissolved and contained therein. A preferred embodiment of 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 colloidal silver. And a hydrophilic colloid layer. In the present invention, the hydrophilic colloid layer containing colloidal silver is coated between the support and the photosensitive emulsion layer.

A photosensitive silver halide emulsion layer may be directly provided on the hydrophilic colloid layer containing colloidal silver, or one or a plurality of non-photosensitive hydrophilic colloid layers may be interposed therebetween. A photosensitive emulsion layer may be provided. When a non-photosensitive hydrophilic colloid layer is provided, the total thickness of these layers is preferably 3 μm or less. Further, it is preferably 1 μm or less. These non-photosensitive hydrophilic colloid layers can contain various photographically useful substances, if necessary. For example, a surface active agent (coating aid), a film hardener, a dye, an antifoggant, or the like. Further, a dye dispersed in a solid state or a dye dyed with a cationic polymer may be contained to form a colored layer capable of being decolorized during development processing. 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 coloring layer which is preferably used as the non-photosensitive hydrophilic colloid layer and which can be decolorized by the development treatment may be in direct contact with the emulsion layer, and may be an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. You may arrange | position so that it may contact through. 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 the colored layers corresponding to the emulsion layers sensitized to have sensitivity in different wavelength regions, or to install only a part of them arbitrarily. It is also possible to provide a coloring layer having absorption in a wide wavelength range so as to correspond to a plurality of emulsions having different sensitizing wavelength ranges.

The pH value of the base paper used for the paper support of the light-sensitive material of the present invention must be 5 or more and 9 or less.
It is more preferably 6.0 or more and 8.0 or less. When the pH of the base paper is less than 5, the latent image stability is deteriorated, and when the pH of the base paper is higher than 9, the yellow density of the unexposed area becomes high due to the passage of time after the production of the light-sensitive material, which cannot be applied. In this specification, the pH value of the base paper is JIS-P.
It shall be the value measured by the regulation of the hot water extraction method of -8133. The outline of the hot water extraction method of JIS-P-8133 is described below. Approximately 1.0 g of the test piece is weighed out, placed in a 100 ml volume of an Erlenmeyer flask, 20 ml of distilled water is added, and the test piece is soaked with a flat stir bar until it becomes evenly moistened to be softened. Next, 50 ml of distilled water is further added and stirred, and the flask is equipped with a condenser. The flask is then placed in a water bath which keeps the contents of the flask at 95-100 ° C without boiling the water. After heating for 1 hour with occasional shaking at this temperature, it is cooled to 20 ° C. ± 5 deg and the pH value of the extract is measured as it is using a glass electrode pH meter.
For details of the above measurement method and the instruments used for the measurement, see 1
According to the Japanese Industrial Standard of 963.

The constitution of the paper support used in the present invention and specific means for adjusting the pH value of the base paper to 5 to 9 will be described below. The base paper used for the paper support is produced by making wood pulp as a main raw material and making paper. As wood pulp,
Although both softwood pulp and hardwood pulp can be used, it is preferable to use a large amount of short fiber hardwood pulp in the present invention. Specifically, it is preferable that 60% by weight or more of the pulp constituting the base paper is hardwood pulp. If necessary, part of the wood pulp may be replaced with synthetic pulp made of polyethylene, polypropylene or the like, or synthetic fiber made of polyester, polyvinyl alcohol, nylon or the like. The freeness of the pulp used is preferably 150 to 500 cc, more preferably 200 to 400 cc according to the CSF regulation. Furthermore, regarding the fiber length after beating, JI
It is preferable that the 24 + 42 mesh residue defined by SP-8207 is 40% by weight or less. In general, a sizing agent is internally added to the base paper, but in the present invention, since the pH value of the paper support needs to be 5 to 9, epoxidized fatty acid amide, fatty acid anhydride, rosin acid anhydride, alkenyl Succinic anhydride, succinamide,
It is preferable to use a neutral sizing agent such as isopropenyl stearate, an aziridine compound and an alkyl ketene dimer as the internally added sizing agent. Further, a sizing agent is generally added internally to the base paper, but in the present invention, since the pH value of the base paper needs to be 5 to 9, a sulfuric acid band (aluminum sulfate) usually used as a fixing agent is used. Instead, it is preferable to use a neutral or weakly alkaline compound such as cationized starch, polyamide polyamine epichlorohydrin, polyacrylamide, or polyacrylamide derivative, or to neutralize with an alkali after adding a sulfuric acid band.

Further, a filler such as calcium carbonate, talc, clay, kaolin, titanium dioxide or urea resin fine particles may be internally added to the base paper for the purpose of improving smoothness. As internal additives other than the above-mentioned internal sizing agent, fixing agent, and filler, paper-strengthening agents such as polyacrylamide, starch, and polyvinyl alcohol; reaction products of maleic anhydride copolymer and polyalkylene polyamines; A softening agent such as a quaternary ammonium salt; a colored dye; a fluorescent dye or the like may be added to the base paper as needed. In principle, these internal additives also have pH values of the base paper of 5-9.
It is preferable to select and use a drug having a value close to neutrality. Further, it is preferable to use as little acidic or alkaline chemical as possible.

The base paper used for the paper support can be produced by using the raw materials described above and using a Fourdrinier paper machine or a cylinder paper machine. The basis weight of the base paper is 20 to 300 g /
is preferably m ^2, and particularly preferably 50 to 200 g / m ^2. The thickness of the base paper is 25-350 μm
Is preferable, and 40 to 250 μm is particularly preferable. The base paper is preferably subjected to a calendering treatment such as an on-machine calender in a paper machine or a super calender after paper making for the purpose of improving smoothness. As a result of the above calendering process, the density of the base paper is 0.7 to 1 according to JIS-P-8118.
It is preferably ² g / m ^2, and 0.85 to 1.10
It is particularly preferable that it is g / m ² . The pH value of the base paper to be produced can be adjusted to 5 to 9 by the method for producing the base paper as described above, particularly by selecting the internally added chemicals (internally added sizing agent, fixing agent, etc.) and the surface sizing agent. In the light-sensitive material of the present invention, the base paper as described above can be used as it is as a paper support. A surface sizing agent may be applied to the surface of the raw paper. Examples of surface sizing agents include polyvinyl alcohol, starch, polyacrylamide, gelatin, casein, styrene maleic anhydride copolymer,
Examples thereof include alkyl ketene dimer, polyurethane and epoxidized fatty acid amide. In the present invention, the pH of the base paper refers to the pH of the base paper containing the sizing agent and the filler, or the pH of the base paper having the surface coated with the sizing agent. ,

A coating layer may be further provided on one or both surfaces of the above-mentioned base paper (including those coated with a surface sizing agent). There is no particular limitation on the structure of the coating layer,
It preferably comprises a hydrophobic polymer. By providing the coating layer containing the hydrophobic polymer, the water absorption of the paper support is lowered, and the strain of the support which occurs during the coating of the photosensitive layer can be reduced. The hydrophobic polymer may be a homopolymer or a copolymer. Further, in the case of the copolymer, it may have a hydrophilic repeating unit in a part thereof as long as it is hydrophobic as a whole. Examples of the hydrophobic polymer include polyethylene, polypropylene, vinylidene chloride, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylic acid ester copolymer, and styrene-methacrylate-acrylic acid ester copolymer. You can

A pigment may be added to the coating layer for the purpose of improving resolution. As the pigment, a known pigment used for coated paper can be used. Examples of pigments include inorganic pigments such as titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, crystalline silica, and synthetic alumina silica;
And organic pigments such as polystyrene resin, acrylic resin and urea formalin resin. The amount of the pigment added is appropriately 5 to 60% by weight, preferably 8 to 30% by weight, and more preferably 14% in the hydrophobic polymer.
~ 30% by weight. As a method for providing the coating layer, an extrusion coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, a gravure coating method, or the like can be used. For the purpose of improving the smoothness of the paper support, it is preferable to carry out a calender treatment such as a gloss calender or a super calender during or after coating.

It is also possible to use a support having a surface of the diffuse reflection property 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 type diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 3 μm with respect to the center plane.
It is 1.2 μm. The frequency of surface irregularities has a roughness of 0.1.
0.1 to 2000 cycles / m for unevenness of μm or more
It is preferably m, and more preferably 50 to 600 cycles / mm. Details of such a support are described in JP-A-2-239244.

At least one layer (preferably all layers) of the silver halide emulsion layer used in the present invention is preferably silver chlorobromide or silver chloride containing 90 mol% or more of silver chloride. . The content of silver chloride is preferably 95 mol% or more, more preferably 98 mol% or more. In the present invention, it is preferable that substantially no silver iodide is contained in order to accelerate the development processing time. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, 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-
No. 84,545 with an emulsion surface of 0.0
In some cases, high silver chloride grains containing 1 to 3 mol% of silver iodide are 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 and the core and the inside of the silver halide grains are used. Particles having a so-called layered structure having a different halogen composition with the shell (shell) surrounding the layer, or a structure having a non-layered portion having a different halogen composition inside or on the surface (when it is on the surface of the particle, Particles having a structure in which different composition portions are bonded to the edges, corners, or surfaces of the particles can be appropriately selected and used. For high sensitivity,
It is advantageous to use either of the latter two types of particles 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 structure as described above, 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 a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol% and up to 100 mol%. The silver bromide content of the silver bromide localized phase can be determined by X-ray diffractometry (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, the silver chloride content is 98 mol% to 100 mol%
An almost pure silver chloride emulsion having the following formula is also preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a 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. 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, and 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 is one having 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, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver chlorobromide emulsion or silver chloride emulsion used in the present invention is a Chimieet Phisique Photogr by P. Glafkides.
aphique (Paul Montel, 1967), GFDuffi
n Photographic Emulsion Chemistry (Focal Press, 1966), VL Zelikman et al Making and
Coating Photographic Emulsion (Focal Press, 1
964) and the like. That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method,
And any combination thereof may be used. 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 metal ion contained in the silver halide grain of the present invention is a periodic group VIII metal such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt, preferably iron ion. Alternatively, it is an iridium ion. Hexacyanoferrate (II) ion is more preferable as the iron ion. More preferably, it contains both iron ions and iridium ions. Further, metal ions such as copper, gold, zinc, cadmium or lead may be used together therewith. The content of these metal ions is 10 ^-9 per mol of silver halide.
More than mol, preferably from 10 ^-9 per mol of silver halide
It is 10 ^-2 mol, more preferably 10 ^-8 to 10 ^-3 mol per mol of silver halide. The molar ratio of the iron compound to the iridium compound can be selected in the range of 10 ^-5 to 10 ⁵ , and preferably 10 ^-2 to 10 ⁵ .
Further, the iron compound is preferably more than the iridium compound, and specifically, it is preferably 10 ² to 10 ³ times (molar ratio).

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 a metal ion 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
It is usually chemically sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound or selenium sensitization with a selenide compound, tellurium sensitization with a tellurium compound) is performed. Sensitization), noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272, page 18, lower right column to second column.
Those described in the upper right column on page 2 are preferably used. The emulsion used in the present invention is 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 EP 0447647
5-Arylamino-1,2,3,4-
A thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

In the light-sensitive material of the present invention, the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions of the light-sensitive emulsion is, for example, Heterocyclic compounds- by FM Harmer.
Cyanine dyes and related compounds (John Wiley & S
ons [New York, London] 1964). As specific examples of compounds and spectral sensitization methods, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a dye which can be used as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable and has strong adsorption. It is very preferable from the viewpoint of temperature dependence of exposure. In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, JP-A-3-15049
No. 12 upper left column to No. 21 lower left column, or JP-A-3-2
0730, page 4, lower left column to page 15, lower left column, EP-0,42
0,011, page 4, line 21 to page 6, line 54, EP-0,42
0,012, page 4, line 12 to page 10, line 33, EP-0, 4
The sensitizing dyes described in US Pat. No. 43,466 and US Pat. 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, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089, an acid or a base is allowed to coexist to prepare an aqueous solution, or as described in US Pat. No. 3,822,135, US Pat. No. 4,006,025, an aqueous solution is prepared by coexisting a surfactant. Alternatively, a colloidal dispersion may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to be added to the emulsion. JP-A-53-102733, JP-A-58-10
It may be directly dispersed in a hydrophilic colloid as described in 5141 and the dispersion 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 the application, but in US Pat. No. 3,628,
No. 58-113928, the spectral sensitization can be carried out simultaneously with the chemical sensitization by adding the chemical sensitizer at the same time as described in JP-A No. 969 and 4,225,666.
It can be carried out prior to the chemical sensitization as described in the publication, 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 mol range. In the present invention, particularly when using a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region,
It is preferable to use the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column. By using these compounds, the storability of the light-sensitive material, the processing stability, 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 5.0 mol per mol of silver halide.
× 10 ^-2 mol, preferably 5.0 × 10 ^-5 mol to 5.0
An amount of × 10 ^-3 mol is used, and is 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous amount used in the range of 0 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. The use of a semiconductor laser is preferable for designing a device that is particularly compact, inexpensive, and has a long life and high stability.
It is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, it is less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of this pixel. The size of this pixel is 50 to 2000 dpi as a practical range depending on the pixel density. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Also, upon exposure, U.S. Pat. No. 4,880,72
It is preferable to use the band stop filter described in No. 6. 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 perform bleach-fixing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

The color developing solution used in the present invention more preferably contains an organic preservative in place of hydroxylamine sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent due to air,
Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, α-amino acids, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines , Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. are particularly effective organic preservatives. These are Japanese Patent Publications
6, JP-A-52-143020 and 63-4235.
No. 63, No. 63-30845, No. 63-21647, No. 63-44655, No. 63-53551, No. 63-.
43140, 63-56654, 63-583.
No. 46, No. 63-43138, No. 63-146041.
Nos. 63-44657, 63-44656, and U.S. Pat. Nos. 3,615,503 and 2,494,903.
JP-A-1-97953, JP-A-1-186939,
1-186940, 1-187557, 2-
306244, European Patent Publication EP0530921
It is disclosed in A1 and the like. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-63-239447 and 63-1.
28340, JP-A-1-186939 and 1-18.
Amines such as those described in Japanese Patent No.
Alkanolamines described in 3532, JP-A-56-
Polyethyleneimines described in 94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be used as necessary. Especially alkanolamines such as triethanolamine, N, N-diethylhydroxylamine and N, N-di (sulfoethyl)
Addition of dialkylhydroxylamines such as hydroxylamine, α-amino acid derivatives such as glycine, alanine, leucine, serine, threonine, valine, isoleucine or aromatic polyhydroxy compounds such as catechol-3,5-disulfonate sodium. preferable.

In particular, a dialkylhydroxylamine and an alkanolamine are used in combination, or a dialkylhydroxylamine described in European Patent Publication EP0530921A1 and α-represented by glycine are used.
The combined use of amino acids and alkanolamines is more preferable from the viewpoint of improving the stability of the color developing solution and, in turn, improving the stability during continuous processing. The amount of these organic preservatives added may be an amount having a function of preventing deterioration of the color developing agent, and is preferably 0.01 to 1.0.
The mol / liter is more preferably 0.03 to 0.30 mol / liter.

The silver halide emulsion and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process the light-sensitive material. As the treatment additives, those described in the following patent publications, particularly European Patent No. 0,355,660A2 or JP-A-2-139544 are preferably used.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

The high-boiling organic solvent for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention is a compound which has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher and is immiscible with water. Any solvent can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high boiling point organic solvents are described in JP-A No. 62-215272, page 137, lower right column to page 144, upper right column. Further, the cyan, magenta, or yellow coupler is impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high-boiling organic solvent, or is insoluble in water. It can be dissolved with an organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, No. 7 of U.S. Pat. No. 4,857,449
Columns to 15 and the homopolymers or copolymers described in International Publication WO88 / 00723, pages 12 to 30 are used, more preferably methacrylate or acrylamide polymers, especially acrylamide polymers. Is preferable 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 above-mentioned patent specification which chemically bonds with the aromatic amine-based 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, JP-A-2-
In addition to the diphenylimidazole type cyan coupler described in Japanese Patent No. 33144, European Patent EP 0,333,185
The 3-hydroxypyridine cyan coupler described in A2 specification (among others, the coupler (42) listed as a specific example, which is a 4-equivalent coupler having a chlorine-releasing group to make it a 2-equivalent compound, or a coupler (6) or (9) is particularly preferable) and the cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples are particularly preferable),
Pyrrolopyrazole-type cyan couplers described in European Patent EP0,456,226A1, European Patent EP0,
It is preferable to use the pyrroloimidazole type cyan couplers described in 484,909 and the pyrrolotriazole type cyan couplers described in EP 0,488,248 and EP 0,491,197A1. 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, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, and a malondianilide type yellow coupler having a cyclic structure described in EP 0,482,552A1.
The acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 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.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the above-mentioned publicly known documents are used, and among them, hue, 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
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.

The method for processing the color light-sensitive material of the present invention includes:
In addition to the methods described in the above table, JP-A-2-207250, 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 18 The processing materials and processing methods described in the lower right column, line 20 are preferable.

[0056]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. In the following examples, parts representing composition represent parts by weight.

Example 1 (Preparation of Paper Support) 70 parts of LBKP and 30 parts of LBSP of wood pulp were subjected to CSF29 using a disc refiner.
Beated to 0 cc and used as a neutral sizing agent for alkyl ketene dimer (Dick Hercules Co., Ltd., Accorpel 12)
1.0 part, anion polyacrylamide (Polytron 194-7 manufactured by Arakawa Chemical Industry Co., Ltd.) 1.0 part, cationic polyacrylamide (Polystron 705 manufactured by Arakawa Chemical Industry Co., Ltd.)
) 0.7 part, polyamide polyamine epichlorohydrin (Kymen 557, manufactured by Dick Hercules).
All 3 parts were added in an absolutely dry weight ratio to the pulp.
Then, using a Fourdrinier paper machine, paper was made into a base paper having a basis weight of 170 g / m ² and a thickness of 165 μm. The base paper prepared as described above is referred to as (A). The pH value of the base paper (A) is JIS-
When measured by the hot water extraction method of P-8133, 6.
It was 0. 0.6 parts of epoxidized fatty acid amide (manufactured by Modern Chemical Industry Co., Ltd., NS-715) as a neutral sizing agent on the same beaten pulp as the base paper (A), anion polyacrylamide (Polystron 194-7 manufactured by Arakawa Chemical Industry Co., Ltd.) 1.
2 parts, aluminum sulfate 1.0 part, NaOH 1.1
And 1.0 part of cationized starch were added in an absolutely dry weight ratio to the pulp. Then, similarly to the base paper (A), the base paper (B) having a basis weight of 170 g / m ² and a thickness of 165 μm
Was made. The pH value of the base paper (B) was 8.0. Next, using the same beaten pulp as the base paper (A), 1.0 part of sodium stearate and 1.0 anion polyacrylamide (manufactured by Arakawa Chemical Industry Co., Ltd., Polystron 194-7) 1.0
Parts and 1.5 parts of aluminum sulfate were added in an absolutely dry weight ratio to the pulp. Then, in the same manner as the base paper (A), a base paper having a basis weight of 170 g / m ² and a thickness of 166 μm was made into a paper to obtain a base paper (C). The pH value by the hot water extraction method is 3.
It was 8. A base paper (D) was prepared in the same manner as the base paper (C) except that 0.4 part of sodium aluminate was added after the aluminum sulfate was added to the base paper (C). The pH value by the hot water extraction method was 4.5.

Sodium aluminate of the base paper (D) was added to 0.2%.
Base paper (E) similar to base paper (D) except that 6 parts were added.
It was created. The pH value by the hot water extraction method was 5.0. A base paper (F) was prepared in the same manner as the base paper (B) except that 1.8 parts of NaOH of the base paper (B) was added. The pH value by the hot water extraction method was 9.0. NaO of base paper (B)
A base paper (G) was prepared in the same manner as the base paper (B) except that 5.7 parts of H was added. The pH value by the hot vinegar extraction method is 9.5.
Met. The surface of each of the above-mentioned base papers (A) to (G) (the surface on which the photosensitive material is applied) is extruded and coated with polyethylene having a density of 0.94 / cm ² containing 10% by weight of titanium oxide at a thickness of 35 μm, and paper Support (A)
(G) was prepared.

Coating liquids (I, II, III) for the antihalation layer and coating liquids (IV, V, VI) for the comparative antihalation layer relating to the present invention were prepared as follows. (Coating liquid I) A mixture prepared by adding 3.488 kg of distilled water to 112 g of gelatin was heated at about 45 ° C to dissolve the gelatin, and calcium acetate 4.0 and potassium borohydride 2.0 were added thereto.
g was added. Immediately after that, 1 liter of a 6.0 g / liter silver nitrate aqueous solution dissolved was added in a state of being rapidly stirred. Next, distilled water was added so that the final weight was 5.0 kg. The product obtained here was cooled to near the gelling temperature, passed through a smaller hole, and then put into cooled water to form fine noodles. A solution prepared by adding 6.5 g of potassium hydroquinone monosulfonate and 10.29 g of KC to 81 g of distilled water was added to 650 g of borohydride reduced silver nuclei. The noodle slurry was cooled to about 6 ° C. A solution a in which 119.5 g of sodium sulfite and 0.98 g of sodium bisulfite were dissolved in 122 g of distilled water and a solution b in which 9.75 g of silver nitrate was dissolved in 122 g of distilled water were prepared. Solution a and solution b were mixed and stirred to form a white precipitate (soluble silver salt), then this mixture was immediately added to the noodle slurry with rapid stirring. Amplification was allowed to proceed for 80 minutes at a temperature of 10 ° C. until all soluble silver salts were reduced on the nuclei. The resulting slurry particles were washed with tap water in a nylon mesh pack for about 30 minutes for desalting. The water was drained until the weight of the product was 412 g so that the silver dispersed and washed in the gel slurry became a silver dispersion having a concentration of 1.5% by weight when melted.

(Coating liquid II) A colloidal dispersion was prepared in the same manner as in the coating liquid I except that the reduction time in the amplification step was changed from 80 ° C for 10 minutes to 120 minutes for 15 ° C in the method for preparing the coating liquid I. Obtained. (Coating liquid III) Coating liquid III was prepared in the same manner as in the preparation of the above coating liquid I, except that a solution c prepared by dissolving 10 g of sodium sulfite and 0.98 g of sodium bisulfite in 61 g of distilled water was used instead of the solution a used in the amplification step of A colloidal dispersion was obtained in the same manner as in liquid I. (Coating liquid IV) 5 g of anhydrous sodium carbonate was added to 1000 g of a 10% gelatin aqueous solution, and the mixture was kept at 45 ° C. To this, 500 cc of a 10% silver nitrate aqueous solution was added, and 1000 cc of a developing solution containing 60 g of anhydrous sodium sulfite and 25 g of hydroquinone was added at 15 ° C. for 10 minutes. After leaving for 10 minutes after the addition is completed, about 100 c of 1N sulfuric acid is added.
c 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 and desalted to obtain a colloidal silver dispersion. (Coating liquid V) A colloidal dispersion was prepared in the same manner as in the coating liquid IV except that the amount of the developer containing 60 g of anhydrous sodium sulfite and 25 g of hydroquinone was changed from 1000 cc to 2000 cc in the preparation of the coating liquid IV. Obtained. (Coating liquid VI) 2 g of anhydrous sodium carbonate was added to 1000 g of a 10% gelatin aqueous solution, and the mixture was kept at 45 ° C. To this, 500 cc of a 10% silver nitrate aqueous solution was added, and 1000 cc of a developing solution containing 35 g of anhydrous sodium sulfite and 25 g of hydroquinone was added at 15 ° C. for 10 minutes. After leaving for 10 minutes after the addition is completed, about 100 c of 1N sulfuric acid is added.
c 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 and desalted to obtain a colloidal silver dispersion.

As a result of observing the transmission electron micrographs of the coating liquids I to VI, it was confirmed that the colloidal silver particles had the following particle shapes.

[0062]

[Table 6]

(Preparation of Emulsion) A silver halide emulsion was prepared as follows. (1 liquid) H ₂ O 1000 ml NaCl 3.3 g Lime-treated gelatin 32 g (2 liquid) Sulfuric acid (1N) 24 ml (3 liquid) N, N′-dimethylimidazolidine-2-thione (1% aqueous solution) 3 ml (4 liquid) ) NaCl 10.7g H ₂ O were added 200 ml (5 fluid) AgNO ₃ 32.00g H ₂ O were added 200 ml (6 solution) was added to NaCl 32.1g H ₂ O 420ml (7 solution) AgNO ₃ 96 g H ₂ O were added 420 ml (8 fluid) was added NaCl 10.7g H ₂ O 140ml (9 solution) was added AgNO ₃ 32g H ₂ O 140ml

(Liquid 1) was heated to 74 ° C., and (2nd liquid) and (3rd liquid) were added. After that, (4 solution) and (5 solution) were added at the same time while spending 14 minutes while stirring vigorously.
After 6 minutes, (6 solution) and (7 solution) were added simultaneously spending 11 minutes while stirring vigorously. After 5 minutes (8 solution) and (9
(Liquid) was added simultaneously with vigorous stirring over 5 minutes, and 5 minutes after the addition, the temperature was lowered to desalt. Water and dispersed gelatin were added, and the pH was adjusted to 6.2. At 58 ° C., a silver bromide fine grain emulsion (average grain size 0.04 μm) corresponding to 0.8 mol% based on silver halide was added. , Silver chloride host grains have silver bromide-rich regions formed thereon, and have an average grain size of 0.
A monodisperse cubic silver chlorobromide emulsion having a thickness of 85 μ and a coefficient of variation (standard deviation divided by average grain size: s / d) of 0.08 was obtained. Optimal chemical sensitization was carried out by adding triethylthiourea to each emulsion at 58 ° C. The obtained emulsion was designated as A-1. A
Emulsion A-2 was prepared in the same manner as in A-1, except that potassium hexacyanoferrate (II) was added to Solution 8 in the amount of 1 × 10 ⁻⁴ mol per 1 mol of silver halide. Further, an emulsion having a different grain size is prepared in the same manner as Emulsion A-1 except that the temperature at the time of forming silver halide grains is changed, and a blue-sensitizing dye, a green-sensitizing dye or a red-sensitizing dye is used. Thus, each photosensitive emulsion used below was prepared.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0066]

[Chemical 1] (2.5 × 10 ⁻⁴ mol per mol of silver halide)

Green-sensitive emulsion layer

[0068]

[Chemical 2] (Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × for small size emulsion)
10 ^-4 mol) and

[0069]

[Chemical 3] (7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × for small size emulsion per mol of silver halide)
10 ^-4 mol)

Red-sensitive emulsion layer

[0071]

[Chemical 4] (1.0 × 10 ⁻⁴ mol per mol of silver halide)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0073]

[Chemical 5] After the corona discharge treatment was applied to the surface of the paper support (C) laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constitutional layers were further applied to form a layer constitution shown below. A multilayer color printing paper (101) was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for first layer 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, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. This emulsified dispersion A and the above-mentioned silver chlorobromide emulsion A-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50.0, respectively.
It was added to be mg / m ² . Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, in an amount of 8.5 × 10 ^-5 mol and 7. 7
× 10 ^-4 mol and 2.5 × 10 ^-4 mol were added. Further, 4-hydroxy-6- is added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 mol, respectively, per mol of silver halide.
^-4 mol was added. Also, to prevent irritation,
The following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0076]

[Chemical 6]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (C)

AH layer (antihalation layer) A gelatin layer having the following composition using the colloidal silver dispersion (coating solution IV) shown above. Colloidal silver 0.10 Gelatin 0.30

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A-1 0.25 Gelatin 1.30 Yellow coupler (ExY) 0.74 Color image stabilizer (Cpd-1) 0.08 colors Image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.06 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1.30 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag mol The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride in each size emulsion) 0 .12 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.15 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 1.00 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, emulsion C with average grain size 0.50 μm, grain size distribution variation coefficient 0.08, AgBr 0.8 mol% to silver chloride) 0.22 gelatin 0.95 cyan coupler (ExC) 0.33 ultraviolet absorber (UV-2) 0.20 color image stabilizer (Cpd-1) ) 0.33 color image stabilizer (Cpd-6) 0.01 color image stabilizer (Cpd-8) 0.01 color image stabilizer (Cpd-9) 0.01 color image stabilizer (Cpd-10) 0 .01 color image stabilizer (Cpd-11) 0.01 solvent (S olv-1) 0.01 solvent (Solv-6) 0.22

Sixth Layer (UV Absorbing Layer) Gelatin 0.50 UV Absorber (UV-1) 0.35 Color Image Stabilizer (Cpd-5) 0.02 Color Image Stabilizer (Cpd-12) 0.15

The compounds used for preparing the above-mentioned sample 101 are described below.

[0085]

[Chemical 7]

[0086]

[Chemical 8]

[0087]

[Chemical 9]

[0088]

[Chemical 10]

Samples 102 to 136 were prepared in the same manner as in Sample 101, except that the paper support, the coating liquid for the antihalation layer, and the emulsion for the blue-sensitive layer were as shown in Table 7.

[0090]

[Table 7]

A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for each sample which had been stored for 1 day at room temperature after coating, and for sensitometry through a blue filter. Gradation exposure. The exposure at this time
The exposure time was 1/10 seconds and the exposure amount was 250 CMS. The exposed sample was treated using the following treatment process and treatment liquid composition.

Color development processing (Processing step) (Temperature) (Time) Color development 35 ° C. 45 seconds Bleach fixing 35 ° C. 45 seconds Water washing 28 to 35 ° C. 95 seconds

Color developer Triethanolamine 8.12 g N, N-diethylhydroxylamine 4.93 g Fluorescent 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. 36g Add water 1000ml pH 10.05

Bleach-fixing solution Ammonium thiosulfate (54 wt%) 103.0 ml NH ₄ [EDTA.Fe] 54.10 mg Ammonium chloride 5.4 g Sodium sulfite 16.71 g Glacial acetic acid 8.61 1000 ml pH was added at pH 5.44

The residual silver amount of the treated sample was measured by fluorescent X-ray at the maximum density part. In addition, in order to examine the stability of the latent image, the same exposure as above was performed using the sample that had been applied for 2 weeks at 50 ° C., and the same treatment as described above was performed 5 ″, 30 ″ and 2 hours after exposure. I went. The reflection density of the processed sample thus prepared was measured to obtain a characteristic curve. The sensitivity S was defined as the reciprocal of the exposure amount that gives a density 1.0 higher than the fog density. For the change in latent image stability, the value derived by the following mathematical formula was used. ΔS _S = S _10M −S _30S ΔS _l = S _2h −S _30S Here, the letter at the lower right of S is the time from exposure to development.
0S represents 30 seconds, 10M represents 10 minutes, and 2h represents 2 hours. Short-term latent image stability is ΔS _S , long-term latent image stability is ΔS _l
The latent image stability is better as the value of each is closer to zero. Table 8 shows the residual silver amount of each sample, the yellow fog change and the latent image stability after the processing of the sample aged at 50 ° C. for 2 weeks with respect to the sample aged 1 day at room temperature after coating.

[0096]

[Table 8]

From the results, it can be seen that only the structure of the present invention has a small amount of residual silver and is excellent in latent image stability. That is, it can be seen that the residual silver amount is remarkably reduced in the samples (Samples 113 to 136) in which the antihalation layer contains tabular silver particles having a thickness of 0.02 μm or less. But,
Among these samples in which the residual silver amount was decreased, in the samples (133 to 136) in which the base paper pH of the paper support was higher than 9, the yellow density of the unexposed portion was high and the base paper pH was 5
It can be seen that the latent image stability is deteriorated in the samples (113 to 120) below. It is clear that only the constitution of the present invention has a small amount of residual silver and is excellent in latent image stability.

Example 2 In the preparation of Emulsions A-1 and A-2, the first iridium (III) chloride ion was contained in silver bromide fine grains in an amount of 1 × 10 ^-6 mol per mol of silver halide. Only that,
Emulsions A-3 and A-4 were prepared in the same manner as emulsions A-1 and A-2, respectively. Sample (201) to Sample (201) to Sample (124) except that the emulsion A-1 for the blue sensitive layer of Sample (124) was replaced with A-2, A-3 and A-4.
(203) was created. Samples (124), (201)-
Table 9 shows the addition amounts of iron ions and iridium ions in Emulsions A-1 to A-4 contained in (204).

[0099]

[Table 9]

Samples (124), (201) to (203)
The same evaluation as in Example 1 was performed. The results are shown in Table 10.

[0101]

[Table 10]

As is clear from Table 10, the sample containing the periodic group VIII ion in the silver halide grains (2
In 01) to (203), the latent image stability is further improved. Among them, it can be seen that the latent image stability is remarkably improved in the sample (203) in which the silver halide grains contain both iron ions and iridium ions.

Example 3 Photosensitive materials 101 to 136, 20 produced in Examples 1 and 2
With respect to Nos. 1 to 203, the same evaluation as in Example 1 was performed except that the following exposure and treatment were performed. The results obtained are from Example 1,
Same as 2. (Exposure) YAG solid-state laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source is KNbO ₃ SHG
A YVO ₄ solid-state laser (oscillation wavelength: 10 nm, 473 nm wavelength-converted by a crystal, semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm) was used as an excitation light source.
The wavelength is 532 nm extracted from the KTP SHG crystal of 64 nm) and taken out by AlGaInP (oscillation wavelength of about 6 nm).
80 nm: Toshiba type No. TOLD9211) was used. The laser light is an apparatus capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. With this device,
The relationship D-logE between the density (D) of the photosensitive material and the light amount (E) was obtained by changing the light amount. At this time, the laser light of three wavelengths was modulated in light quantity using an external modulator to control the exposure quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature.

Treatment process Temperature Time Replenishment amount Tank capacity Color development 35 ° C. 45 seconds 161 ml 17 liters Bleach fixing 35 ° C. 45 seconds 215 ml 17 liters Stable (1) 35 ° C. 20 seconds −10 liters Stable (2) 35 ° C. 20 seconds −10 liters Stable (3) 35 ° C. for 20 seconds −10 liters Stable (4) 35 ° C. for 20 seconds 248 ml Dry 80 ° C. for 60 seconds * Replenishment amount per 1 m ² of light-sensitive material * Rinse from (4) to (1) 4-tank countercurrent method

The composition of each processing liquid is as follows. [Color developer] Tank solution Replenisher Water 800 ml 800 ml Lithium polystyrene sulfonate solution (30%) 0.25 ml 0.25 ml 1-Hydroxyethylidene-1,1-diphosphonic acid solution (60%) 0.8 ml 0.8 ml Lithium sulfate ( Anhydrous) 2.7 g 2.7 g Triethanolamine 8.0 g 8.0 g Potassium chloride 1.8 g-Potassium bromide 0.03 g 0.025 g Diethylhydroxylamine 4.6 g 7.2 g Glycine 5.2 g 8.1 g Threonine 4.1 g 6.4 g Potassium carbonate 27 g 27 g Potassium sulfite 0.1 g 0.2 g N-ethyl-N- (β-methanesulfonamidoamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 4.5 g 7.3 g Fluorescent sensitizer (4,4′- Diaminostilbene type) 2.0 g 3.0 g Water added 1000 ml 1000 ml pH (adjusted with potassium hydroxide and sulfuric acid) 10.12 10.70

[Bleach-fixing solution] (tank solution and replenisher are the same) 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 Ammonium chloride 10.7 g Glacial acetic acid 9 g Water added 1000 ml pH (25 ° C) (adjusted with acetic acid and ammonia) 5.40

[Stabilizer] (tank solution and replenisher are the same) 1,2-benzisothiazolin-3-one 0.02 g polyvinylpyrrolidone 0.05 g Water was added to 1000 ml pH 7.0

[0108]

The silver halide color photographic light-sensitive material of the present invention has an antihalation layer containing tabular silver particles, is excellent in rapid processability and desilvering property, and has elapsed time after the production of the light-sensitive material. Even when the latent image is stable. Further, according to the image forming method of the present invention, a color photograph having excellent image quality can be quickly produced.
In addition, it can be stably obtained, and is particularly suitable as a method for carrying out the method in a commercial developing laboratory.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one light-sensitive silver halide emulsion layer and at least one antihalation layer on a paper support, wherein the silver halide emulsion layer contains silver chloride. 90 mol% or more of silver chlorobromide particles or silver chloride particles, the antihalation layer contains tabular silver particles having a thickness of about 0.02 μm or less, and the paper support has a pH of 5 or more and 9 or less. A silver halide color photographic light-sensitive material characterized by comprising the base paper of 2. The silver halide grain contains a periodical periodicity
The silver halide color photographic light-sensitive material according to claim 1, containing at least one selected from Group VIII metal ions. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide grains contain iron ions and iridium ions.