JP2529570B2 - Silver halide photographic emulsion with improved coating solution retention - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic emulsion, more specifically, it has a silver halide emulsion layer containing silver halide grains having a silver chloride composition of 80 mol% or more. A silver halide photographic emulsion used for producing a silver halide color photographic light-sensitive material in which the stagnation of a coating solution is improved in producing a silver halide color photographic light-sensitive material and the sensitivity is uniform in the same coating lot. Regarding

[Prior art]

Usually, in the method of forming a dye image using a silver halide color photographic light-sensitive material, after the imagewise exposure, the oxidized p
A phenylenediamine based color developing agent is reacted with a dye image-forming coupler to form a dye image. In this method, the color reproduction method based on the ordinary color reduction method is applied, and red, green,
Cyan, magenta, and yellow dyes are formed on the respective photosensitive layers corresponding to and blue. recent years,
In forming such a dye image, in order to shorten the development processing time, the high temperature development processing and the processing steps are generally omitted. In particular, in order to shorten the development processing time by high temperature development processing,
Increasing the developing speed in color development is extremely important. The development speed in color development is affected from two aspects. One is a silver halide color photographic light-sensitive material, and the other is a color developing solution.

In the former case, the shape, size, and composition of the grains of the photosensitive silver halide emulsion used have a great influence on the development speed, and in the latter case, they affect the conditions of the color developing solution, especially the type of development inhibitor. It has been found that silver chloride grains, in particular, are susceptible to susceptibility and, in particular, exhibit a significantly higher development rate under certain conditions.

The silver halide color photographic light-sensitive material is generally composed of silver chloride (meaning that it has a silver chloride composition of 80 mol% or more. The same applies hereinafter). Instead of commonly used bromides such as potassium bromide and sodium bromide (bromide ion acts as an antifoggant), chlorides such as potassium chloride and sodium chloride and / or specific organic development inhibitors such as adenine and guanine, Using a 5-membered, 6-membered or condensed nitrogen-containing heterocyclic compound such as benzimidazole, benzotriazole and derivatives thereof, an extremely high developing speed can be obtained while maintaining good photographic performance. Especially, adenine and water-soluble chlorides are particularly preferable.

Therefore, a silver halide color photographic material having a silver halide emulsion layer containing silver halide grains substantially consisting of silver chloride contains a water-soluble chloride or adenine as a development inhibitor, and is a p-phenylenediamine type. Processing with a color developer containing a color developing agent can significantly reduce the development time compared to conventional color development, which in turn leads to downsizing of automatic processors and reduction of development replenisher in rapid development processing. Therefore, it has great practical value such as reduction of pollution load. (For example, JP-A-58-95345 and JP-A-60-19140
No. When producing a silver halide color photographic light-sensitive material using such a silver halide emulsion containing silver chloride as a main component, the silver halide emulsion containing 80 mol% or more of silver chloride is usually used. When a hydrophobic coupler is mixed with a coupler dispersion liquid which is emulsified and dispersed using a high boiling point organic solvent and becomes stagnant, there is a drawback that the sensitivity is likely to be lowered particularly during the stagnant state of the coating liquid. The decrease in sensitivity during the stagnation of the coating solution is considered to be due to the desorption of the sensitizing dye used in the silver halide emulsion mainly composed of silver chloride from the silver halide grains, but such a defect was stabilized. It is extremely difficult to produce a high quality silver halide color photographic light-sensitive material, and its improvement is strongly desired.

Conventionally, in order to prevent sensitivity fluctuation during stagnation of the coating solution, the sensitizing dye is limited to a specific one, or JP-A-59-28783, 59-5238, and 59-9653. No. and No.
Add a water-soluble halide to the coating solution as described in No. 60-80841. Alternatively, as described in JP-A-58-7629, a technique such as adding a sensitizing dye to a coating solution may be used to use a silver halide emulsion having 80 mol% or more of silver chloride and to make it hydrophobic. It was difficult to say that a sufficient level was obtained when a coating solution using an emulsion dispersion of a functional coupler was used.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains having a silver chloride composition of 80 mol% or more. It is an object of the present invention to provide a silver halide photographic emulsion which is used for producing a silver halide color photographic light-sensitive material in which a coating solution stagnation property is improved and a sensitivity is uniform in the same coating lot.

[Structure of Invention]

The above object of the present invention is to chemically ripen high silver chloride-containing silver halide grains having a silver chloride content of 80 mol% or more, and 0.001 to 0.00 mol per mol of the silver halide grains.
It is achieved by a silver halide photographic emulsion having an improved stagnation property of a coating solution, which is characterized by performing chemical ripening by forming 8 mol of silver bromide.

The high silver chloride-containing silver halide grains of the present invention contain silver chloride.
The silver halide grains contain 80 mol% or more, preferably the silver chloride content is 95 mol% or more, and most preferably 99 mol% to 99.9 mol%.

This silver halide emulsion may contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride, but the silver bromide content is 20 mol% or less, preferably 5 mol% or less.
Most preferably, it is 1 mol% or less, and when silver iodide is present, it is usually 1 mol% or less, preferably 0.5 mol% or less, and most preferably 0%. Such a silver halide grain having a silver chloride composition of 80 mol% or more according to the present invention is contained in a weight percentage of all silver halide grains in a silver halide emulsion layer containing the silver halide grain.
It is preferably 80% or more, more preferably 90% or more, and most preferably 100% of the light-sensitive silver halide emulsion is the high silver chloride emulsion.

This silver halide may be produced by any of the ammonia method, the neutral method, the acidic method, etc., or by the simultaneous mixing method, the forward mixing method, the back mixing method, the conversion method, etc. It may be one. A silver halide emulsion formed by a neutral method or an acidic method is preferable because it has high sensitivity, low fog, and excellent pressure resistance and celite property.

When adding a water-soluble silver salt and a water-soluble halide, the simultaneous mixing method is particularly preferable, and pA is more preferable.
g is preferably added while controlling, and in this case, it is not always necessary to control at the same pAg over the entire period of silver halide grain formation, and in the range of pAg3 to 9, the critical growth rate of silver halide grains, It is possible to arbitrarily change the temperature in consideration of the temperature of the additive liquid, the mixing temperature, the method of mixing (the so-called premix, the shape of the stirrer, the shape of the mixing vessel, etc.).

When the silver bromide composition has a silver bromide composition, the crystal structure of the high silver chloride silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. . The silver halide may be a surface latent image type which forms a latent image mainly on the surface, or an internal latent image type which forms a latent image mainly inside the grain.

In the silver halide emulsion of the present invention, a metal salt such as lead, cadmium, iridium or rhodium can be appropriately used during grain formation.

The silver halide emulsion of the present invention is preferably a cubic crystal, and the grain size of silver halide is preferably 0.2 to 1.0 μm, more preferably 0.3 to 0.8 μm.

The silver halide emulsion of the present invention needs to be subjected to chemical ripening after removing unnecessary salts after the formation of silver halide grains to enhance the surface sensitivity. When chemically sensitized, the silver halide 1
It is necessary to form silver bromide in an amount of 0.001 to 0.08 mol, preferably 0.01 to 0.06 mol per mol for chemical ripening.

When the amount of silver bromide formed during the chemical ripening is less than 0.001 mol per mol of silver halide in the silver halide grains having a high silver chloride content, the effect of the present invention, that is, the sensitivity when the coating solution is stagnant, is reduced. The effect of prevention cannot be obtained, and in the case where the content is more than 0.08 mol, the maximum concentration in the case of performing chemical aging to the point of maximum sensitivity is lowered.

This silver bromide may be formed by separately adding a water-soluble silver salt and a water-soluble bromide to the above-mentioned high silver chloride-containing silver halide emulsion, and further, in advance, fine silver bromide particles or silver chlorobromide. Fine grains may be formed in advance, and the fine grain silver chloride (or silver chlorobromide) emulsion may be added to the high silver chloride-containing silver halide emulsion. Further, the water-soluble bromide may be added to the high silver chloride-containing silver halide emulsion. In addition, silver bromide may be formed by causing conversion.

In this case, when the unchemically sensitized emulsion is silver chloride,
Silver bromide within the above range is particularly preferable, but the unchemically sensitized emulsion contains 0.001 silver bromide per mol of silver halide in the emulsion.
In the case of a silver chlorobromide emulsion containing more than 1 mol, the silver bromide added during chemical ripening is in the range of 0.001 mol to 0.02 mol with respect to 1 mol of silver halide of the silver chlorobromide emulsion. Is preferred.

 Hereinafter, the method for forming silver bromide will be described in detail.

When silver bromide is added to a high-silver chloride emulsion, a water-soluble silver salt, (preferably silver nitrate) and a water-soluble bromide (preferably potassium bromide or sodium bromide) may be added at the same time. , Or the silver salt may be added in advance, and then the bromide may be added, or vice versa. At this time, it is possible to use a part of the water-soluble bromide together with a water-soluble bromide or a water-soluble iodide within the range not impairing the effects of the present invention, but the water-soluble chloride is preferably water-soluble silver. 50 mol% or less with respect to salt,
The water-soluble iodide content is 2 mol% or less, preferably 0.5 mol% or less, based on the water-soluble silver salt.

Water-soluble silver salt and water-soluble bromide to be added are in molar ratio
It is used between 1: 0.8 and 1:10, preferably between 1: 1 and 1: 6.

On the other hand, when silver bromide is formed by using fine grain silver bromide, the addition timing may be similar to that of using the above water-soluble bromide and silver salt. Alternatively, silver iodide may be contained as a component constituting fine grain silver halide. The ratio is the same as when the above water-soluble bromide and water-soluble silver salt are used.

The silver bromide fine particles used have an average particle diameter of 0.08 μm to 0.
30 μm, preferably about 0.1 μm to 0.25 μm
belongs to.

Furthermore, when silver bromide is formed by conversion by adding a water-soluble bromide to a silver halide emulsion containing a high amount of silver chloride, it can be achieved by simply adding the water-soluble bromide. It is also possible to add a neutral chloride together.

The water-soluble bromide used is in the range of 0.001 mol to 0.08 mol, and preferably 0.002 mol to 0.02 mol, per mol of the high silver chloride silver halide emulsion.

The time for forming silver bromide in the present invention may be at the start of chemical ripening (that is, when a chemical sensitizer is added), before or after that, and any time can be used before the completion of chemical ripening. It may be time. Preferably 90% of the total time of chemical ripening (more preferably 50
%) Should be added before the lapse of%). Further, when it is formed before the start of chemical ripening, it may be performed after the desalting step subsequent to the formation of silver halide grains is completed, but preferably within 10 minutes, more preferably 5 minutes after the start of chemical ripening. It is preferably formed within.

The compound preferably used as the chemical sensitizer in the present invention is an unstable sulfur compound such as sodium thiosulfate, but in addition to the unstable sulfur compound, a noble metal salt such as ruthenium, rhodium, palladium, iridium, platinum and gold. (For example, ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium chloroaurate, etc.), noble metal sensitization, active gelatin, sulfur sensitization, selenium sensitization with selenium compounds, stannous salt, polyamines , Thiourea dioxide, etc. and low pA
Reduction sensitization under g can be performed.

Further, these silver halide emulsions can be spectrally sensitized by using various sensitizing dyes in order to impart photosensitivity in a desired light-sensitive wavelength region. Preferred sensitizing dyes include, for example, U.S. Pat.Nos. 1,939,201 and 2,072,908,
No. 2,739,149, No. 2,213,995, No. 2,493,748
No. 2,519,001, West German Patent No. 929,080, and British Patent No. 505,979, the cyanine dyes, merocyanine dyes, or complex cyanine dyes can be used alone or in combination of two or more. . Such various spectral sensitizing dyes are used for purposes other than their original purpose, for example, prevention of fogging, prevention of deterioration of photographic performance due to storage of silver chloride color photographic light-sensitive materials, development adjustment (eg gradation control, etc.). It can also be used for such purposes.

The coating solution containing the silver halide emulsion containing 80 mol% or more of silver chloride according to the present invention is particularly effective under the relatively diluted conditions. In particular, the effect of the present invention is particularly large when the silver halide emulsion content in the coating solution is 0.2 mol or less, preferably 0.15 mol or less.

If the present invention is compared with the conventionally known technique of forming or adding silver halide during chemical ripening, JP-B Nos. 57-25825 and 57-25828 disclose that a silver halide containing a high silver bromide content is used. A technique for chemically ripening a silver emulsion (silver bromide composition: 50 mol% or more) in the presence of fine grain silver chloride is disclosed, but the present invention has a technically different constitution from this. Moreover, as for the effect, the above-mentioned invention is required to improve the low fog, the storability of the light-sensitive material and the reciprocity law failure characteristic, and the effect of the present invention is not mentioned at all. Furthermore, Japanese Patent Publication No. 58-3531 discloses that silver bromide or silver iodobromide is added during chemical ripening, and here also, a silver halide emulsion having a high silver bromide content is used as a silver halide emulsion. Is a technique which is preferably used, and is different from the high silver chloride-containing silver halide emulsion of the present invention. Moreover, the purpose of the invention is to stabilize the latent image. Is clearly different.

The silver halide emulsion of the present invention contains, during the chemical ripening, at the end of the chemical ripening, for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage, or during photographic processing, or keeping the photographic performance stable, and After the completion of the chemical ripening, a compound known as an antifoggant or a stabilizer in the photographic art can be added by the time of coating on the silver halide emulsion.

Antifoggants and stabilizers include U.S. Patent No. 2,713,54
No. 1, 2,743,180, pentazaindenes described in 2,743,181, U.S. Pat.Nos. 2,716,062, 2,4
No. 44,607, No. 2,444,605, No. 2,756,147, No. 2,
No. 835,581, No. 2,852,375, tetrazaindenes described in Research Disclosure 14851, triazaindenes described in US Pat. No. 2,772,164, and JP-A-57-211142. Azaindenes such as the polymerized azaindenes described;
U.S. Pat.Nos. 2,131,038, 3342,596 and 3,954,4
Thiazolium salts described in US Pat. No. 3,148,06
Pyrylium salt described in No. 7 and Japanese Patent Publication No. 40-40665
Quaternary onium salts such as phosphonium salts described in No.
U.S. Pat.Nos. 2,403,927, 3,266,897, 3,708,
303, JP-A-55-135835, mercaptotetrazoles described in JP-A-59-71047, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat.No. 2,824,001, U.S. Pat. 3,39
Mercaptobenzthiazoles described in 7,987,
Mercaptobenzimidazoles, U.S. Pat.No. 2,843,49
Mercapto-substituted dicyclic compounds such as mercapto oxadiazoles described in No. 1 and mercapto thiadiazoles described in US Pat. No. 3,364,028; US Pat.
3,236,652, catechols described in JP-B-43-10256, resorcins described in JP-B-56-44413,
And polyhydroxybenzenes such as gallic acid esters described in JP-B-43-4133; tetrazoles described in West German Patent No. 1,189,380, triazoles described in U.S. Patent No. 3,157,509, U.S. Patent No. 2,704,721. Benzene triazoles described in U.S. Pat.
Urazols described in 7,135, U.S. Pat.
Pyrazoles described in 67, U.S. Pat.No. 2,271,229
Indazoles, and azoles such as polymerized benztriazoles described in JP-A-59-90844 and pyrimidines described in U.S. Pat.No. 3,161,515, described in U.S. Pat.No. 2,751,297. 3-pyrazolidones and heterocyclic compounds such as polymerized pyrrolidone described in US Pat. No. 3,021,213, that is, polyvinylpyrrolidones; JP-A-54-130929, JP-A-59-137945,
14,0445, British Patent 1,356,142, U.S. Patent 3,575,
Various inhibitor precursors described in 699 and 3,649,267; sulfinic acid and sulfonic acid derivatives described in U.S. Pat. No. 3,047,393; U.S. Pat. No. 2,566,263
No. 2,839,405, 2,488,709, 2,728,66
Inorganic salts listed in No. 3 are available.

Although gelatin is advantageously used as the binder (or protective colloid) of the silver halide emulsion of the present invention, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, and cellulose derivatives. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or copolymer can also be used.

Gelatin includes lime-treated gelatin, acid-treated gelatin, Bulletin of Society of Science of Photography of Japan (Bull.So
C.Sci.Phot.Japan) No. 16, page 30 (1966), oxygen-treated gelatin may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.
Specific examples thereof are U.S. Patents 2,614,928 and 3,132,945.
No. 3,186,846, No. 3,312,553, British Patent No. 86
1,414, 1,033,189, 1,005,784, Japanese Patent Publication 4
It is described in No. 2-26845.

The protein is preferably albumin, casein, the cellulose derivative is hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, and the sugar derivative is sodium alginate and a starch derivative.

As the graft polymer of a polymer with gelatin, a homopolymer or a copolymer of vinyl monomers such as acrylic acid, methacrylic acid, their derivatives such as esters and amides, acrylonitrile and styrene can be grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are U.S. Pat.
No. 763,625, No. 2,831,767, No. 2,956,884.

Typical synthetic hydrophilic polymer substances are polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N.
-Vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole and the like single or copolymers, for example West German patent application (OLS) 2,312,708, U.S. Patent No. 3,620,751, the same 3,879,205 and Japanese Patent Publication No. 43-7561.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners that crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardening agent can be added in such an amount that the light-sensitive material can be hardened to such an extent that the hardening agent does not need to be added to the processing solution, but it is also possible to add the hardening agent to the processing solution.

As a hardener, aldehyde-based, aziridine-based (e.g., PB Report, 19,921, U.S. Patent Nos. 2,950,197, 2,964,404, 2,983,611, and 3,271,175 each specification, JP-B-46-40898). , Those described in JP-A No. 50-91315), isoxazole-based (for example, those described in US Pat. No. 331,609), epoxy-based (for example, US Pat. No. 3,047,394, West German patent). 1,085,6
63, each specification of British Patent No. 1,033,518, Japanese Patent Publication No. 48-35
No. 495), vinyl sulfone type (for example, PB Report 19,920, West German Patent No. 1,100,942, the same).
No. 2,337,412, No. 2,545,722, No. 2,635,518, No. 2,742,308, No. 2,749,260, and British Patent No. 1,251,09.
No. 1, Japanese Patent Application No. 45-54236, No. 48-110996, U.S. Pat.
539,644, those described in each specification of 3,490,911), acryloyl series (for example, Japanese Patent Application No. 48-27949,
U.S. Pat. No. 3,640,720), carbodiimide-based compounds (e.g., U.S. Pat.Nos. 2,938,892, 4,043,818, 4,061,499, Japanese Patent Publication No. 46).
-38715, Japanese Patent Application No. 49-15095), triazine (for example, West German Patent 2,410,973).
No. 2,553,915, each specification of U.S. Pat.No. 3,325,287, those described in JP-A-52-12722), polymer type (for example, U.S. Pat.No. 822,061, U.S. Pat.No. 3,623,878).
Nos. 3,396,029, each specification of No. 3,226,234, those described in JP-B Nos. 47-18578, 47-18579 and 47-48896) Other maleimides, acetylenes, methane Sulfonate-based and (N-methylol-based) hardeners can be used alone or in combination. Examples of useful combination techniques include West German Patent Nos. 2,447,587, 2,505,746, 2,514,245, and U.S. Patent 4,047,95.
No. 7, No. 3,832,181, each No. 3,840,370 specifications,
JP-A-48-43319, JP-A-50-63062, JP-A-52-127329,
The combinations described in Japanese Patent Publication No. 48-32364 are listed.

When color development processing is performed using the silver halide emulsion of the present invention, a coupling reaction is formed with an oxidation product of an aromatic primary amine developer (eg, p-phenylenediamine derivative or aminophenol derivative) to form a dye. Dye-forming couplers are used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers are 1
It is necessary to reduce four silver ions in order to form a dye of the molecule. It may be either four equivalents or only two silver ions need to be reduced. . Dye-forming couplers include development accelerators, bleaching accelerators, developers, silver halide emulsions, toning agents, hardeners, fog agents, antifoggants, and chemical sensitizers by coupling with an oxidized product of a developing agent. , Spectral sensitizers, and compounds that release photographically useful fragments such as desensitizers. These dye-forming couplers are color couplers that have the effect of color correction, or DI that releases a development inhibitor with development and improves image sharpness and image graininess.
An R coupler may be used in combination. At this time, the DIR coupler is preferably the same type of dye formed from the dye-forming coupler used in the same emulsion layer as the dye formed from the coupler, but when the color turbidity is not conspicuous, a different type of DIR coupler is used. Those that form a dye may be used. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as a colorless compound is formed by a coupling reaction with an oxidized product of a developing agent may be used in combination with or in combination with the DIR coupler.

The DIR coupler and the DIR compound used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and within the group which is released by the coupling reaction. (A timing DIR coupler and a timing DIR compound) in which an inhibitor is released by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, or the like. Further, as the inhibitor, those having a diffusivity after release and those having a low diffusivity can be used alone or in combination depending on the application. A colorless coupler that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent No. 1,077,874,
Tokiko Sho 45-40757, JP-A 47-1031, 47-26133,
48-94432, 50-87650, 51-3631, 52-1152
No. 19, No. 54-99433, No. 54-133329, No. 56-30127,
U.S. Pat.Nos. 2,875,057, 3,253,924, 3,265,
No. 506, No. 3,408,194, No. 3,551,155, No. 3,55
No. 1,156, No. 3,664,841, No. 3,725,072, No. 3,7
No. 30,722, No. 3,891,445, No. 3,900,483, No. 3,
929,484, 3,933,500, 3,973,968, and
No. 3,990,896, No. 4,012,259, No. 4,022,620, No. 4,029,508, No. 4,057,432, No. 4,106,942,
No. 4,133,958, No. 4,269,936, No. 4,286,053
No. 4,304,845, 4,314,023, 4,336,32
No. 7, No. 4,356,258, No. 4,386,155, No. 4,401,7
No. 52, etc.

Examples of magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
Pyrazoloazole couplers and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used include Japanese Patent Application No. 58-164882.
No. 58, No. 58-167326, No. 58-206321, No. 58-214863,
58-217339, 59-24653, JP-B-40-6031, 40
-6035, 45-40757, 47-27411, 49-37854
No. 50-13041, No. 51-26541, No. 51-37646,
51-105820, 52-42121, 53-123129, 53-1
No. 25835, No. 53-129035, No. 54-48540, No. 56-29236
No. 56, No. 56-75648, No. 57-17950, No. 57-35858, No. 57
-146251, 59-99437, British Patent 1,252,418, U.S. Patents 2,600,788, 3,005,712, 3,062,65
No. 3, No. 3,127,269, No. 3,214,437, No. 3,253,9
No. 24, No. 3,311,476, No. 3,419,391, No. 3,519,
No. 429, No. 3,558,319, No. 3,582,319, No. 3,58
2,322, 3,615,506, 3,658,544, 3,7
05,896, 3,725,067, 3,758,309, 3,
823,156, 3,834,908, 3,891,445, and
No. 3,907,571, No. 3,926,631, No. 3,928,044, No. 3,935,015, No. 3,960,571, No. 4,076,533,
No. 4,133,686, No. 4,237,217, No. 4,241,168
No. 4, No. 4,264,723, No. 4,301,235, No. 4,310,62
It is described in No. 3 etc.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used are British Patent Nos. 1,038,331 and 1,543,040, Japanese Patent Publication No. 48-36894,
JP-A-48-59838, 50-137137, 51-146828, 53-105226, 54-115230, 56-29235, 56
-104333, 56-126833, 57-133650, 57-1555
No. 38, No. 57-204545, No. 58-118643, No. 59-31953,
59-31954, 59-59656, 59-124341, 59-16
6956, U.S. Pat.Nos. 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,698,794,
No. 2,772,162, No. 2,801,171, No. 2,895,826
No. 3, No. 3,253,924, No. 3,311,476, No. 3,458,31
No. 5, No. 3,476,563, No. 3,591,383, No. 3,737,3
No. 16, No. 3,758,308, No. 3,767,411, No. 3,790,
No. 384, No. 3,880,661, No. 3,926,634, No. 4,00
No. 4,929, No. 4,009,035, No. 4,012,258, No. 4,0
52,212, 4,124,396, 4,134,766, 4,
No. 138,258, No. 4,146,396, No. 4,149,886, No. 4
4,178,183, 4,205,990, 4,254,212, 4,264,722, 4,288,532, 4,296,199,
No. 4,296,200, No. 4,299,914, No. 4,333,999
No., No. 4,334,011, No. 4,386.155, equivalent 4,401,75
No. 2 and No. 4,427,767, etc.

In addition to the above compounds, various photographic additives can be added to the silver halide photographic light-sensitive material containing the silver halide emulsion of the present invention.

As such an example, for example, an ultraviolet absorber (for example, a benzophenone compound, a benzotriazole compound, etc.), a development accelerator (for example, a 1-aryl-3-pyrazolidone compound), a surfactant (for example, an alkylnaphthalene sulfonate). , Alkyl succinate sulfonates, itaconic acid salts, polyalkylene oxide compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxonol compounds,
Anthraquinone compounds and triphenylmethane compounds, etc.), film physical property improving agents (eg glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin etc.), color turbidity preventing agents (diffusion-resistant hydroquinone compounds etc.), Dye image stabilizers (eg hydroquinone derivatives, gallic acid derivatives, phenol compounds, hydroxychroman compounds, polyalkylpiperidine compounds, aromatic amine compounds, etc.), water-soluble or oil-soluble fluorescent whitening agents, ground color adjustment Agents (oil-soluble coloring dyes, etc.) and the like.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color fogging inhibitors, ultraviolet absorbers, fluorescent brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid Various methods such as a dispersion method, a latex dispersion method, and an oil-in-water type emulsification dispersion method can be used, and these can be appropriately selected according to the chemical structure of a hydrophobic compound such as a coupler. The oil-in-water emulsion dispersion method can be applied with various methods of dispersing hydrophobic additives such as couplers, and usually has a low boiling point and / or a water-soluble organic solvent having a boiling point of about 150 ° C. or higher as necessary. Emulsify by using a dispersing agent such as a stirrer, homogenizer, colloid mill, flowgit mixer, or ultrasonic device, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion liquid or dispersion.

The ratio of high boiling organic solvent to low boiling organic solvent is 1: 0.1 to
It is preferably 1:50, more preferably 1: 1 to 1:20.

Organic compounds having a boiling point of 150 ° C or higher such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesic acid esters, etc. which do not react with the oxidized form of the developing agent as high-boiling oils A solvent is used.

As the high-boiling point organic solvent that can be used, U.S. Patent Nos. 2,322,027, 2,533,514, and 2,835,579.
No. 3,287,134, No. 2,353,262, No. 2,852,38
No. 8, No. 3,554,755, No. 3,676,137, No. 3,676,1
No. 42, No. 3,700,454, No. 3,748,141, No. 3,779,
No. 765, No. 3,837,863, British Patent No. 958,441, No.
1,222,753, OLS 2,538,889, JP-A-47-1031, 49
-90523, 50-23823, 51-26037, 51-27921
No. 51, No. 51-27922, No. 51-26035, No. 51-26036, No. 50
-62632, 53-1520, 53-1521, 53-15127,
54-119921, 54-119922, 55-25057, 55-3
No. 6869, No. 56-19049, No. 56-81836, Japanese Patent Publication No. 48-29060
No. etc.

Low boiling or water soluble organic solvents that can be used with or instead of high boiling solvents are U.S. Pat.No. 2,801,171,
Examples thereof include those described in No. 2,949,360. The low-boiling substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and the water-soluble organic solvent includes acetone, Methyl isobutyl ketone,
β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile,
Examples include dioxane, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol and the like.

Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polysulfonates. Anionic surfactants such as oxyethylene alkylphenyl ether, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkyl sulfonic acids,
And amphoteric surfactants such as alkyl betaines,
And, it is preferable to use a cationic surfactant such as quaternary ammonium salt. Specific examples of these surfactants are described in "Surfactant Handbook" (Industrial Books, 1966) and "Collection of Emulsifier / Emulsification Equipment Research / Technical Data" (Kagakugenron, 1978).

As a latex dispersion method, for example, U.S. Pat.
No. 363, No. 4,214,047, No. 4,203,716, No. 4,24
7,627, JP-A-49-74538, 51-59942, 51-5994
The methods described in No. 3, No. 54-32552 and the like are preferable.

When color development processing is carried out using a silver halide color photographic light-sensitive material containing the silver halide emulsion of the present invention, color development processing, bleaching processing step, fixing processing step, washing processing step if necessary, and / or stability A bleach-fixing process can be performed by using a one-bath bleach-fixing solution instead of the bleaching-solution-using process and the fixing-solution-using process. It is also possible to carry out a monobath processing step using a one-bath development bleach-fixing processing solution capable of fixing in one bath.

A pre-hardening treatment step, a neutralization step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed in combination with these treatment steps. In these processes, instead of the color development processing step, a color developing agent or its precursor may be contained in the material and an activator processing step in which the development processing is performed with an activator solution may be performed, or the activator processing step may be performed instead of the monobath processing. It may be performed at the same time as the beta treatment and the bleaching and fixing treatments. Typical processes during these processes will be described.
(These treatments include any one of a washing treatment step, a stabilizing treatment step, a washing treatment step and a stabilizing treatment step as the final step.) (1) Color development processing step-bleaching step-fixing step (2) ) Color development processing step-bleach fixing processing step (3) Pre-hardening processing step-neutralization processing step-color development processing step-stop fixing processing step-water washing processing step-bleaching processing step-
Fixing treatment step-Water washing treatment step-Post-hardening treatment step (4) Color development treatment step-Water washing treatment step-Supplementary color development treatment step-Stop treatment step-Bleaching treatment step-Fixing treatment step (5) Monobath treatment step (6) ) Activator processing step-bleach-fixing processing step (7) Activator processing step-bleaching processing step-fixing processing step The following is preferably used when processing a silver halide color photographic light-sensitive material containing the silver halide emulsion of the present invention. The processing step (2) that is performed will be described in detail.

As the color developing agent used in the color developing solution, aromatic primary amine compounds, particularly p-phenylenediamine type compounds are typical, and preferable examples include N, N-
Diethyl-p-phenylenediamine hydrochloride, N-ethyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p
-Phenylenediamine hydrochloride, 2-amino-5- (N-
Ethyl-N-dodecylamino) -toluene, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-
Hydroxyethylaminoaniline, 4-amino-N-
(2-Methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate, N, N-diethyl-3
-Methyl-4-aminoaniline, N-ethyl-N- (β
-Hydroxyethyl) -3-methyl-4-aminoaniline and the like can be mentioned.

These color developing agents may be used alone or in combination of two or more kinds, and one or more color developing agents and other black and white developing agents such as hydroquinone and 1-phenyl-3-pyrazolidone may be used. , N-methyl-p
-It may be used in combination with aminophenols. This color developing agent may be contained in the silver chloride color photographic light-sensitive material of the present invention. In this case, the amount of the color developing agent added is in the range of 0.2 to 2 mol, preferably 0.4 to 0.7 mol, based on 1 mol of silver halide contained in the silver chloride color photographic light-sensitive material. .

When the silver halide color photographic light-sensitive material of the present invention is subjected to color development processing, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-, among the compounds described above, is particularly used as a color developing agent. Aminoaniline sulfate is particularly preferred.

Examples of the color developing solution include, in addition to the above color developing solutions, sodium hydroxide, potassium hydroxide, sodium carbonate, and
Alkaline agents such as sodium phosphate, potassium carbonate, potassium hydrogen carbonate, N, N-bis (methoxyethyl) hydroxylamine, N, N-diethylhydroxylamine, triethanolamine, diethanolamine, preservatives such as glucose, methanol, Organic solvents such as ethanol, butanol, ethylene glycol, diethylene glycol,
If necessary, various photographic additives known in the photographic field such as a development regulator such as citrazinic acid and polyethylene glycol, a fluorescent brightening agent, a heavy metal ion concealing agent and a development accelerator can be contained.

The silver chloride color photographic light-sensitive material of the present invention is developed with a color developing solution containing no water-soluble bromide or containing a very small amount thereof. When the water-soluble bromide is contained in excess, the development speed of the silver chloride color photographic light-sensitive material is drastically reduced, and the object of the present invention cannot be achieved. The bromide ion concentration in the color developing solution is converted into potassium bromide, and is generally 0.1 g or less per color developing, preferably 0.
It is less than 05g.

When continuously processing the light-sensitive material of the present invention while continuously replenishing the color developing replenisher, when a trace amount of bromide ions is eluted from the color light-sensitive material as a result of development,
A small amount of bromide ions will accumulate in the color developer,
Even in this case, it is preferable to appropriately select the replenishment ratio of the color developing solution replenisher with respect to the total amount of bromide contained in the light-sensitive material so that the bromide ion amount in the color developing solution falls within the above range.

When a water-soluble chloride is used as a development regulator in the color developing solution, the rapid processing property of the silver halide photographic light-sensitive material containing the silver halide grains of the present invention is further improved, which is preferable. The water-soluble chloride used is converted to potassium chloride and used in the range of 0.5 g to 5 g, preferably 1 g to 3 g, per color developing solution.

An organic development inhibitor described in JP-A-58-95345 can be further used in the color developing solution within the range not impairing the present invention. Preferably, adenine and guanine are used in the color developer in the range of 0 to 0.02 g / l.

The pH of the developer of the present invention is 9.5 or higher, preferably 13
It is the following. It has been conventionally known that the development is promoted by raising the pH of the developer, but in the silver halide color photographic light-sensitive material of the present invention, the pH of 11 or less provides the most sufficient rapid developability.

The temperature of the color developer is 15 to 45 ° C, preferably 20 to 40 ° C.

As the bleaching agent used in the bleach-fixing treatment carried out subsequent to the color developing treatment, metal complex salts of organic acids are preferable, and aminopolycarboxylic acids or oxalic acid, organic acids such as citric acid and the like metals such as iron, cobalt and copper. It is a coordination of ions. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] ethyl Etherdiaminetetraacetic acid [10] glycol etherdiaminetetraacetic acid [11] ethylenediaminetetrapropionic acid [12] phenylenediaminetetraacetic acid [13] ethylenediaminetetraacetic acid disodium salt [14] ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt These bleaching agents are preferably 5-450 g / l. Is 20-25
Use at 0g / l.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a halogenide such as ammonium bromide other than the above halogenating fixing agent are added, or conversely, a halide such as ammonium bromide. A bleach-fixing solution having a composition containing a large amount of added, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide are also used. I can do things. Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds.
Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
Various bleaching accelerators described in JP-B Nos. 45-8836, 53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally p
Used at H5.0 or higher and pH9.5 or lower, preferably pH5.0 or higher
Used below 8.5, more preferably the most preferred pH is 5.0
It is processed at above pH.5. The processing temperature is 80 ° C. or less and 3 ° C. or more, preferably 5 ° C., higher than the temperature of the processing solution in the color developing tank.
Although it is used at a lower temperature, it is desirably used at a temperature of 55 ° C. or less while suppressing evaporation and the like.

The bleach-fixing time is within 90 seconds, preferably within 60 seconds.

The color light-sensitive material which has been subjected to color development and bleach-fixing treatment needs to be washed with water to remove unnecessary processing chemicals, but instead of washing with water, JP-A-58-14834, 58-105145 and 58-13 are used.
4634 and 58-18631 and Japanese Patent Application Nos. 58-2709 and 5
You may perform water washing alternative stabilization treatment as shown in 9-89288 etc. When processing is carried out while continuously replenishing each of the color developing, bleach-fixing and stabilizing solutions of the present invention, the replenishment rate of each replenishing solution is 100 to 1000 m per 1 m ² of the color light-sensitive material.
l, preferably 150-500 ml.

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

〔Example〕

Example 1 A 1 mol aqueous solution of sodium chloride and a 1 mol aqueous solution of silver nitrate were added at 40 ° C. under conditions of pAg = 5.5 over 30 minutes to obtain a cubic monodispersed silver chloride emulsion having an average particle size of about 0.22 μm. Obtained.
To this silver chloride emulsion, 2 mol of sodium chloride aqueous solution and 2 mol of silver nitrate aqueous solution were further added over 45 minutes to grow a silver chloride emulsion having an average grain size of about 0.67 μm.

The obtained silver chloride emulsion was subjected to chemical ripening under the conditions shown in Table 1 below, using sodium thiosulfate as a chemical sensitizer, after removing unnecessary salts according to a conventional method. .

The following blue sensitizing dye (BSD-
1) was added in an amount of 3 × 10 ^-4 mol per mol of silver halide,
Further, as a stabilizer, 1.1 g of 4-per mol of silver halide is used.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

Em-1: Does not form silver bromide during chemical ripening. PAg during chemical aging
= 7.3 Em-2: 0.02 mol of a fine grain silver bromide emulsion having an average grain size of about 0.10 μm was added to a silver chloride emulsion (3 minutes before addition of sodium thiosulfate). pAg = 7.4 Em-3: Same as Em-2. However, 1 mol of fine grain silver bromide emulsion
Add 0.05 mol. pAg = 7.4 Em-4: Same as Em-2. However, 0.10 mol of fine grain silver bromide emulsion was added per mol of silver chloride emulsion.

Em-5: 0.034 mol of silver nitrate and 0.
Chemical sensitization was carried out by adding 042 mol of potassium bromide in this order and then sodium thiosulfate.

In Em-6: Em-5, the order of addition of silver nitrate and potassium bromide was changed.

In Em-7: Em-5, silver nitrate and potassium bromide were added in this order 2 minutes after the addition of sodium thiosulfate.

In Em-8: Em-6, silver nitrate and potassium bromide were added in this order 2 minutes after the addition of sodium thiosulfate.

In Em-9: Em-5, silver nitrate and potassium bromide were added to sodium thiosulfate, 85 minutes later in this order, and 10 minutes later a stabilizer.

In Em-10: Em-5, potassium bromide was increased to 0.06 mol.

In Em-11: Em-5, 0.032 mol of potassium bromine and 0.010 mol of sodium chloride were added in place of 0.042 mol of potassium bromide.

In Em-12 Em-5, 0.042 mol of sodium chloride was added instead of 0.042 mol of potassium bromide.

The following multi-layer color photographic sensitizers were prepared using 12 kinds of the blue-sensitive silver chlorobromide emulsion chemically sensitized as described above.

That is, 170 g / m ² of polyethylene support on one side of the paper support,
Corona discharge is applied to the titanium dioxide-containing polyethylene side on a support laminated with polyethylene containing 11% by weight of anatase titanium dioxide on the other side, and the following layers are sequentially applied. The addition amount is shown in 1 m ² unless otherwise specified.

Incidentally, the coating was carried out for two types, that is, the coating was carried out 2 hours after the adjustment of each coating solution (A) and the coating was carried out 10 hours (B).

Layer 1: dissolved in 1.2 g of gelatin, 0.28 g (in terms of silver, the same applies below) of the above blue-sensitive silver chlorobromide emulsion, and 0.50 g of tri- (2-ethylhexyl) phosphate (hereinafter abbreviated as TOP). A layer containing 0.78 g of the yellow coupler (Y-1), 0.35 g of the following image stabilizer STB-1 and 0.04 g of the color stain inhibitor HQ-1.

Layer 2 ... an interlayer containing 0.07 g gelatin, 15 mg anti-irradiation dye (AI-1), 10 mg (AI-2) and 0.05 g DOP with 0.05 g HQ-1 dissolved.

Layer 3: 1.25 g of seratin, 0.22 g of green light-sensitive silver chlorobromide emulsion (Note-1, AgBr10 mol%, average particle size 0.40 μm) 0.30 g of D
Layer containing 0.45g magenta coupler (M-1) 0.20g light stabilizer STB-2 dissolved in OP, and 0.01g HQ-1.

Layer 4 ... an intermediate layer containing 1.2 g gelatine, 0.08 g HQ-1 and 0.4 g UV absorber (UV-1) and 0.25 g (UV-2) dissolved 0.35 g DOP.

Layer 5: 1.4 g of gelatin, 0.20 g of red-sensitive silver chlorobromide emulsion (Note-2, AgBr5 mol%, average particle size 0.65 μm), 0.20 g
Dissolved in DOP.

A layer containing 0.25 g of cyan coupler (C-1), 0.25 g of cyan coupler (C-2), 0.15 g of STB-1, and 0.01 g of HQ-1.

Layer 6 ... 0.30 g dissolved in 1.0 g seratin and 0.20 g DOP
UV-1 and a layer containing 0.05 g of polyvinylpyrrolidone.

Layer 7: Layer containing 0.5 g of gelatin.

As a hardener, 2,4-dichloro-6-hydroxy-
Sodium s-triazine was added to the above layer, and to layer 4 a 4: 1 (molar ratio) reactant of (tetrakisvinylsulfonylmethyl) methane and sodium taurine was added immediately before coating.

Further, the blue-sensitive silver halide emulsion-containing coating solution used for coating Layer 1 contains 0.16 mol of silver halide emulsion per coating solution.

(Note-1) Green photosensitive silver chlorobromide emulsion 3.5 × 1 sodium thiosulfate per mole of silver halide
0 ⁵ mols subjected to chemical sensitization, a green sensitized (GSD-1) were sensitized optically by the dye. 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a, 7-tetrazaindene compound was added in an amount of 1.2 g per mol of silver halide.

(Note-2) Red light-sensitive silver chlorobromide emulsion 3.5 × 1 sodium thiosulfate per mole of silver halide
Red sensitizing dye (RSD-1) with chemical sensitization by adding 0 ³ mol
Optically sensitized by. As a stabilizer, 1.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene compound was added per mol of silver halide.

After subjecting the obtained sample to optical wedge exposure, it was processed according to the following processing steps.

Processing step Color development 35 ° C. 50 seconds Bleach fixing 35 ° C. 50 seconds Water wash 30-34 ° C. 90 seconds Dry 50-70 ° C. 60 seconds The composition of the color developing solution and the bleach-fixing solution used is as follows. (Per 1) Color developing solution Pure water 800 ml Diethylene glycol 12 ml N, N-diethylhydroxylamine 12 ml Potassium chloride 2.2 g Potassium sulfite 0.2 g N-ethyl-N-β-methanesulfonamide ethyl-3
-Methyl-4-aminoaniline sulfate 5.0 g Add pure water to adjust the pH to 1 and adjust the pH to 10.1.

Bleach-fixing solution Pure water 800 ml Ethylenediaminetetraacetate iron (III) ammonium 65 g Ethylenediaminetetraacetate disodium 5 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Sodium chloride 10 g Hydroxylamine sulfate 2 g Add pure water to 1 and dilute sulfuric acid Adjust pH to 6.2.

The sensitivity and the maximum density of each of the obtained samples were obtained from the characteristic curve with blue monochromatic light. The results are shown in Table 1. Table-
The sensitivity of each sample for 2 hours was
Expressed as 100.

From the results shown in Table-1, emulsion Em-1 which does not form silver bromide during chemical ripening, and Em-1 which silver chloride was formed during chemical ripening
It can be seen that in No. 2, the sensitivity is greatly reduced due to the stagnant coating solution for 10 hours.

On the other hand, according to the present invention, Em-2,3,5 ~ 11, all are improved desensitization at the time of coating solution stagnation, especially silver bromide formation, before the addition of sodium thiosulfate It turns out that the result is large when it is performed.

In addition, the maximum concentration of Em-4 formed during the chemical ripening of 0.1 mol of silver bromide decreased, especially when the coating solution stagnated for 10 hours.

Example 2 Example 1 was repeated by diluting with 0.09 mol of silver halide per coating solution forming Layer 1 in Example 1. Table 2 shows the results. The results shown in Table 2 show that the effect of the present invention is particularly large when the silver halide concentration in the coating solution is lowered.

Example 3 In Example 2, 1.6 × 10 ⁻⁴ mol of BSD-1 and 1 mol of silver halide were added to each coating solution for forming layer 1, respectively.
The same experiment as in Example 2 was repeated with the addition of 0.3 g of potassium bromide. The results are shown in Table-3. From the results shown in Table 3, it can be seen that the effects of the present invention are significantly improved by using the water-soluble bromide and the sensitizing dye in the coating solution.

Example 4 The following unchemically sensitized silver chlorobromide emulsion was prepared in the same manner as in Example 1.

Each of the emulsions obtained was chemically sensitized with the sensitizing dyes shown in Table 4, sodium thiosulfate and chloroauric acid. Next, the mercapto compounds shown in Table 4 were added at the end of the chemical ripening.

At this time, an emulsion containing water-soluble bromide as shown in Table 4 was prepared.

Then, the following layers were sequentially coated on the same paper support as in Example 1 using the chemically sensitized silver halide emulsions shown in Table 4.

In addition, the coating was carried out for two kinds after 2 hours and 10 hours after preparation of each coating solution as in Example 1.

Layer 1 ... 1.2 g of gelatin, 0.31 g of blue-sensitive silver chlorobromide emulsion shown in Table 5, 0.40 g of dinonyl phthalate (hereinafter referred to as DNP
0.81 g of yellow coupler (Y-)
2), 0.31g below STB-3, 0.24g below STB-4, and 0.04g
HQ-1 containing layers.

Layer 2 ... dissolved 0.8 g of gelatin and 0.10 g of HQ-1
A layer containing 0.13 g of di-i-decyl phthalate.

Layer 3 ... 1.25 g gelatin, 0.24 g green light sensitive silver chlorobromide emulsion shown in Table 5, 0.41 g magenta coupler (M-2) dissolved in 0.30 g DOP, 0.20 g STB-5 below. , 0.10g of the following STB-6,
A layer containing 0.01 g of HQ-1, and 10 mg of AI-3 below.

Layer 4 ... 1.2 g gelatin, 0.08 g HQ-1, 0.4 g UV-1 and
Layer containing 0.35 g DOP, 10 mg AI-1 with 0.2 g UV-2 dissolved.

Layer 5: 1.4 g of gelatin, 0.21 g of the red-sensitive silver chlorobromide emulsion shown in Table 5, 0.21 g of cyan coupler (C-3 below), 0.12 g of cyan coupler dissolved in 0.30 g of DOP. (C-below
4), 0.15g STB-3, 0.10g STB-7 below, and 0.01g HQ-
Layer containing 1.

Layer 6 ... 1.0 g gelatin, 0.20 g UV-1 and 0.10 g UV-2
A layer containing 0.175 g of DOP dissolved therein, 0.03 g of polyvinylpyrrolidone, 5 mg of AI-1, and 5 mg of AI-4 below.

Layer 7: Layer containing 0.5 g of gelatin.

As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium was added to the above layer, and layer 4 was formed with (tetrakisvinylsulfonylmethyl) methane and taurine sodium at a ratio of 4: 1 (molar ratio). Each reaction was added just prior to coating.

After subjecting the obtained sample to optical wedge exposure with white light, the sample was treated according to the following treatment steps.

Processing process Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Stability (3-tank cascade) 30 to 34 ℃ 90 seconds Dry 60 to 80 ℃ 60 seconds The composition of color developing solution, bleach-fixing solution and stabilizing solution used is as follows. Is the street.

Color developer 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.01 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol- 3,5-Disulfonic acid disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.5 g Potassium carbonate 27 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1 g Water is added to adjust pH to 10.1.

Bleach-fixing solution Pure water 700 ml Ethylenediaminetetraacetic acid Ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 6.2 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 20g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0 g Ammonium sulfite 3.0g Optical brightener (4,4'-diaminostilbenediphosphonic acid derivative) 1.5g Add water to make the pH 1 and add sulfuric acid or potassium hydroxide to adjust the pH.
= 7.0.

The density of the obtained sample was measured with blue, green, and red monochromatic light, and the results shown in Table 5 were obtained.

In Table 5, B, G, and R indicate the results obtained by measuring the concentration with blue, green, and red monochromatic light, respectively, and the sensitivities were obtained when the coating solution stagnation time was 2 hours for each sample. The relative value is set to 100.

From the results shown in Table 5, in each of the blue, green and red emulsion layers, in the sample in which silver bromide was not formed during the chemical ripening, the sensitivity was lowered in all layers due to the stagnant coating solution. I understand. On the other hand, it can be seen that in Samples 39 to 45 in which silver bromide was formed during the chemical ripening, the sensitivity deterioration was prevented while the coating solution was stagnant.

On the other hand, looking at the maximum red concentration of the sample in which the silver bromide ratio was changed in the red light-sensitive emulsion layer, it was found that the maximum concentration gradually decreased as the silver bromide ratio increased. A marked decrease in the maximum concentration is observed when is added.

Example 5 All unchemically sensitized emulsions used in Example 4 were replaced with blunt silver chloride emulsions (average grain size is for blue light sensitivity = 0.71 μm).
m, green sensitivity = 0.40 μm, red sensitivity = 0.42 μm),
The same experiment as in Example 4 was repeated. As a result, as in Example 4, it was confirmed that the decrease in sensitivity when the coating solution was stagnant was prevented by the formation of silver bromide during the chemical ripening.

〔The invention's effect〕

According to the present invention, when a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains having a silver chloride composition of 80 mol% or more is produced, the coating solution for the emulsion layer is stagnant. The sensitivity variation in the medium is improved, which improves the uniformity of sensitivity in the same coating lot and also provides a high maximum density.

Claims (1)

(57) [Claims] 1. When chemically ripening high silver chloride-containing silver halide grains having a silver chloride content of 80 mol% or more, 0.001 to 0.08 mol of silver bromide is formed per mol of the silver halide grains. A silver halide photographic emulsion characterized by being at least chemically ripened.