JPH0731380B2 - Silver halide photographic material with improved pressure resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, more specifically, it suppresses fogging, enables rapid development processing, and has high processing stability in the rapid development processing. The present invention relates to a silver halide photographic light-sensitive material which is improved and has excellent resistance to pressure effect.

BACKGROUND OF THE INVENTION In recent years, in the industry, a silver halide photographic light-sensitive material that can be rapidly processed, has high image quality, is excellent in processing stability, and is low in cost has been particularly desired. ,
A silver halide photographic light-sensitive material capable of rapid development processing is desired.

That is, the silver halide photographic light-sensitive material is run by an automatic processor provided at each development site. Therefore, it is required to return it to the user, and recently it is even required to return it in a few hours from the reception desk, and development of rapid processing is urgently required.

On the other hand, when a silver halide photographic light-sensitive material is continuously processed while replenishing a replenisher with a replenisher for a long period of time at a developing station, a change in composition of the processing solution causes a change in photographic characteristics (especially gradation change). There's a problem. This problem,
With the recent trend toward lower replenishment of processing liquid, it is becoming even larger. To reduce the replenishment of processing solutions, accumulation of development inhibitors from silver halide photographic light-sensitive materials (hereinafter abbreviated as "light-sensitive materials"), mixing of bleaching solutions, fixing solutions or bleach-fixing solution components into color developing solutions. , And bromide ion concentration in the color developing solution is liable to change, and such a change in the composition of the color developing solution changes photographic performance, which is a major obstacle to stable and favorable color reproduction and gradation reproduction. ing. Above all, the bleaching solution, the fixing solution or the bleach-fixing solution is completely removed from the developer even if the strict setting of the replenishing rate of the replenishing solution, the prevention of evaporation, and the elution from the light-sensitive material are eliminated. It is almost impossible to do so, especially in the roller transfer and automatic developing machine, the processing amount and the mixing amount of the bleach-fixing solution into the developing solution are significantly different depending on the squeeze method, and the replenishment rate of the processing solution is lowered. In this case, since the rotation speed of the treatment liquid decreases, a difference in the mixing ratio actually occurs.

Various improvement measures have been studied to meet the current situation and needs of the market. For example, in order to achieve rapid processing, a light-sensitive material and a processing solution are approached from two sides. Many attempts have been made to optimize the temperature and pH of processing solutions and to add additives such as development accelerators.However, these processing solution improvement measures alone do not achieve sufficient swiftness and increase in fog. Often accompanied by performance degradation.

On the other hand, the shape, size, and composition of the silver halide grains of the photosensitive silver halide emulsion used for the light-sensitive material have a great influence on the development rate, etc., and particularly the silver halide composition has a great influence. It has been found that when a high chloride silver halide is used, a particularly high development rate is exhibited.

However, in the light-sensitive material using the high chloride silver halide emulsion, which is the best from the viewpoint of rapid processability, fog is likely to occur, and the influence of the performance fluctuation due to the incorporation of the bleach-fix solution into the developer is It had a problem of being very susceptible and needed improvement. As a means for solving one of the above problems, in order to prevent the fog of the silver halide emulsion,
Although various inhibitors are known, among them, the inhibitor described in U.S. Pat.No. 4,565,774 is very effective in suppressing fog in a high chloride silver halide emulsion, and has a rapid processability. Although there was almost no inhibition, it was excellent, but the effect of improving performance fluctuations (hereinafter referred to as “BF solution mixing variability”) due to mixing of the bleach-fixing solution into the developing solution was very slight.

It is also known that by adding a certain mercapto compound to the light-sensitive material, fluctuations in the BF solution mixing can be reduced to some extent, but simply adding a mercapto-based compound to the light-sensitive material using high chloride silver halide. However, the effect is very small, and if a mercapto compound is added to bring about a sufficient effect, there is a drawback that the sensitivity is significantly decreased, the processing speed is significantly decreased, and further desilvering failure occurs. I couldn't solve the points at the same time.

To solve the above two problems at the same time, Japanese Patent Laid-Open No.
No. 58-108533 discloses a technique using a silver halide light-sensitive material containing high chloride silver halide grains having a layer mainly consisting of silver bromide on the surface. However, the silver halide photographic material described in the above publication has a fog property and
It was found that the BF liquid mixing variability was improved, but there was a serious drawback in practical use of the silver halide photographic light-sensitive material that the pressure resistance was significantly deteriorated.

The present inventors have made the present invention as a result of continuing the study of a silver halide photographic light-sensitive material in which the fog is suppressed, the BF liquid mixture variability is good, and the pressure resistance is excellent. Is.

The pressure characteristics of silver halide grains will be described below.

Generally, various pressures are applied to the light-sensitive material. During the production of the photosensitive material, for example, a large pressure is applied in the step of cutting the photosensitive material.

In addition, when the photosensitive material is used, the sheet-shaped photosensitive material is often bent because humans handle it by hand, and pressure is applied to the bent portion.

On the other hand, it has become more common in recent years to subject a photosensitive material to automatic exposure by a printer and automatic development processing using an automatic processor. As a result, the photosensitive material is increasingly exposed to mechanical pressure in these devices. When various pressures are applied to the light-sensitive material in this manner, pressure is also applied to the silver halide grains in the light-sensitive material through gelatin which is a binder of the silver halide grains. When pressure is applied to silver halide grains, photographic characteristics are changed, and phenomena such as pressure desensitization and pressure fog occur. This phenomenon is well known in the art as the photographic pressure effect, and is described in, for example, TH James: The Theory of the Photographic Proces.
s), 4th edition, Macmillan Publishers, New York, 24th
D, Dautrich, F. Granzer and E. Moisa
r): Journal of Photographic Science (J.Phot.Sci.), 21,221 (1973), etc.

Further, it is well known in the art that the higher sensitivity silver halide grains having a larger grain size are more sensitive to pressure and more susceptible to pressure desensitization and pressure fog.

Furthermore, when the light-sensitive material is applied with pressure in a dry state,
The pressure may be applied in a wet state during the phenomenon treatment. Therefore, the effect cannot be said to be sufficient unless the pressure resistance is improved in both states.

Therefore, it has been attempted to provide a light-sensitive material that has little influence on pressure.

As a means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer and a method of reducing the silver halide / gelatin ratio are known.

For example, British Patent No. 738,618 describes a heterocyclic compound as 738,6
No. 37 is alkyl phthalate, No. 738,639 is alkyl ester, U.S. Pat.No. 2,960,404 is polyhydric alcohol, No. 3,121,060 is carboxyalkyl cellulose, and JP-A No. 49-5017 is paraffin and carboxyl. Japanese Patent Publication No. 53-28086 discloses a method of using an acid salt with an alkyl acrylate and an organic acid.

However, these techniques have the drawbacks that the pressure resistance effect is insufficient in both the dry state and the wet state, and further the binder properties such as stickiness and drying property on the surface of the photosensitive material are significantly deteriorated.

Further, as a means for improving the pressure characteristics of silver halide grains, Japanese Patent Publication No. 57-23248 discloses a method of adding a mercapto compound and a water-soluble iridium compound at the time of forming halogen grains, and U.S. Pat. A method using a modified emulsion is disclosed.

However, the above-mentioned conventional methods cannot obtain a satisfactory improvement effect, and often cause deterioration of photographic performance.

When fog or desensitization occurs due to these pressure effects, the quality of the silver halide photographic light-sensitive material is significantly impaired. Further, with rapid processing, the pressure effect is more likely to occur with the increase in transport speed, etc., and development of a silver halide photographic light-sensitive material with improved resistance to the pressure effect (hereinafter referred to as "pressure resistance") Is becoming more and more important.

[Object of the Invention] Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is suitable for rapid processing, in which fogging is suppressed, processing stability is excellent, and pressure resistance is also excellent.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers comprises
To provide a silver halide photographic light-sensitive material containing silver halide grains having a silver chloride content of 80 to 99 mol% formed by forming a high silver bromide phase on a high silver chloride phase in the presence of a sensitizing dye. Achieved by

[Specific Structure of the Invention] In the silver halide grain according to the present invention, 80 to 99 mol% of the total silver halide composition constituting the grain is silver chloride, and more preferably 90 to 99 mol%. It is a range. The silver halide composition other than silver chloride is not particularly limited, but it is preferably substantially silver bromide. Here, "substantially silver bromide" means silver bromide having a silver iodide content of 1 mol% or less.

The high silver bromide phase according to the present invention means that the silver halide composition of the phase is 70 mol% or more, and preferably 90 mol% or more is silver bromide.

The high silver bromide phase may cover the entire surface of the silver halide grains of the high silver chloride phase mainly consisting of silver chloride, may cover a part of the surface, or may be epitaxially bonded to the surface. It may be The boundary between such high silver bromide and other phases may have a clear phase boundary or may change continuously. 1 to 20 mol% of the total silver halide constituting the silver halide grains according to the present invention
Consists of silver bromide. The silver bromide may be present not only in the outermost shell portion of the silver halide grain but also inside the grain, but most of the silver bromide is preferably contained in the outermost shell portion of the grain.
The high silver bromide phase at the outermost shell of the grain is particularly preferably 1 to 10 mol% constituting the grain.

To more clearly define the high silver bromide phase according to the present invention, when the silver halide grains having the above composition are analyzed by an X-ray diffraction method, the peak attributed to the high silver bromide phase is the high silver bromide. It shows a diffraction pattern that can be clearly distinguished from the peaks attributed to a high silver chloride phase other than the phase.

The silver halide emulsion layer containing the silver halide grains according to the present invention may contain silver halide grains other than the silver halide grains according to the present invention. The ratio of the silver halide grains according to the present invention to the total amount of silver halide contained is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more.

The silver halide grain used in the present invention, whether it has a (100) face or a (111) face,
Or even if it has both, it can be preferably used.

The grain size of the silver halide grains used in the present invention may be within the range generally used, but the average grain size is from 0.05 μm to
It is preferably 1.0 μm. The particle size distribution may be polydisperse or monodisperse, but monodisperse emulsions are more preferably used.

The silver halide grains used in the present invention can be prepared by a method commonly used by those skilled in the art. For these methods, see, for example, The Theory
The Theory of
It can be adjusted by various methods such as the ammonia method, the neutral method and the acidic method, which are generally accepted and described in the books such as Photographic Process: Mac Mitton).

Regarding the method of adding the halide salt and the silver salt,
Akira Hirata, All of the forward mixing method, the reverse mixing method, and the simultaneous mixing method described in Chapter 3 of "The Basics of Photographic Engineering-Silver Salt Photography" (Corona Publishing Co., Ltd.) edited by the Photographic Society of Japan are used. However, a conversion method can also be used when forming a layer mainly composed of silver bromide. The silver halide grains according to the present invention can be prepared by injecting a halide salt solution and a silver salt solution into a reactor at the same time and preparing the silver halide grains in the presence of a suitable protective colloid. Are particularly preferably used. Even in the simultaneous mixing method, the so-called balanced double jet method, in which mixing is performed while adjusting the addition rates of the halide salt solution and the silver salt solution so as to keep pAg within a certain range, is more preferably used. pH as well as pAg
The temperature is also preferably controlled during the precipitation to a suitable value.
In the case of forming a layer mainly composed of silver bromide, a bromide ion solution is added after all silver salts used in the reaction have been added by a method such as a simultaneous mixing method.
A so-called conversion method can also be preferably used.

In adjusting the silver halide, the pH value is 2.0 to 8.5,
Particularly, 3.0 to 7.5 is preferable. The pAg value is slightly different depending on each stage of silver halide grain preparation (depending on the halogen composition), but in the preparation of the high silver chloride silver halide grains according to the present invention, 6.0 to 8.5 is preferable, and particularly preferable. Is 7.0
~ 8.0. When forming a phase mainly composed of silver bromide, pAg = 7.0 to 10.0 is preferable, and 8.0 to 9.5 is particularly preferable. As for humidity
40 to 85 ° C, particularly 45 to 75 ° C is preferable.

Various devices for preparing such silver halide grains have been proposed. For example, a rapid precipitation reaction is carried out by vigorous stirring in a relatively small precipitation chamber described in JP-B-48-21045. A method in which physical ripening is carried out in a large volume ripening chamber, and the dispersion liquid thus formed is recirculated into the precipitation chamber to be used as a medium for the precipitation of silver halide.
The precipitate is submerged in the reactor described in JP-B-49-48964.
A silver salt solution and a halide salt solution are introduced into the liquid at different parts in the precipitation chamber, diluted with the liquid in the reactor, mixed, and then subjected to a rapid precipitation reaction, and then dispersed in the reactor outside the precipitation chamber. There is a method in which the substance is discharged, physical ripening is carried out, the dispersion is introduced into the precipitation chamber again, and the dispersion is used as a medium for the precipitation of silver halide. These devices can be particularly preferably used for the preparation of the silver halide emulsion according to the present invention.

The silver halide emulsion may or may not be physically ripened. Emulsions are usually freed of soluble salts after precipitation or physical ripening. The means used for this purpose is to use inorganic noodle washing methods known from ancient times, such as inorganic salts having polyvalent anions (for example, ammonium sulfate). Magnesium sulfate), anionic surfactants, polystyrene sulphonic acid, other anionic polymers, or precipitation methods (flocculation) using gelatin derivatives such as aliphatic- or aromatic-acylated gelatin good.

The silver halide grains according to the present invention are formed in the presence of a sensitizing dye.

The sensitizing dye used in the present invention is not particularly limited, but a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus. , Quinoline nucleus and so on. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied. Examples of useful sensitizing dyes used in the present invention include West German Patent 929,080 and U.S. Pat.
31,658, 2,493,748, 2,503,776, 2,519,00
No. 1, No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, No. 52-24844 and the like. Further, useful sensitizing dyes include, for example, U.S. Pat.
2,908, 2,739,149, 2,945,763, British patent 50
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in 5,979. Examples of useful sensitizing dyes include
For example, U.S. Patents 2,269,234, 2,270,378, 2,442,
Representative examples thereof include cyanine dyes, merocyanine dyes or complex cyanine dyes as described in No. 710, No. 2,454,629, No. 2,776,280 and the like. Furthermore, U.S. Patents 2,213,995, 2,493,748, and
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in 2,519,001 and West German Patent 929,080 can be advantageously used.

In the present invention, the sensitizing dye used in the blue-sensitive silver halide emulsion layer is preferably a sensitizing dye represented by the following general formula [A].

General formula [A] In the general formula [A], Z ₁₁ and Z ₁₂ are respectively a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus and a pyridine nucleus. Or, it represents a group of atoms necessary for forming a quinoline nucleus, and these heterocycles include those having a substituent. Examples of the substituent of the hetero ring formed by Z ₁₁ and Z ₁₂ include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group or an alkoxycarbonyl group, and among these substituents, a preferable substituent is It is a halogen atom, a cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and particularly preferable substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R_{twenty one}And R_{twenty two}Are alkyl and alkenyl groups, respectively.
Or an aryl group, preferably an alkyl group.
And more preferably a carboxyl group or a sulfo group
Substituted alkyl group, most preferred carbon atom
It is a sulfoalkyl group having a child number of 1 to 4. Also R_{twenty three}Is hydrogen
It is selected from an atom, a methyl group and an ethyl group. X Is Yin Io
And 1 represents 0 or 1.

Among the sensitizing dyes represented by the general formula [A], particularly useful dyes are the sensitizing dyes represented by the following general formula [A '].

General formula [A '] Here, Y ₁ and Y ₂ each represent an atom group necessary for completing an optionally substituted benzene ring or naphthalene ring. The benzene ring and naphthalene ring formed by Y ₁ and Y ₂ also include those having a substituent, and the substituent is preferably a halogen atom, a hydroxyl group, a cyano group, an aryl group,
It is an alkyl group, an alkoxy group or an alkoxycarbonyl group. More preferred substituents are halogen atoms, cyano groups, aryl groups, alkyl groups or alkoxy groups having 1 to 6 carbon atoms, and particularly preferred substituents are halogen atoms, cyano groups, methyl groups, ethyl groups, methoxy groups or ethoxy groups. Is.

R_{twenty one}, R_{twenty two}, R_{twenty three}, X And l are represented by the general formula [A]
It is the same as

Specific examples of the sensitizing dye represented by the general formula [A] used in the present invention are shown below.

General formula [A] In the present invention, the sensitizing dye used in the green-sensitive silver halide emulsion layer is preferably a sensitizing dye represented by the following general formula [B].

General formula [B] In the formula, Z ₁₁ and Z ₁₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring condensed with an oxazole. The heterocyclic nucleus formed may be substituted with various substituents, and these preferable substituents are a halogen atom, an aryl group, an alkyl group or an alkoxy group. More preferable substituents are a halogen atom, a phenyl group and a methoxy group, and the most preferable substituent is a phenyl group.

According to a preferred embodiment of the present invention, Z ₁₁ and Z ₁₂ both represent a benzene ring fused to an oxazole ring, and at least one of these benzene rings has a 5-position substituted with a phenyl group, or The 5-position of one benzene ring is substituted with a phenyl group and the 5-position of the other benzene ring is substituted with a halogen atom.

R ₂₁ and R ₂₂ each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. More preferably, R ₂₁ and R ₂₂ are each an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferably, it is a sulfoethyl group.

R ₂₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
It preferably represents a hydrogen atom or an ethyl group.

X₁ Represents an anion, for example, chlorine, bromine, iodine
Halogen ions,CH₃SO_Four, C₂H_FiveSO_FourAnd the like anions. n is 1
Or represents 0. However, when the compound forms an inner salt
In this case, n represents 0.

Hereinafter, specific examples of the sensitizing dye represented by the general formula [B] which is preferably used in the invention will be shown.

In the present invention, the sensitizing dye used in the red-sensitive silver halide emulsion layer is preferably a sensitizing dye represented by the following general formula [C] and a sensitizing dye represented by the following general formula [D].

General formula [C]General formula [D]In the formula, R represents a hydrogen atom or an alkyl group, and R₁Through
R_FourRepresents an alkyl group and an aryl group, respectively, and Z₁,
Z₂, Z_FourAnd Z_FiveIs a thiazole ring or selenazo, respectively
Form a benzene or naphthalene ring fused to a ring
Represents the atomic group necessary for₃Is necessary to form a 6-membered ring
Represents a necessary hydrocarbon atom group, l represents 1 or 2,
Z represents a sulfur atom or a selenium atom, and X Is an anion
Represents

In the above general formula, the alkyl group represented by R includes a methyl group, an ethyl group and a propyl group, and R is preferably a hydrogen atom, a methyl group or an ethyl group. Particularly preferred are hydrogen atom and ethyl group.

Further, R ₁ , R ₂ , R ₃ and R ₄ are each a linear or branched alkyl group, and this alkyl group may have a substituent.
(For example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl,
Carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy-γ-sulfopropyl, sulfopropyl, allyl, benzyl, etc.) or an aryl group, which aryl group has a substituent. Good. (For example, phenyl, carboxyphenyl, sulfophenyl, etc.) represents a group selected from, and the heterocyclic nucleus formed by Z ₁ , Z ₂ , Z ₄ and Z ₅ may have a substituent,
The substituent is preferably a halogen atom, an aryl group, an alkyl group or an alkoxy group, more preferably a halogen atom (eg chlorine atom), a phenyl group or a methoxy group.

X is an anion (eg Cl, Br, I, CH ₃ SO ₄ , C ₂ H ₅ SO _{4 and the} like), and 1 represents 1 or 2.

However, 1 represents 1 when the compound forms an inner salt.

Hereinafter, typical specific examples of the sensitizing dyes represented by the general formulas [C] and [D] which are preferably used in the invention will be shown.

As a method of adding a sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes are dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of such solvents), and in some cases diluted with water, or In some cases they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibration for this dissolution. Further, the sensitizing dye used in the present invention, as described in US Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid,
A method of adding this dispersion, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion, as described in JP-B-46-24185 and the like, can also be used. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method. Other addition methods are described in U.S. Pat.
The methods described in 3,342,605, 2,996,287, 3,425,835 and the like can also be used.

The sensitizing dye contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvent, and these solutions may be mixed or added separately prior to addition to the silver halide emulsion. . When they are added separately, their order, time, and interval can be arbitrarily determined depending on the purpose. The timing of adding the sensitizing dye used in the present invention to the emulsion is, specifically, before the nucleation of high silver chloride grains having a silver chloride content of 80 to 99 mol% and before forming the high silver bromide silver halide phase. It may be added at any time up to and may be added in portions. It is preferably added from the end of the formation of the high silver chloride silver halide grains to the formation of the high silver bromide silver halide phase, that is, on the surface of the high silver chloride silver halide phase.

The addition amount of the sensitizing dye is not particularly limited as long as the effect of the present invention is achieved, but is preferably in the range of 2 × 10 ⁻⁶ to 1 × 10 ⁻³ mol per mol of silver halide. And more preferably in the range of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol. Furthermore, after adding the sensitizing dye, the sensitizing dye may be inactivated by an oxidizing agent such as hydrogen peroxide, if necessary, which is one of the preferable embodiments. In this case, an optional sensitizing dye can be newly added at the stage of chemical sensitization depending on the purpose.

The silver halide grain having the sensitizing dye according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one type of simultaneous mixing method, Japanese Patent Laid-Open No. 54-4
It is also possible to use the PAg-controlled double-jet method described in 8521 and the like.

If necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit controlling agent such as a mercapto group-containing compound may be used.

The silver halide grain having a sensitizing dye according to the present invention, in the process of forming and / or growing the grain, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, A metal ion can be added using an iron salt or a complex salt so as to be incorporated into the inside of the particle and / or on the surface of the particle, and by placing it in an appropriate reducing atmosphere, reduction and increase in the inside of the particle and / or the surface of the particle can be achieved. It can give a feeling of nuclei.

The silver halide grain used in the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

However, in order to sufficiently bring out the effect of the present invention, when chemical sensitization is carried out after silver halide grain formation, that is, before chemical sensitization, and when chemical sensitization is carried out during silver halide grain formation, After the silver particles are finally formed,
It is preferred to avoid applying silver halide grains of the type that primarily form a latent image therein. Whether or not the silver halide grains are of the internal latent image type can be determined by the method described in JP-B-52-34213.

That is, the emulsion to be evaluated is coated on a polyethylene-coated support at a silver coverage of about 300-400 mg / ft ² . This sample was divided into two, and each was subjected to a light-intensity scale to obtain 1 × 10 ^-2 ~
Exposure is carried out using a 500 W tungsten lamp for a fixed time of 1 second. One of the samples is the following developer Y
(“Internal type” developer) 18.3 ° C., 5 minutes development, the other one is the following developer X (“surface type” developer) 20
Develop at 6 ° C for 6 minutes.

In the present invention, it is preferable to use silver halide grains in which the maximum density after internal development / the maximum density after surface development is 5 or less, and more preferably 2 or less. Present
Image liquid X N-methyl-p-aminophenol sulphate 2.5g Ascorbic acid 10.0g Potassium metaborate 35.0g Potassium bromide 1.0g Add water 1 (pH = 9.6) Developer Y N-methyl-p-aminophenol sulphate 2.0g Sodium sulfite (dry) 90.0g Hydroquinone 8.0g Sodium carbonate ・ 1H ₂ O 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Add water 1 (pH = 10.06) Contains silver halide grains according to the present invention In the silver halide emulsion (hereinafter referred to as the silver halide emulsion of the present invention) to be used, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. The salts can be removed by the method described in Research Disclosure No. 17643.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
Until silver halide emulsion is applied during chemical ripening for the purpose of preventing fog during storage or during photographic processing, or for the purpose of keeping photographic performance stable, after chemical ripening, and / or after chemical ripening. In addition, compounds known as antifoggants or stabilizers in the photographic industry can be added.

Antifoggants and stabilizers include U.S. Patent No. 2,713,541
Nos. 2,743,180 and 2,743,181, pentazaindenes, U.S. Pat.Nos. 2,716,062 and 2,444,607.
No. 2, No. 2,444,605, No. 2,756,147, No. 2,835,581,
No. 2,852,375, Research Disclosure (Resea
rch Disclosure) 14851, tetrazaindenes described in US Pat. No. 2,772,164, and azaindenes such as polymerized azaindenes described in JP-A-57-211142; US Patent No. 2,
Thiazolium salts described in 131,038, 3,342,596, and 3,954,478, pyrylium salts described in U.S. Pat. No. 3,148,067, and quaternary onium salts such as phosphonium salts described in Japanese Patent Publication No. 50-40665; United States Patent No. 2,403,
927, 3,266,897, 3,708,303, JP-A-55-1358
No. 35, mercaptotetrazole described in 59-71047, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat.No. 2,824,001, mercaptobenzthiazole described in U.S. Pat. , Mercaptobenzimidazoles, mercaptooxadiazoles described in U.S. Pat.No. 2,843,491, mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in U.S. Pat.No. 3,364,028; U.S. Pat. Kosho 4
Catechols described in 3-10256, Japanese Patent Publication No. 56-44413
Resorcins described in Japanese Patent Publication No. 43-4133 and polyhydroxybenzenes such as gallic acid esters described in Japanese Patent Publication No. 43-4133; tetrazoles described in West German Patent No. 1,189,380, described in US Patent No. 3,157,509 Triazoles, benzenetriazoles described in U.S. Patent No. 2,704,721, urazoles described in U.S. Patent No. 3,287,135, pyrazoles described in U.S. Patent No. 3,106,467, indazole described in U.S. Patent No. 2,271,229. And azoles such as polymerized benztriazoles described in JP-A-59-90844 and US Pat.
Pyrimidines described in 161,515, U.S. Pat.
Heterocyclic compounds such as 3-pyrazolidones described in 1,297, and polymerized pyrrolidone described in US Pat. No. 3,021,213, that is, polyvinylpyrrolidones; JP-A-54-130922, 59-137945, and JP-A-59-137945; 140445, British Patent 1,356,142, U.S. Patents 3,575,699, 3,649,267
Various inhibitor precursors described in US Pat. No. 3,047,393; sulfinic acid and sulfonic acid derivatives described in US Pat. No. 3,047,393; US Pat. Nos. 2,566,263, 2,839,405, and
Inorganic salts described in 2,488,709 and 2,728,663 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.

As gelatin, lime-treated gelatin, acid-treated gelatin, Bulletin of Society of Science of Photography of Japan (Bull. Soc.
Sci. Phot. Japan) No. 16, page 30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are U.S. Patent Nos. 2,614,928 and 3,132,945,
3,186,846, 3,312,553, British patent 861,414,
1,033,189, 1,005,784, and Japanese Examined Patent Publication No. 42-26845.

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 gelatin and other polymers, gelatin is a homopolymer or copolymer of acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene. What grafted 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 copolymer, etc., for example West German Patent Application (OLS) 2,312,708, U.S. Patent Nos. 3,620,751, 3,879,205. , JP-B-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 hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

As a hardener, aldehyde-based, aziridine-based (for example, PB Report, 19,921, U.S. Patent Nos. 2,950,197, 2,964,404, 2,983,611, 3,271,175,
, Those disclosed in JP-B-46-40898 and JP-A-50-91315), isoxazole-based compounds (for example, those described in US Pat. No. 331,609), and epoxy-based compounds. For example, U.S. Patent No. 3,047,394 and West German Patent No. 1,085,663.
, British Patent No. 1,033,518, each specification, Japanese Patent Publication No. 48-3549
5), vinyl sulfone type (for example, PB Report 19,920, West German Patent Nos. 1,100,942 and 2,3).
37,412, 2,545,722, 2,635,518, 2,742,30
No. 8, No. 2,749,260, British Patent No. 1,251,091, Japanese Patent Application No. 4
5-54236, 48-110996, U.S. Pat.No. 3,539,644,
No. 3,490,911), acryloyl series (for example, Japanese Patent Application No. 48-27949, U.S. Pat. No. 3,640,
720), carbodiimide-based compounds (for example, U.S. Patent Nos. 2,938,892, 4,043,818, and
4,061,499, Japanese Patent Publication No. 46-38715, Japanese Patent Application No. 49-15095), triazine (for example, West German Patents 2,410,973, 2,553,915, U.S. Patent 3,325,287) , Each of which is described in JP-A-52-12722), a polymer type (for example, British Patent No. 822,061).
U.S. Pat.Nos. 3,623,878, 3,396,029, 3,226,
No. 234, Japanese Patent Publication Nos. 47-18578, 18579, 47
Other than those described in Japanese Patent Publication No. 48896) Other maleimide-based, acetylene-based, methanesulfonic acid ester-based, (N
-Methylol type) hardeners can be used alone or in combination. West German Patent No. 2 as a useful combination technology,
447,587, 2,505,746, 2,514,245, U.S. Pat.Nos. 4,047,957, 3,832,181, 3,840,370, JP-A-48-43319, 50-63062, 52-127329.
And the combinations described in Japanese Patent Publication No. 48-32364.

Using the silver halide emulsion of the present invention, a dye formation which forms a dye by a coupling reaction with an oxidized product of a color-developing aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.). A coupler is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the 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. Further, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye. Even if they are 4-equivalent, only 2 molecules of silver ions need to be reduced. Either equivalence may be used. The dye-forming coupler includes a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener fog agent, an antifoggant, a chemical sensitizer, by coupling with an oxidized product of a developing agent. Compounds that release photographically useful fragments, such as spectral sensitizers, and desensitizers can be included. 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, it is preferable that the DIR coupler is of the same type as the dye formed from the coupler and the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not conspicuous, a different type is used. It may form a dye. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used in combination with the DIR coupler.

The DIR coupler and the DIR compound used are those in which the 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 which are separated by the coupling reaction. Intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like so that the inhibitor is released (referred to as timing DIR coupler and timing DIR compound) are included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A coupling reaction is performed with an oxidized product of an aromatic primary amine developer, but it can also be used in combination with a colorless coupler which does not form a dye and 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 U.S. Pat.No. 1,077,874, JP-B-45-40757, JP-A-47-1031, 47-26133 and 48-.
94432, 50-87650, 51-3631, 52-115219
No. 54-99433, No. 54-133329, No. 56-30127, U.S. Patent Nos. 2,875,057, 3,253,924, 3,265,506.
No. 3,408,194, 3,551,155, 3,551,156,
3,64,841, 3,725,072, 3,730,722, 3,8
91,445, 3,900,483, 3,929,484, 3,933,50
No. 0, 3,973,968, 3,990,896, 4,012,259,
4,022,620, 4,029,508, 4,057,432, 4,1
06,942, 4,133,958, 4,269,936, 4,286,05
No. 3, No. 4,304,845, No. 4314,023, No. 4,336,327,
No. 4,356,258, No. 4,386,155, No. 4,401,752, etc.

As the magenta dye forming coupler, 5-pyrazolone type couplers, prazolobenzimidazole type couplers, pyrazoloazole type couplers and open chain acylacetonitrile type couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used include Japanese Patent Application No. 58-164882,
58-167326, 58-206321, 58-214863, 58-
No. 217339, No. 59-24653, Japanese Patent Publication No. 40-6031, No. 40-6035
Nos. 45-40757, 47-27411, 49-37854, JP-A-50-13041, 51-26541, 51-37646, 51-105.
820, 52-42121, 53-123129, 53-125835
No. 53-1,29035, No. 54-48540, No. 56-29236, No. 5
6-75648, 57-7950, 57-35858, 57-146251
No. 59-99437, British Patent No. 1,252,418, U.S. Patent No. 2,600,788, No. 3,005,712, No. 3,062,653, No. 3,1.
27,269, 3,214,437, 3,253,924, 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,319,
3,582,322, 3,615,506, 3,658,544, 3,7
05,896, 3,725,067, 3,758,309, 3,823,15
No. 6, No. 3,834,908, No. 3,891,445, No. 3,907,571,
3,926,631, 3,928,044, 3,935,015, 3,9
No. 60,571, No. 4,076,533, No. 4,133,686, No. 4,237,21
No. 7, No. 4,241,168, No. 4,264,723, No. 4,301,235,
It is described in No. 4,310,623.

As the cyan dye forming coupler, a naphthol type coupler and a phenol coupler can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent Nos. 1,038,331, 1,543,040, JP-B-48-36894, JP-A-48-59838, 50-137137, 51-146828, and 53.
-105226, 54-115230, 56-29235, 56-10433
No. 3, No. 56-126833, No. 57-133650, No. 57-155538,
57-204545, 58-118643, 59-31953, 59-3
1954, 59-59656, 59-124341, 59-166956
U.S. Pat.Nos. 2,369,929, 2,423,730, 2,434,
No. 272, No. 2,474,293, No. 2,698,794, No. 2,772,162
No., No. 2,801,171, No. 2,895,826, No. 3,253,924,
3,311,476, 3,458,315, 3,476,563, 3,5
91,383, 3,737,316, 3,758,308, 3,767,41
No. 1, 3,790,384, 3,880,661, 3,926,634,
4,004,929, 4,009,035, 4,012,258, 4,0
52,212, 4,124,396, 4,134,766, 4,138,25
No. 8, 4,146,396, 4,149,886, 4,178,183,
4,205,990, 4,254,212, 4,264,722, 4,2
88,532, 4,296,199, 4,296,200, 4,299,91
No. 4, No. 4,333,999, No. 4,334,011, No. 4,386,155,
No. 4,401,752, 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.),
Development accelerator (eg 1-aryl-3-pyrazolidone compound etc.), surfactant (eg alkyl naphthalene sulfonate, alkyl succinate sulfonate,
Itaconic acid salts, polyalkylene oxide compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds and doryphenylmethane compounds), film physical property improving agents ( For example, glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin, etc., color turbidity inhibitor (diffusion-resistant hydroquinone compound etc.), dye image stabilizer (eg hydroquinone derivative, gallic acid derivative, phenol compound, hydroxy) Chroman compounds, polyalkylpiperidine compounds, aromatic amine compounds, etc.), water-soluble or oil-soluble fluorescent whitening agents, ground color tone regulators (oil-soluble coloring dyes, etc.) and the like.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, the hydrophobic compounds are solid. Various methods such as a dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsion dispersion method can be applied with various methods of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point and / or an aqueous solution having a boiling point of about 150 ° C. or higher in an organic solvent having a high boiling point. Using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and an ultrasonic device using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing, 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 the dispersion.

The ratio of high boiling organic solvent to low boiling organic solvent is 1: 0.1 to 1: 5
It is preferably 0, more preferably 1: 1 to 1:20.

As a high-boiling point oil agent, a phenol derivative, a phthalic acid alkyl ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester, etc. having a boiling point of 150 ° C or higher that does not react with the oxidized product of the developing agent 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, 2,835,579 and 3,2.
87,134, 2,353,262, 2,852,383, 3,554,75
No. 5, No. 3,676,137, No. 3,676,142, No. 3,700,454,
3,748,141, 3,779,765, 3,837,863, British Patents 958,441, 1,222,753, OLS2,538,889, JP Sho.
47-1031, 49-90523, 50-23823, 51-26037
No. 51, No. 51-27921, No. 51-27922, No. 51-26035, No. 51
-26036, 50-62632, 53-1520, 53-1521,
53-15127, 54-119921, 54-119922, 55-2
No. 5057, No. 55-36869, No. 56-19049, No. 56-81836,
It is described in Japanese Patent Publication No. 48-29060.

Low boiling or water soluble organic solvents that can be used with or instead of high boiling solvents are described in U.S. Pat.
Examples include those described in No. 2,949,360. The low boiling point substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene and the like, 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 alkyl phenyl ether, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkyl sulfonic acids, and alkyl betaines. It is preferable to use cationic amphoteric surfactants and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants are "Surfactant Handbook" (Sangyo Tosho, 1966),
"Emulsifier emulsifier research and technical data collection" (Kagakugenronsha,
1978).

As the latex dispersion method, for example, U.S. Pat.
No. 3, No. 4,214,047, No. 4,203,716, No. 4,247,627,
JP-A-49-74538, 51-59942, 51-59943, 54
The method described in, for example, No. 32552 is preferable.

When color development processing is carried out using the silver halide photographic light-sensitive material of the present invention, a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step, and / or a stabilization processing step are carried out if necessary. Instead of the processing step using the bleaching solution and the processing step using the fixing solution, the bleach-fixing processing step can be carried out by using the one-bath bleach-fixing solution, and color development, bleaching and fixing can be performed in one bath. It is also possible to carry out a monobath processing step using a one-bath development bleach-fixing processing solution which can be carried out.

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. 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. A typical process is shown among these processes. (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 processing (2) preferably used when processing the silver halide color photographic light-sensitive material of the present invention. The steps will be described in detail.

The color developing agent used in the color developing solution is typically an aromatic primary amine compound, particularly a P-phenylenediamine type, and a preferable example thereof is N, N-diethyl-P-phenol. Nylenediamine hydrochloride, N-ethyl-
P-phenylenediamine hydrochloride, N, N-dimethyl-P-
Phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dotecilamino) -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 kinds of the color developing agents and other black and white developing agents,
For example, it may be used in combination with hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-P-aminophenol. 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, per 1 mol of silver halide contained in the silver chloride color photographic light-sensitive material.

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

Examples of the color developing solution include, in addition to the above color developing solutions, alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate and potassium hydrogen carbonate, and N, N-diethylhydroxylamine. , Preservatives such as triethanolamine and diethanolamine glucose, organic solvents such as methanol, ethanol, butanol, ethylene glycol and diethylene glycol, development regulators such as citrazinic acid and polyethylene glycol and fluorescent brightening agents, heavy metal indulgents, If necessary, various photographic additives known in the photographic field such as 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 it contains an excess of water-soluble bromide,
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 to potassium bromide,
About 0.1 g or less per color developing solution, preferably 0.05
It is less than or equal to g.

The effect of the present invention becomes particularly remarkable when a water-soluble chloride is used as a development modifier in the color developer.

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. Adenine and guanine are preferably 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 preferably 9.5 or higher, more preferably 13 or lower. It has been conventionally known that the development is promoted by increasing the pH of the developer, but in the silver halide photographic light-sensitive material of the present invention, sufficient rapid developability can be obtained even if the pH is 11 or less. .

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

As the bleaching agent used in the bleach-fixing treatment which is carried out subsequent to the color development processing, metal complex salts of organic acids are preferable, and aminopolycarboxylic acids or acids, organic acids such as citric acid and 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] Diethylenetriamine pentaacetic 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 5 to 450 g / l, more preferably 20 ~ 250g
Use with / 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 containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition composed of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

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-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, 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-A-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-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
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower and 3 ° C. or higher, preferably 5 ° C. higher than the processing solution temperature in the color developing tank.
Although it is used at a lower temperature, it is preferably used at 55 ° C or lower while suppressing evaporation and the like.

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

The color light-sensitive material that 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 JP-A-58-2709 and 5
You may perform water washing alternative stabilization treatment as shown in 9-89288 etc.

Color development of the present invention, if the respective liquid bleach-fixing and stabilizing sequentially processes while continuously replenished, replenishment rate of each replenisher color light-sensitive material 1 m ² per 100~1000ml preferably 150
~ 500 ml.

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

(Example-1) A silver halide emulsion was prepared as follows.

Preparation of EM-A Pure Silver Chloride Emulsion A silver nitrate solution and a sodium chloride solution were added to an inert gelatin aqueous solution for 60 minutes by the double jet method. At this time, the temperature was kept at 50 ° C pAg = 7.0.

Then, desalting and washing with water were carried out by a conventional method to obtain EM-A. EM-A
Consists of cubic silver chloride grains with an average grain size of 0.8 μm.

The EM-B silver nitrate solution and the sodium chloride solution were added to the inert gelatin aqueous solution by the double jet method for 60 minutes. Temperature at this time
It was kept at 50 ° C pAg 7.0. Then, a 5 mol% aqueous solution of potassium bromide containing silver nitrate was added for 10 minutes. After that, desalting and washing with water gave EM-B.

The average grain size of silver halide grains contained in EM-B is 0.8 μm.
Met.

EM-C A 95 mol% amount of the silver nitrate aqueous solution and the sodium chloride aqueous solution used in the preparation of EM-A were added to the inert gelatin aqueous solution for 58 minutes by the double jet method. At this time, the temperature is 50 ° C pAg
I tried to keep it at 7.0. However, just before the end, sensitizing dye A
-24 in 0.1% methanol was added.

Next, an aqueous solution of silver nitrate containing 5 mol% of silver nitrate and an aqueous solution of potassium bromide used in the preparation of EM-A were added by a double jet method for 15 minutes. At this time, the temperature was kept at 55 ° C. Then, it was desalted and washed with water to obtain EM-C.

The average grain size of silver halide grains contained in EM-C is 0.8 μm.
Met.

EM-D Same as EM-C except that after adding silver nitrate aqueous solution and potassium bromide aqueous solution, adding hydrogen peroxide, desalting and washing with water.

EM-E In the same manner as EM-C, 75 mol% of the total amount of silver used for grain formation was added during silver chloride formation, and 25 mol% during silver bromide phase formation.
EM-D was obtained by preparing under the conditions to be added.

The average grain size of silver halide grains contained in EM-D is 0.8 μm.
Met.

Sodium thiosulfate was added to the EM-A to E obtained above for sulfur sensitization, and for EM-A, B and D, the sensitizing dye A-24 was added 5 minutes before the end of sulfur sensitization. . After completion of sensitization, 4-hydroxy-6-methyl-1,3,3 was used as a stabilizer.
a, 7-Tetrazaindene was added. Then, 0.4 mol of yellow coupler YC-1 dissolved in dioctyl phthalate was added to 1 mol of silver halide to obtain a silver halide emulsion.
The amount of silver coated on polyethylene resin-coated paper is 0.
The silver halide emulsion was coated so as to have a concentration of 4 g / m ² and gelatin of 2.0 g / m ² . On top of that, gelatin is used as a protective layer.
2.0 g / m ^{2 was} applied to obtain a silver halide photosensitive material sample.

Each of the samples prepared as described above was subjected to wedge exposure using a sensitometer KS-7 type (manufactured by Konishi Rokusha Kogyo Co., Ltd.), and then the following evaluations were performed.

[Evaluation of rapid processability] Each exposed sample was processed according to the following color development processing steps.

[Processing process] Temperature Time Color development 34.7 ± 0.3 ℃ 30 seconds, 50 seconds, 90 seconds Bleach fixing 34.7 ± 0.5 ℃ 50 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Color developer [A ]] Pure water 800 ml Ethylene glycol 10 ml N, N-diethylhydroxylamine 10 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamide ethyl-3
-Methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1g Add water to adjust the total amount to 1 and adjust the pH to 10.08. .

(Bleach-fixing solution) ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g Water was added to adjust the pH to 1 with sulfuric acid or potassium hydroxide.
Adjust to 7.0.

After the treatment was completed, sensitometric measurement was performed with PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.).

Table 1 shows the minimum density (Dmin) at each development time and the relative sensitivity (represented by the relative sensitivity when the sensitivity at 90 seconds is 100 for each sample).

[Evaluation of Variability of BF Solution Mixing] 0.1 ml / l, 0.2 ml of the bleach-fix solution was added to the color developing solution [A].
The color developing solutions [B] and [C] to which each ml / l was added were prepared, and the color developing solutions [A] to [C] were used for processing according to the color developing processing step. However, the color development time was 50 seconds.

After the treatment, sensitometric measurement was performed with a PDA-65 type densitometer. Table 1 shows Δγ _B and Δγ _C.

Here, Δγ _B and Δγ _C are the differences between γ when processed with the color developing solution [B] or [C] and γ when processed with the color developing solution [A]. Represents poor variability.

[gamma]: a value showing the gradation represented by the reciprocal of the logarithmic difference of the respective exposure doses for obtaining the densities of 0.8 and 1.8. The results are shown in Table 1.

The evaluation method of the pressure characteristics is as follows.

[Dry Pressure Property] A ball point needle having a sphere diameter of 0.1 mm was erected vertically on the sample surface, and the sample surface was translated at a speed of 1 cm / sec while a load was applied to the ball point needle at the same time.

After that, each sample was subjected to stepwise exposure with white light using a sensitometer (KS-7 type manufactured by Konishi Rokusha Kogyo Co., Ltd.), and the treatment was performed according to the above-mentioned treatment process. The color density of the applied part and the part not applied pressure can be measured by Sakura Micro Densitometer (PDM-
The measurement was performed in 5) and the following evaluations were performed. In this case, the smaller the ΔD ^D value, the better the pressure resistance.

ΔD ^D = (concentration of a portion where pressure is applied) − (concentration of a portion where pressure is not applied) However, the color development processing time was set to 50 seconds.

The results are shown in Table-1.

From the results shown in Table-1, when silver chloride grains are used, it has a high developing rate, but fog is likely to occur, and BF
Liquid mixing variability is extremely poor. When a high silver chloride grain is used, which has a high silver bromide phase in the outermost shell of the silver halide but no sensitizing dye is added at the time of silver halide grain formation, fogging and BF liquid contamination variability Is improved, but the pressure resistance is poor. On the other hand, when the silver halide grains according to the present invention are used, fogging is suppressed, rapid processability is achieved, and the BF liquid mixture variability and pressure resistance are excellent.

Further, the effects of the present invention can be further enhanced by treating with hydrogen peroxide after the completion of silver halide grains.

However, when silver halide grains having a silver bromide content exceeding the range of the present invention are used, sensitivity in short-time processing is low and rapid processability is largely impaired.

(Example-2) EM-F to J were prepared in the same manner as in EM-C except that the sensitizing dyes shown in Table-2 were used instead of A-24.

EM-F to J were sensitized with sulfur by the method described in Example-1, and then coated samples were prepared and evaluated.

The results are shown in Table-2.

From the results shown in Table-2, it can be seen that even if the sensitizing dye according to the present invention is changed, the excellent effect of the present invention can be similarly obtained.

(Example-3) The following seven layers were sequentially coated on a polyethylene resin-coated paper to prepare a multilayer silver halide photographic light-sensitive material. The addition amount shown below is the amount per 1 m ² unless otherwise specified.

First layer: 1.2 g of gelatin, 0.35 g (in terms of metallic silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion (average particle size 0.8 μm), and
0.9g of yellow coupler YC-1 and 0.015g of 2,5-di-t-
A layer containing dioctyl phthalate (hereinafter referred to as DOP) in which octyl hydroquinone (hereinafter referred to as HQ-1) is dissolved.

Second layer: DOP with 0.7g gelatin and 0.06g HQ-1 dissolved
Containing layers.

Third layer: 1.25 g of gelatin, 0.35 g of green-sensitive silver chlorobromide emulsion (average particle size 0.5 μm), and 0.53 g of magenta coupler MC
-1 and a layer containing DOP with 0.015 g HQ-1 dissolved.

Fourth layer: a layer containing 1.3 g of gelatin, 0.08 g of HQ-1 and 0.5 g of UV absorber (UV-1) dissolved in DOP.

Fifth layer: 1.4 g of gelatin, 0.3 g of red-sensitive silver chlorobromide emulsion (average particle size 0.5 μm), and 0.5 g of cyan coupler CC-1
And a layer containing DOP with 0.02 g of HQ-1 dissolved.

6th layer: a layer containing 0.14 g of DOP in which 1.0 g of gelatin, 0.032 g of HQ-1 and 0.2 g of UV-1 are dissolved.

7th layer: a layer containing 0.5 g of gelatin.

Sample No. 11 was prepared as described above.

As a hardening agent, 0.03 g of 2,4-dicycloro-
6-Hydroxy-S-triazine sodium salt was added. However, as the blue-sensitive silver chlorobromide emulsion for the first layer, an emulsion in which EM-C was sulfur-sensitized by the method described in Example 1 was used.

As the green-sensitive silver chlorobromide emulsion for the third layer, silver halide grains having an average grain size of 0.5 μm were prepared in the same manner as in EM-G, and the emulsion was sulfur-sensitized by the method described in Example-1. Was used.

As the red-sensitive silver chlorobromide emulsion for the fifth layer, silver halide grains having an average grain size of 0.5 μm were prepared in the same manner as in EM-I, and sulfur-sensitized by the method described in Example-1. Was used.

Next, the following sample No. 12 was prepared.

Sample No. 11: The same sample as No. 10 except for the following changes, and the blue-sensitive silver chlorobromide emulsion of the first layer was a blue-sensitive silver chloride emulsion (average grain size 0.8 μm).

The green-sensitive silver chlorobromide emulsion of the third layer was used as a green-sensitive silver chloride emulsion (average particle size 0.5 μm).

The red-sensitive silver chlorobromide emulsion of the fifth layer was used as a red-sensitive silver chloride emulsion (average particle size 0.5 μm).

Sample Nos. 11 and 12 were evaluated by the method described in Example-1.

The results are shown in Table-3.

From the results shown in Table 3, it is clear that the effects of the present invention can be obtained even when applied to a multilayer silver halide photographic light-sensitive material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-55-26589 (JP, A) JP-A-59-48756 (JP, A) JP-A-60-196749 (JP, A) JP-A 58- 95736 (JP, A) JP 59-210437 (JP, A) JP 60-162246 (JP, A) JP 61-205929 (JP, A) JP 61-210345 (JP, A) JP 61-249053 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer of the silver halide emulsion layer is highly sensitive in the presence of a sensitizing dye. A silver halide photographic light-sensitive material characterized by containing silver halide grains having a silver chloride content of 80 to 99 mol% formed by forming a high silver bromide phase on a silver chloride phase.