JPS62254139A - Silver halide photographic sensitive material having improved pressure resistance - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material suitable for rapid processing by forming a silver halide emulsion layer contg. silver halide particles having a specified silver chloride content and obtd. by forming a high bromide type silver halide phase on a high chloride type silver halide phase in the presence of a sensitizing dye. CONSTITUTION:At least one silver halide emulsion layer of this sensitive material contains high chloride type silver halide particles having 80-99mol%, preferably 90-99mol% silver chloride content. The particles have a high bromide type silver halide phase in the outermost shell parts and a sensitizing dye on the inside of the high bromide type silver halide phase. The high bromide type silver halide phase has >=70mol%, preferably >=90mol% silver bromide content. The especially preferred amount of the high bromide type silver halide phase in the outermost shell parts of the particles is 1-10mol% of the amount of the particles.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and specifically, a silver halide photographic material that suppresses fog, is capable of rapid development, and has stable processing in the rapid development path q+2. The present invention relates to a silver halide photographic material having improved properties and excellent resistance to pressure effects.

[Background of the Invention] In recent years, there has been a demand in the industry for silver halide photographic materials that can be processed quickly, have high image quality, have excellent processing stability, and are low cost. ,
Silver halide photographic materials that can be rapidly developed are desired.

In other words, silver halide photographic materials are subjected to running processing in automatic processing machines installed at each processing laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that the development is received. In recent years, there has been a demand for returns to users within a few hours of receipt, and there is an increasing need to develop faster processing methods.

On the other hand, when a silver halide photographic light-sensitive material is continuously processed over a long period of time in a developing laboratory while replenishing a replenisher, changes in the composition of the processing solution may cause photographic properties (particularly gradation fluctuations).
There is a problem in that it causes fluctuations in This problem has become even more serious as processing liquids have become less replenishable in recent years. Silver halide photographic materials (
Hereinafter, it will simply be referred to as a photosensitive material. ), contamination of bleach, fixer, or bleach-fix components into the color developer, and fluctuations in the bromide ion concentration in the color developer. Changes in color change photographic performance and are a major hindrance to achieving stable and good color and gradation reproduction. Among these, contamination of bleach, fixer, or bleach-fixer with developing solution must be completely eliminated, even if strict replenishment rates are set, evaporation is prevented, and eluates from photosensitive materials are eliminated. It is almost impossible to do so, especially in roller conveyance and automatic processing machines, the amount of bleach-fix solution mixed into the developer solution varies greatly depending on the amount of processing and the method of squeezing, and the replenishment rate of processing solution decreases. In this case, the rotational speed of the processing liquid decreases, and the actual situation is that there is a further difference in the mixing rate.

Various improvement measures are being considered in response to the current state and needs of the market. For example, in order to achieve rapid processing, approaches are being taken from two aspects: photosensitive materials and processing solutions. Many attempts have been made to optimize the temperature and pH of the processing solution, and to add additives such as development accelerators, but these methods alone do not achieve sufficient speed, resulting in problems such as increased fog, etc. This is often accompanied by performance deterioration.

On the other hand, the shape, size, and composition of the silver halide grains in the photosensitive silver halide emulsion used in the photosensitive material greatly affect the development speed, etc. It has been found that when a high chloride silver halide is used as the silver, a particularly high development rate is exhibited.

However, light-sensitive materials using high chloride silver halide emulsions, which are the most excellent in terms of rapid processing, are prone to fog, and the above-mentioned effects of performance fluctuations due to mixing of the bleach-fix solution into the developer solution. The problem was that it was very easy to accept, and there was a need for improvement. As a means to solve one of the above problems, in order to prevent fogging of silver halide emulsions,
Various inhibitors are known, and among these, the inhibitor described in U.S. Pat. No. 4,565,774 is very effective in suppressing fog in high chloride silver halide emulsions and is highly processable. There was almost no inhibition, which is excellent, but the effect of improving performance fluctuations due to mixing of the bleach-fixing solution into the developing solution (hereinafter referred to as "BF solution mixing variability") was very small.

Furthermore, it is known that by adding a certain type of mercapto compound to a photosensitive material, fluctuations in BF liquid contamination can be reduced to some extent, but simply adding a mercapto compound to a photosensitive material using high chloride silver halide is known. Adding a mercapto compound alone will have a very small effect, and if a mercapto compound is added before a sufficient effect is achieved, there will be a significant decrease in sensitivity, a severe decrease in processing speed, and furthermore, there will be defects in desilvering. The above two problems could not be solved at the same time.

In order to simultaneously solve the above two problems, a silver halide photosensitive material containing high chloride silver halide grains having a layer mainly composed of silver bromide on the surface is used, as disclosed in JP-A-58-108533. The technology has been disclosed. However, although the silver halide photographic material described in the previous publication has improved fogging properties and BF liquid contamination variability, its pressure resistance has deteriorated considerably, which is a practical problem for silver halide photographic materials. It was found that it had some drawbacks.

The present inventors have continued to study a silver halide photographic material that suppresses the above-mentioned fog, has good BF liquid contamination variability, and has excellent pressure resistance, and as a result, has arrived at the present invention. It is.

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

Generally, various pressures are applied to photosensitive materials.

During the production of photosensitive materials, for example, in the process of cutting the photosensitive materials, a large amount of pressure is applied.

Further, when a photosensitive material is used, especially a sheet photosensitive material, it is often bent because it is handled by humans, and pressure is applied to the bent portion.

On the other hand, in recent years, it has become common for photosensitive materials to undergo automatic exposure using a printer and automatic development using an automatic processor. For this reason, the photosensitive materials are increasingly subjected to mechanical pressure in these devices. When various pressures are applied to the photosensitive material in this way, pressure is also applied to the silver halide grains in the photosensitive material through gelatin, which is a binder for the silver halide grains. When pressure is applied to silver halide grains, photographic properties change, resulting in phenomena such as pressure desensitization and pressure blur.

The theory of tbe P
photographicand E 1M oisa
r): Journal of 7 Autographic Science (J, Photo, Sci, ) +21, 2
21 (1973) etc.

Furthermore, it is well known in the art that silver halide grains of unusually high sensitivity are sensitive to pressure and are prone to pressure desensitization and pressure fog.

In addition, there are cases where photosensitive materials are subjected to pressure in a dry state, and
Pressure may be applied in a wet state during phenomenon processing. Therefore, it cannot be said that the effect is sufficient unless the pressure resistance is improved in both conditions.

For this reason, attempts have been made to provide photosensitive materials that are less affected by pressure.

Known methods for improving the pressure characteristics include a method of incorporating a plasticizer such as a polymer, a method of reducing the silver halide/gelatin ratio, and the like.

For example, British Patent No. 738,618 describes a heterocyclic compound,
Nos. 738 and 637 contain alkyl 7-talates;
No. 38, 639 describes alkyl esters, and U.S. Pat.
, No. 960, 404 contains polyhydric alcohol, No. 3, 12 of the same
No. 1,060 discloses a method using carboxyalkyl cellulose, JP-A No. 49-5017 discloses a method using paraffin and a carboxylic acid salt, and JP-B No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

However, these techniques have the disadvantage that the pressure resistance effect is insufficient in both dry and wet conditions, and furthermore, the binder properties such as stickiness and drying properties of the surface of the photosensitive material are seriously deteriorated.

Furthermore, as a means to improve 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 during the formation of halogen grains, and U.S. Pat. A method using a sensitized modified emulsion is disclosed.

However, the above-mentioned conventional methods do not provide a satisfactory improvement effect and are often accompanied by deterioration of photographic performance.

If fog or desensitization occurs due to these pressure effects, the quality of the silver halide photographic material will be seriously impaired. Furthermore, with rapid processing, pressure effects are becoming more likely to occur due to increased conveyance speeds, and silver halide photographic materials with improved resistance to pressure effects (hereinafter referred to as "pressure resistance") are becoming more susceptible to pressure effects. development is becoming increasingly important.

[Object of the Invention 1 Accordingly, an object of the present invention is to provide a silver halide photographic material which is suitable for rapid processing and has suppressed fog, excellent processing stability, and excellent pressure resistance.

[Structure 1 of the Invention The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers comprises:
High silver chloride grains having a silver chloride content of 80 to 99 mol%, the grains having a high silver bromide silver halide phase in the outermost shell of the grain, and further containing a sensitizing dye in the high silver bromide phase of the outermost shell. This was achieved by providing a silver halide photographic material containing silver halide grains inside a silver halide phase.

[Specific Structure of the Invention] The silver halide grains according to the present invention have silver chloride in an amount of 80 to 99 mol % of the total silver halide composition constituting the grains, and more preferably 90 to 99 mol % of the silver halide grains. range.

There are basically no restrictions on the silver halide composition other than silver chloride, but it is preferable that the silver halide composition consists essentially of silver bromide. Substantially, silver bromide herein refers to 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 in the phase is 70 mol % or more of silver bromide, preferably 90 mol % or more of silver bromide.

The high silver bromide phase may cover the entire surface of the silver halide grains mainly composed of silver chloride, cover a part of the surface, or be epitaxially bonded to the surface. It's okay. The boundary between such high silver bromide and other phases may have a clear phase boundary or may change continuously. Silver bromide accounts for 1 to 20 mol % of the total silver halide constituting the silver halide grains according to the present invention. Although this silver bromide may be present not only in the outermost shell of the silver halide grain but also inside the grain, it is preferable that most of it is contained in the outermost shell of the grain. It is particularly preferable that the high silver bromide phase in the outermost shell of the grain constitutes 1 to 10 mol%.

To define the high silver bromide phase according to the present invention more clearly, when silver halide grains having the above composition are analyzed by X#1 Figure 1 diffraction method, the peak attributed to the high silver bromide phase is as follows: It shows a diffraction pattern that can be clearly distinguished from peaks attributed to a high silver chloride phase other than the high silver bromide 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 80 mol%.
It is particularly preferable that it is above.

The silver halide grains used in the present invention can be preferably used regardless of whether they have Boo) faces, (111) faces, or both. .

The grain size of the silver halide grains used in the present invention may be within the range commonly used, but the average grain size is 0.05 μm.
- ~1.0 μl is preferred. The particle size distribution may be polydisperse or monodisperse, but monodisperse emulsions are more preferably used.

Silver halide grains used in the present invention can be prepared by methods commonly used by those skilled in the art. These methods are described, for example, by Mies, The Theory.
Of Photographic Dispute Process (The T
theory of P photographyP r
It is also described in the fragrance release method such as Mac Ocess (published by MacMittton), and can be adjusted by various generally accepted methods such as the ammonia method, the neutral method, and the acid method.

Regarding the method of adding halide salts and silver salts,
Akari Hirata, Photographic Society of Japan! All of the forward mixing method, back mixing method, and simultaneous mixing method described in Chapter 3 of "Fundamentals of Photographic Engineering - Silver Salt Photography Edition" (Corona Publishing Co., Ltd.) can be used, but mainly bromide Conversion methods can also be used when forming layers made of silver. The silver halide grains according to the present invention are prepared by a simultaneous mixing method in which a halide salt solution and a silver salt solution are simultaneously injected into a reactor and silver halide grains are prepared in the presence of a suitable protective colloid. is particularly preferably used. Is it possible to use simultaneous mixing method? More preferably, a so-called balanced double jet method is used, in which mixing is carried out while adjusting the addition rate of the halide salt solution and silver salt solution so as to maintain the ratio within a certain range. 1) Ag
Preferably, the pH as well as the temperature are controlled at appropriate values during the precipitation.

In the case of forming a layer mainly composed of silver bromide, the bromide ion solution is added after all the 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.

When adjusting silver halide, the pH value should be 2.0~
8.5, especially 3.0 to 7.5 is preferred. The pAg value varies somewhat depending on each stage of silver halide grain preparation (depending on the halogen composition), but in the preparation of high-silver chloride silver halide grains according to the present invention, a value of 6.0 to 8.5 is preferable. However, particularly preferred is the case of 7.0 to 8.0. For the formation of a phase consisting mainly of silver bromide, pAg = 7.0
-10.0 is preferred, and particularly preferred is 8.
．． This is the case when it is 0 to 9.5. The temperature is 40-8
5°C, especially 45-75°C is preferred.

Various apparatuses have been proposed for preparing such silver halide grains. For example, as described in Japanese Patent Publication No. 48-21045, a rapid precipitation reaction is carried out by strong stirring in a relatively small precipitation chamber, and a very rapid precipitation reaction is carried out. A method in which physical ripening is carried out in a large-volume ripening chamber, and the resulting dispersion is recycled into a precipitation chamber to serve as a medium for precipitation of silver halide. A precipitation chamber is submerged in the reactor described in Japanese Patent Publication No. 49-48964, and a silver salt solution and a halide salt solution are introduced into the solution in different parts of the precipitation chamber, diluted with the solution in the reactor, and then mixed. Then, a rapid precipitation reaction is carried out, and then the dispersion is discharged into a reactor outside the precipitation chamber, and physical ripening is carried out.
There is a method of introducing the dispersion into the precipitation chamber again and using it as a medium for precipitation of silver halide. These devices can be particularly preferably used for preparing the silver halide emulsion according to the present invention.

The silver halide emulsion may or may not be physically ripened. After the emulsion is precipitated or physically ripened, soluble salts are usually removed, and methods used for this purpose include the long-known noodle washing method as well as the removal of inorganic salts containing polyvalent anions (e.g. ammonium sulfate). (magnesium sulfate), anionic surfactants, polystyrene sulfonic acid, other 7-ionic polymers, or gelatin derivatives such as aliphatic- or aromatic-acylated gelatin (70 days). May be used.

The silver halide grains according to the present invention have a sensitizing dye inside the high silver bromide silver halide phase in the outermost shell of the grain.

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

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. These colors'#,
The class ends with the application of any of the nuclei commonly utilized in cyanine dyes as basic heterocyclic nuclei. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, 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, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohyguntoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc., may be applied. Sensitizing dyes useful in the present invention include, for example, West German Patent No. 929.080, US Pat. No. 2,231.658, and US Pat.
No. 8, No. 2,503,776, No. 2,519,001
No. 2,912,329, No. 3,656, 9
No. 59, No. 3,672.897, No. 3,694,21
No. 7, No. 4.025,349, No. 4,046,572
No., British Patent 1, No. 242.588, Special Publication No. 1977-1
4030, 52-24844, and the like. Also useful sensitizing dyes include:
For example, US Pat. No. 1,939.201, US Pat. No. 2,072,
No. 908, No. 2,739.149, No. 2,945,
Typical examples include the cyanine dyes, merocyanin dyes, and complex cyanine dyes described in No. 763, British Patent No. 505,979, and the like. Useful sensitizing dyes include, for example, U.S. Pat.
．． No. 234, No. 2,270,378, No. 2,442.
No. 710, No. 2,454.629, No. 2,776.2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes described in No. 80 and the like. Furthermore, U.S. Patent 2.213
, No. 995, No. 2,493,748, No. 2,519
．． Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 001, West German Patent No. 929,080, etc. 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 [AI].

General formula [AI In the general formula [AI, Zl and Zl2 are respectively a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus,
Represents a group of atoms necessary to form a naphthimidazole nucleus, a pyridine nucleus, or a quinoline nucleus, and these heterocycles include those with substituents. Substituents of the heterocycle formed by Zl and Zl□ As, halogen atom,
Examples include a hydroxyl group, a cyano group, an aryl group, an alkyl group, and an alkoxycarbonyl group. Among these substituents, preferred substituents include a halogen atom, a cyano group,
An aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred substituents include a halogen atom,
A cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R21 and R2□ each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably an alkyl group substituted with a carboxyl group or a sulfo group. 1 to 4 sulfoalkyl groups. Also R2
3 is selected from a hydrogen atom, a methyl group, and an ethyl group. Xe
represents an anion, and l represents O or 1.

Among the sensitizing dyes represented by the general formula [AI], a particularly useful dye is a sensitizing dye represented by the following general formula [A″].

General formula [A'1 Here, YI and Y2 each represent an optionally substituted benzene ring or an atomic group necessary to complete the 7talene ring. The benzene ring and naphthalene ring formed by Yl and Y2 include those having a substituent, and the substituent is preferably a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. It is the basis. More preferred substituents are a halogen atom, a Schiff group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. It is the basis.

e R21, R22, R2! , X and l are general formula [A]
This is the same as shown in .

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

-LIj~4 General formula [Heko 8-7 He-9 He-10 8-12 A-13 8-15 8-18 8-23 8-24 In this Komei, used for flavor Aa halogenated milk creation 1. As an A color system. t, the following general 4caJ is Ho' Satoru Yosho 6 series Po@-is.

General Formula [B] In the formula, Zll and Z1□ each represent an atomic group necessary to form a benzene ring or a 7talene ring fused to an oxazole. The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are a halogen atom, a ring group, an alkyl group, or an alkoxy group. More preferred substituents are a halogen atom, a 7-enyl group, and a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the invention, Zll and Z7
2 both represent benzene rings fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or the 5-position of one benzene ring is a phenyl group, and the other benzene ring is substituted with a phenyl group. The 5th position of is substituted with a halogen atom.

R21 and R22 each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group, more preferably R2+ and R22 are
Each is an alkyl group substituted with a carboxyl group or a sulfo group, most preferably having 1 to 4 carbon atoms.
is a sulfoalkyl group. Most preferred is a sulfoethyl group.

RXS represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

X1o represents an anion, such as chlorine, OCHs
Examples include anions such as S 04 and Cx Hs SO4. 1 represents 1 or 0, provided that n represents 0 when the compound forms an inner salt.

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

[3-11 Below Yuzukizu [B -21 [8-3] [B-4] [8-5] [B -6] [8-7] [B-8] [B, -10] [C1 , -11] 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] or a sensitizing dye represented by the following general formula [D]. .

General formula [C] RI R2 (XO) 1-1 General formula [D] (XO) 1-1 In the formula, R represents a hydrogen atom or an alkyl group, R8 to R1 represent an alkyl group and an aryl group, respectively, Z
l, Z2, Z- and Z5 each represent an atomic group necessary to form a benzene ring or a 7talene ring condensed to a thiazole ring or selenazole ring, and Z3 is a hydrocarbon atom necessary to form a hexashell ring. represents a group, p is 1
or 2, Z represents a sulfur atom or a selenium atom, and XO represents an anion.

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, and an ethyl group. Particularly preferred are a hydrogen atom and an ethyl group.

Further, R, , R2, R, and R1 are each a linear or branched alkyl group, and this alkyl group may have a substituent. (e.g. methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy-γ-sulfopropyl, sulfopropyl, (allyl, pencil, etc.) or an aryl group, and this aryl group may have a substituent. (for example, phenyl, carboxyphenyl, sulfophenyl, etc.), and represents a group selected from Zl, Z2, Z
, and the heterocyclic nucleus formed by Z5 may have a substituent, and preferred substituents are a halogen atom, an aryl group, an alkyl group, or an alkoxy group,
Furthermore, halogen atoms (e.g. chlorine atoms), phenyl groups,
A methoxy group is preferred.

X is an anion (e.g. C1', Br, I.

, and l represents 1 or 2.

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

Typical specific examples of the sensitizing dyes represented by the general formulas [C] and [D] that are preferably used in the present invention are shown below.

The method for adding the sensitizing dye is well known in the art (it can be done by using a known method) .

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and If necessary, they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibrations for this dissolution.

Furthermore, the sensitizing dye used in the present invention is disclosed in US Pat.
69,987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added. Similarly, a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. 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 and dispersion method. Other methods of addition include U.S. Patent No. 2,912.3.
No. 45, No. 3, 342,605, No. 2.996.
The methods described in No. 287, No. 3,425.835, etc. can also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvents, and these solutions may be mixed or added separately prior to addition to the silver halide emulsion. . When adding them separately, the order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion so that it is inside the rotten silver bromide silver halide phase of the outermost shell. It may be added at any time during the progress of forming a rotten silver bromide silver halide phase, from before the nucleation of high silver chloride grains of ~99 mol %, or may be added in portions. It is preferable to add it from the end of the formation of high silver chloride silver halide grains to the progress of formation of a rotten silver bromide silver halide phase, that is, to the surface of the high silver chloride silver halide phase.

The amount of the sensitizing dye added is not particularly limited as long as the effects of the present invention are achieved, but it is preferably in the range of 2 x 10-a to 1 x 10-3 mol per mol of silver halide. Yes, more preferably 5 x 10-6 to 5 x 10
−' molar range. Furthermore, after adding the sensitizing dye, the sensitizing dye may be deactivated by using an oxidizing agent such as hydrogen peroxide as needed, which is one of the preferred embodiments. In this case, a new optional sensitizing dye may be added at the stage of chemical sensitization depending on the purpose.

The silver decadenide grains having a sensitizing dye according to the present invention are
It may be obtained by any of the acidic method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the PAg-chondrold double-jet method described in No. 48521 and the like.

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

The silver halide grains having a sensitizing dye according to the present invention can be prepared by using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, a rhodium salt or a complex salt, Metal ions can be added to the interior of the particles and/or on the surface of the particles using iron salts or complex salts, and can be reduced to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

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

However, in order to fully exhibit the effects of the present invention, it is necessary to carry out chemical sensitization after silver halide grain formation, that is, before chemical sensitization, and if chemical sensitization is performed during silver halide grain formation, halogen After the silver particles are finally formed,
It is preferable to avoid the application of silver halide grains of the type that primarily form latent images within them. To determine whether silver halide grains are of the internal latent image type, Japanese Patent Publication No. 52-342
The evaluation may be made according to the method described in No. 13.

That is, about 300 to 400 mg/f of the emulsion to be evaluated.
Coat on a polyethylene coated support at a silver coverage of t2. The sample is divided into two halves and each is subjected to a light-intensity scale exposure using a 500 W tungsten lamp for a fixed time period of I x 10''-2 to 1 second.

One of the samples was prepared in the following developer Y (r internal type developer).
Development was carried out at 8.3°C for 15 minutes, and the other one was developed at 20°C for 6 minutes in the following developer X (r surface type developer).

In the present invention, it is preferable to use silver halide grains in which the maximum density after internal development/maximum density after surface development is 5 or less, more preferably 2 or less.

[X N-methyl-p-aminophenol sal 7A) 2.59 Ascorbic acid 10.0g Potassium metaborate 35.0g Potassium bromide
Add 1.0g water
11 (pH = 9.6) 1 East N-methyl-p-aminophenol sulfate 2.0 g Sodium sulfite (dry) 90.0 g Hydroquinone 8.0 g Sodium carbonate/I H2052, 5 g Potassium bromide
5.0g potassium iodide
Add 0.5g water 11
(pH = 10.06) The silver halide emulsion containing the silver halide grains according to the present invention (hereinafter referred to as the silver halide emulsion of the present invention) is free from unnecessary soluble salts after the growth of the silver halide grains is completed. It may be removed or may remain contained. In the case of removing the salts, it can be carried out based on 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, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention is further spectrally sensitized to a desired wavelength range 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.

Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, after chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing capri during storage or photographic processing, or to maintain stable photographic performance. This can be alleviated by adding compounds known in the photographic industry as anti-capri agents or stabilizers.

As an anti-capri agent and a stabilizer, US Pat. No. 2.713
．． No. 541, No. 2,743,180, No. 2,743.
Pentazaindenes described in U.S. Pat. No. 181, U.S. Pat. No. 2,716.062, U.S. Pat.
, No. 444.605, No. 2.756,147, No. 2.
No. 835.581, No. 2,852,375, Research No. Disclosure + - (Research D 1sc
tetrazaindenes described in US Pat. No. 2,772.164, and JP-A-57-211142.
Azaindenes such as polymerized azaindenes described in U.S. Patent Nos. 2,131.038 and 3,34
2.596, thiazolium salts described in U.S. Pat. No. 3,954.478, biryllium salts described in U.S. Pat. Quaternary onium salts; U.S. Patent Nos. 2.403.927 and 3,266.897
No. 3,708,303, JP-A-55-1:11
Mercaptotetrazoles, mercaptotriazoles, and mercaptothiazoles described in No. 5835 and No. 59-71047; mercaptothiazoles described in U.S. Patent No. 2.824.001;
Mercaptobenzthiazoles described in No. 397,987, Mercaptobenzthiazoles, U.S. Pat.
．． mercapto-substituted heterocyclic compounds such as mercaptooxadiazoles described in US Pat. No. 843,491; mercaptothiadiazoles described in US Pat. No. 3,364,028; US Pat. Catechols described in Japanese Patent Publication No. 43-10256, resorcinols described in Japanese Patent Publication No. 56-44413, and polyhydroxybenzenes such as gallic acid esters described in Japanese Patent Publication No. 43-4133; West German Patent No. 1,189
, 380, U.S. Pat.
．． 157,509, benzenetriazoles described in U.S. Pat. No. 2,704,721, urazoles described in U.S. Pat. No. 3,287,135, U.S. Pat. No. 3,106. , 467, U.S. Patent No. 2,271,22
Ingsols described in No. 9 and JP-A-59-9
Azoles such as polymerized benztriazoles described in US Pat. No. 0844, pyrimidines described in US Pat. No. 3,161,515, US Pat.
Heterocyclic compounds such as the 3-pyrazolidones described in No. 7 and the polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat.
JP 54-130929, JP 59-137945, JP 140445, British Patent No. 1.356,142, U.S. Patent No. 3,575.699, JP 3,649.2
Various inhibitor precursors described in US Pat. No. 67, etc.; sulfinic acids and sulfonic acid derivatives described in US Pat. No. 3,047.393; US Pat. No. 2,566.263
There are inorganic salts described in No. 2,839,405, No. 2,488,709, and No. 2,728.663.

Gelatin is advantageously used as the binder (or protective colloid) in the silver halide emulsion of the present invention, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, and cellulose derivatives may also be used. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as monopolymers or copolymers can also be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bulletin on Society on Science on 7 Oscigraphies on Japan (Bull
, Sac, Sci, Phot, Japan)No,
16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The one obtained by doing so is used. Specific examples include U.S. Patent Nos. 2,614,928 and 3
, No. 132,945, No. 3.186,846, No. 3,
312,553, British Patent No. 861,414, 1.
No. 033,189, No. 1,005,784, Special Publication No. 4
2-28845, etc.

Preferred proteins include albumin and casein; preferred cellulose derivatives include hydroxydityl cellulose, carboxymethyl cellulose, and cellulose sulfate; and preferred sugar derivatives include sodium aluminate and starch derivatives.

The graft polymer of gelatin and other polymers may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. A grafted material can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
, No. 763,625, No. 2,831,767, No. 2.
No. 956.884, etc.

Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N-
Single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrazole, etc., for example, West German patent application (OL S) 2,312.708
No. 3,620,751, U.S. Patent No. 3,879
, No. 205, and Japanese Patent Publication No. 43-7561.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention may contain one or more hardeners that cross-link bainggu (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. The hardening agent can be added in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

Hardening agents include aldehyde-based and aziridine-based (for example, PB Report, 19,921, U.S. Patent No. 2.95).
No. 0.197, No. 2,964,404, No. 2,
Specifications of No. 983.611 and No. 3,271,175, Japanese Patent Publication No. 46-40898, and Japanese Patent Application Laid-open No. 50-913
No. 15 (described in each publication), isoxazole type (
For example, those described in U.S. Pat. No. 331,609), epoxy systems (for example, those described in U.S. Pat. No. 3,047,39)
No. 4, West German Patent No. 1,085゜663, British Patent No. 1
．． Specifications of No. 033,518, Japanese Patent Publication No. 48-3549
(described in Publication No. 5), vinyl sulfone type (e.g. PB Revo) 19,920, West German Patent No. 1,10
No. 0,942, No. 2,337.412, No. 2,545
, No. 722, No. 2,635,518, No. 2,742,
No. 308, No. 2,749°260, British Patent No. 1.2
No. 51.091, Japanese Patent Application No. 45-54236, No. 48-
No. 110996, U.S. Pat. No. 3,539.644, U.S. Pat. , 720), carbodiimide systems (for example, U.S. Pat. No. 2,938
．． No. 892, No. 4,043,818, No. 4.061,
Specifications of No. 499, Japanese Patent Publication No. 46-38715,
(described in Japanese Patent Application No. 49-15095), triazine-based (for example, West German Patent No. 2,410,973,
No. 2,553,915, U.S. Patent No. 3,325.28
7 specifications, those described in JP-A-52-12722), polymer type (for example, British Patent No. 822,06)
No. 1, U.S. Patent No. 3,623,878, U.S. Patent No. 3,396
, No. 029, Specifications of No. 3,226,234, Japanese Patent Publication No. 18578/1978, No. 18579, No. 47-48
896) and other maleimide series,
Acetylene hardeners, methanesulfonic acid ester hardeners, and N-methylol hardeners can be used alone or in combination. West German Patent No. 2.4 as a useful combination technology
No. 47.587, No. 2,505.746, No. 2.51
No. 4,245, U.S. Patent No. 4,047,957, U.S. Patent No. 3
, No. 832.181, No. 3,840,370, JP-A No. 48-43319, No. 50-63082, No. 52-127329, and Japanese Patent Publication No. 48-32364. Examples include combinations.

Pigment formation using the silver halide emulsion of the present invention to form a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-7 enylene diamine derivative, aminophenol derivative, etc.) for color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive 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, depending on the purpose, the silver halide color photographic material may be used in a manner different from the above combination.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are tetravalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye, only two molecules of silver ions need to be reduced. It may be either 2-equivalent. Dye-forming couplers can be combined with oxidized forms of developing agents to produce development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, hardener capri agents, antifoggants, chemical sensitizers, Compounds that release photographically useful 7-ragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or D that releases development inhibitors during development to improve image sharpness and image graininess.
An IR coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and release a development inhibitor at the same time.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. timing DIR couplers, and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler which performs a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that may be used include U.S. Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 4B-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 5B=-30127, U.S. Patent No. 2,8
No. 75,057, No. 3,253.924, No. 3,26
5.506, 3,408,194, 3,551
, No. 155, No. 3,551,158, No. 3,664,
No. 841, No. 3,725,072, No. 3,730.7
No. 22, No. 3,891,445, No. 3,900,48
No. 3, No. 3,929,484, No. 3,933,500
No. 3,973,968, 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
, No. 269.936, No. 4,286,053, No. 4,
No. 304,845, No. 4,314.023, No. 4,
336, 327, 4,356,258, 4,
It is described in No. 386.155, No. 4,401,752, etc.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers, and open-chain acylacetonitrile couplers are preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-1648.
No. 82, No. 5B-167326, No. 58-20632
No. 1, No. 58-214863, No. 58-217339
No. 59-24653, Special Publication No. 40-6031,
No. 40-6035, No. 45-40757, No. 47-
No. 27411, No. 49-37854, Japanese Unexamined Patent Publication No. 1983-1
No. 3041, No. 51-28541, No. 51-3764
No. 6, No. 51-105820, No. 52-42121, No. 53-123129, No. 53-125835,
No. 53-129035, No. 54-48540, No. 5
Ei No. 29236, No. 5B-75648, No. 5 Fu 17950, No. 57-35858, No. 57-14
No. 6251, No. 59-99437, British Patent Nos. 1 and 2
52,418, U.S. Patent No. 2,600,788, U.S. Patent No. 3,005,712, U.S. Patent No. 3,062.653, U.S. Patent No. 3
, No. 127,269, No. 3,214.437, No. 3,
No. 253.924, Id.: ll, No. 311,476, Id. 3
, No. 419,391, No. 3.519,429, No. 3.
55L319, 3,582,322, L615
．． Soe No. 3,658,544, No. 3,705,
No. 896, No. 3,725,067, No. 3,758,3
No. 09, No. 3,823,158, No. 3,834.90
No. 8, No. 3,891,445, No. 3,907.571
No. 3,926,631, No. 3,928,044, No. 3,935,015, No. 3,960.571,
4,076.533, 4,133,686, 4,237,217, 4.241.168, 4
, No. 264, 723, 4. :1101.235, No. 4,310,623, 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 include British Patent No. 1,038.3'31, British Patent No. 1,543.040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838,
No. 50-137137, No. 51-146828, No. 53-105226, No. 54-11'1d30, No. 56-29235%, No. 56-104333, No. 56
-126833, 57-133650, 5fu 155538, 57-204545, 58-1
No. 18643, No. 59-31953, No. 59-319
No. 54, No. 59-59656, No. 59-124341
No. 59-186956, U.S. Patent No. 2,369.
No. 929, No. 2,423,730, No. 2,434,2
No. 72, No. 2,474,293, No. 2,698,79
No. 4, No. 2,772.162, No. 2,801.171
No. 2,895,826, No. 3,253.924, No. 3,311,476, No. 3,458.315,
3,476.563, 3,591.383, 3,737,316, 3,758,308, 3
, 767.411, 3,790.384, 3,
No. 880,661, No. 3,926,634, No. 4.0
No. 04,929, No. 4,009,035, No. 4,01
No. 2,258, No. 4,052,212, No. 4,124
, No. 396, No. 4,134,766, No. 4,138,
No. 258, No. 4,146,396, No. 4,149.8
No. 86, No. 4,178,183, No. 4,205,99
No. 0, No. 4,254,212, No. 4,264,722
No. 4,288,532, No. 4,296,199, No. 4,296,200, No. 4,299,914,
No. 4,333,999, No. 4,334.011, No. 4,386.155, No. 4,401,752, No. 4
, No. 427, 767, etc.

P Lid and Below Both Sections 1 In addition to the above-mentioned compounds, various photographic additives can be added to the silver halide photographic material containing the silver halide emulsion of the present invention.

Examples include ultraviolet absorbers (e.g. benzophenone compounds, benzotriazole compounds, etc.),
Development accelerators (e.g. 1-aryl-3-pyrazolidone compounds, etc.), surfactants (e.g. alkylnaphthalene sulfonates, alkyl succinate ester sulfonates,
itafunic acid salts, polyalkylene oxide compounds, etc.), water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds, and do'J7xylmethane compounds, etc.), membranes. Physical property improvers (e.g. glycerin, polyalkylene glycol, polymer latex, solid or liquid paraffin, etc.), color clouding preventive agents (diffusion-resistant hydroquinone compounds, etc.), dye image stabilizers (e.g. hydroquinone derivatives, gallic acid derivatives, phenol) hydroxychroman-based compounds, polyalkylpiperidine-based compounds, aromatic amine-based compounds, etc.), water-soluble or oil-soluble optical brighteners, ground color tone regulators (oil-soluble colored dyes, etc.), and the like.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water soluble one as necessary. Dissolve the gelatin in a gelatin aqueous solution using a surfactant and a stirrer.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, 70-jit mixer, or ultrasonic device,
It may be added to the desired hydrophilic colloid layer. Low boiling point at the same time as dispersion or dispersion 8! A step of removing the solvent may be included.

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

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, 1L fragrant esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with a boiling point of 150°C or higher. of organic solvents are used.

Examples of high-boiling organic solvents that can be used include U.S. Pat. No. 2,322,027, U.S. Pat.
, No. 353,262, No. 2,852,383, No. 3,
No. 554,755, No. 3,676.137, No. 3,6
No. 76.142, No. 3,700,454, No. 3,74
8゜141, 3,779,765, 3,837
, No. 863, British Patent No. 958,441, No. 1,222
．． No. 753, 0LS2.538,889, JP-A-1973-
No. 1031, No. 49-9052:11, No. 50-23
No. 823, No. 51-26037, No. 51-27921
No. 51-27922, No. 51-26035, No. 51-26036, No. 5 (No. 1-62632, No. 53)
-1520, 53-1521, 53-1512
No. 7, No. 54-119921, No. 54-119922
No. 55-25057, No. 55-36869, No. 56-19049, No. 56-81836, Special Publication No. 4
No. 111-29060.

Low-boiling or water-soluble organic solvents that can be used in conjunction with or in place of high-boiling solvents are disclosed in U.S. Pat.
Examples include those described in No. 1 and No. 2,949,360. Low boiling point virtually insoluble in water t9
1 Solvents include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, Methoxyglycol acetate, methanol, ethanol,
Acetonitrile, dioxane, dimethylformamide,
Examples include dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.

Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyesters. Anionic surfactants such as oxyethylene alkylphenyl ether, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkyl sulfonic acids, and alkyl betaines. It is preferred to use amphoteric surfactants, such as, and cationic surfactants, such as No. 41iC ammonium salts. Specific examples of these surfactants can be found in “Surfactant Handbook” (Sangyo Tosho, 196
6th grade) and [Emulsifier, emulsifying equipment research and technical data collection]
(Science Panronsha, 1978).

As a latex dispersion method, for example, US Patent No. 4.19
No. 9,363, No. 4,214,047, No. 4,203
．． No. 716, No. 4,247,627, Japanese Unexamined Patent Publication No. 1977-7
No. 4538, No. 51-59942, No. 51-5994
The method described in No. 3, No. 54-32552, etc. is preferred.

When carrying out color development using the silver halide photographic material of the present invention, a color development process, a bleaching process, a fixing process, and if necessary a water washing process and/or a stabilizing process are carried out. Bleach 8! Instead of the process using a 100% bleach-fixing solution and the processing process using a fixing solution, it is also possible to carry out a whiteboard fixing process using a 100% bleach-fix solution, or to carry out color development, bleaching, and fixing in a 100% solution. It is also possible to carry out a more bath processing step using a 1-yield bleach-fix processing solution.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed instead of the monobath process. Beta treatment, bleaching, and fixing treatments may be performed simultaneously. Representative treatments among these treatments are shown below.

(These treatments are carried out as a cutting process, including a washing process, a stabilization process, a washing process, and a stabilization process.) (1) Color development process - bleaching process, fixed fixation process (2) ) Color development process - Bleach-fixing process (3) Pre-hardening process - Neutralization process - Color development process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Posterior sclerosis treatment step (4) Color development treatment step - Water washing treatment step - Supplementary color development treatment step - Stop treatment step - Bleaching treatment process Constant fixation treatment step (5) Morebath treatment step (6) Activator treatment step - Bleach fixing Processing step (7) Activator treatment step - Bleaching treatment step Fixed fixation treatment step The treatment step (2) which is preferably used in processing the silver halide color photographic light-sensitive material of the present invention will be described in detail below.

The color developing agent used in the color developing solution is typically an aromatic primary amine compound, particularly a P-7 di-2-diamine compound, and preferred examples include it, N, N.
-7 Ethyl-P-phenylenediamine hydrochloride, N-ethyl-P-'phenylenediamine hydrochloride, N,N-dimethyl-P-7 2-2-diamine hydrochloride, 2-7 Minnow 5-
(N-ethyl-N-dotecylamino)-toluene, N-
Ethyl-N-(β-methanesulfonamidoethyl)-3
-Methyl-4-7minoaniline sulfate, N-ethyl-N
-β-hydroxyethylaminoaniline, 4-amino-
N-(2-methoxyethyl)-N-ethyl-3-methylaniline-P-)luenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N
-(β-hydroxyethyl)-3-methyl-4-7minoaniline and the like can be mentioned. These color developing agents may be used alone or in combination of two or more, and one or more of these color developing agents and other black and white developing agents such as hydroquinone, 1-phenyl-3-
It may be used in combination with pyrazolidone and N-methyl-P-aminophenols.

This color developing agent may be included 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 mol to 2 mol per mol of silver halide contained in the silver chloride color photographic light-sensitive material.
Preferably it is in the range of 0.4 mol to 0.7 mol.

When color developing the silver halide photographic material of the present invention, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amino may be used as a color developing agent. Aniline sulfate is particularly preferred.

In addition to the above-mentioned color developing solution, the color developing solution includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, and N,N-diethylhydroxylamine. , preservatives such as triethanolamine, jetanolamine glucose, organic mw such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol,
Various photographic additives known in the photographic field, such as development regulators such as citradinic acid and polyethylene glycol, optical brighteners, heavy metal ion moderating agents, and development accelerators, can be contained as necessary.

The silver chloride color photographic light-sensitive material of the present invention is developed with a color developing solution that does not contain any water-soluble bromide or contains a very small amount of water-soluble bromide. When containing excess water-soluble bromide,
The development speed of the silver chloride color photographic light-sensitive material is drastically reduced, making it impossible to achieve the object of the present invention. The bromide ion concentration in the color developer is converted to potassium bromide,
The amount is approximately 0.1 g or less, preferably 0.05 g or less per color developer 11.

The effects of the present invention are particularly apparent when a water-soluble chloride is used as a development regulator in the color developing solution.

The water-soluble chloride used is converted into potassium chloride in an amount of 0.5. ~5g, preferably 1g to 3g.

In the color developing solution, an organic development inhibitor described in Japanese Patent Application Laid-open No. 58-95345 can be further used as long as it does not impair the present invention. Preferably, adenine and guanine are used in the color developing solution in an amount of O 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 conventionally been known that development is promoted by increasing the pH of the developing solution, but in the silver halide photographic material of the present invention, the pH
Even if it is 11 or less, sufficient rapid developability can be obtained.

The temperature of the color developing solution is 15-45°C, preferably 20-40°C.
It is carried out between ℃.

The bleaching agent used in the bleach-fixing process that is carried out subsequent to the color development process is preferably a metal complex salt of an organic acid. It is a coordinated ion. The most preferred organic acids used to form such metal complex salts of organic acids include polycarboxylic acids. 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.

[11 Ethylenediaminetetraacetic acid [21 Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
'-Triacetic acid [41 Propylenediaminetetraacetic acid [51 Nitrilo[lyacetic acid] [6] Cyclohexanediaminetetraacetic acid [71 Iminodiacetic acid] [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] Glyfur ether diamine tetraacetic acid [11] Ethylenediamine tetraprobionic acid [12]7. Nylenediaminetetraacetic acid [131 Ethylenediaminetetraacetic acid disodium salt [141 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt] [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt 1171 Ethylenediamine-N-(β-oxyethyl )
N,N',N''-Triacetic acid sodium salt [181 Propylenecyamine tetraacetic acid sodium salt [19] 2) Liloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches are 5-450g #!, More preferably, it is used in a range of 20 to 250.71.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I[[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, ammonium bromide Bleach-fix solutions containing a large amount of halides such as iron ethylenediaminetetraacetate (
[1] A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, 17 um bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples thereof include thiosulfate such as ammonium sulfate, potassium thiocyanate, fluorium thiocyanate, thiocyanate such as ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g/l or more, within the range that can be dissolved, but generally 70 g/l to 250 g/l.
Use with.

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 may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydroxyl, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfamide, dimethyl An organic solvent such as sulfoxide can be appropriately contained.

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

The pH of the bleach-fix solution is used at 4.0 or higher, but it is generally used at a pH of 5.0 or higher and 9.5 or lower, preferably at a pH of 6.0 or higher and 8.5 or lower, and more specifically, the most preferred pH is is processed at 6.5 or more and 8.5 or less. The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation.

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

Color photosensitive materials that have been subjected to color development and bleach-fixing processes need to be washed with water to remove unnecessary processing chemicals, but instead of washing with water, Japanese Patent Application Laid-Open Nos. 58-14834 and 58-105
No. 145, No. 5B-134634 and No. 5B, -18
[! No. 31 and JP-A-58-2709 and JP-A-58-2709-
A stabilization treatment as an alternative to water washing as shown in No. 89288 may also be performed.

When processing is carried out while continuously replenishing the color developing, bleach-fixing and stabilizing solutions of the present invention, the replenishment rate of each replenisher is 100 to 100k per 112 liters of color photosensitive material.
It is preferably 150 to 500 mN.

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

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

EM-A Preparation of 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 a double jet method. At this time, the temperature was maintained at 50° C. pAg=7.0.

Next, desalting and washing with water were performed by a conventional method to obtain EM-A.

EM-A consists of cubic silver chloride grains with an average grain size of 0.8 microns.

EM-B A silver nitrate solution and a sodium chloride solution were added to an inert aqueous gelatin solution for 60 minutes using a double jet method. At this time, the temperature was maintained at 50'CpA g7.0. Then, 1 mol% potassium bromide aqueous solution of silver nitrate was added.
Added for 0 minutes. Thereafter, EM-B was obtained by desalting and washing with water.

The average grain size of the silver halide grains contained in EM-B is 0.
It was an 8μ ship.

EM-C A silver nitrate aqueous solution in an amount of 95 mol% of the amount used in preparing EM-A and an IJium aqueous solution were added to an inert gelatin aqueous solution for 58 minutes by a double jet method. At this time, the temperature was maintained at 50° C. pAg=7.0. TaP:
t, 0.1% of A color NA-24
A methanol solution was added.

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

The average grain size of the silver halide grains contained in EM-C is 0.
It was an 8μ spear.

EM-D Silver halide emulsion same as EM-C except that hydrogen peroxide was added after addition of silver nitrate aqueous solution and potassium bromide aqueous solution, and then desalted and washed with water.

EM-E By the same operation as EM-C, 75 mol% of the amount of gold and silver used for grain formation was added during silver chloride formation, and silver bromide phase age 2
EM-D was prepared under conditions such that 5 mol% was added.

The average grain size of the silver halide grains contained in EM-D is 0.
It was 8 μm.

EM-A-E obtained above was subjected to sulfur sensitization by adding sodium thiosulfate, and for EM-A, B, and D, sensitizing dye A-24 was added 5 minutes before the end of sulfur sensitization. . After completion of sensitization, 4-hydroxy-6-methyl-1,3,3aI7-tetrazaindene was added as a stabilizer.

Next, 0.4 mol of yellow coupler YC-1 dissolved in dioctyl 7 tallate was added per mol of silver halide to obtain a silver halide emulsion, and the amount of silver coated on polyethylene resin-coated paper was 0.4 g/m2 as metallic silver. , gelatin 2
．． The above silver halide emulsion was coated on a surface of 0g7m2. Furthermore, add 2.0g of gelatin7 as a protective layer on top of that.
m'' coating to obtain a silver halide photosensitive material sample.

Each sample prepared as described above was subjected to wedge exposure using a photosensitive needle KS-7 model (manufactured by Konishiroku Photo Industry Co., Ltd.), and then the following evaluations were performed.

[Evaluation of rapid processability] Each sample of the exposure amount was processed according to the following color development process.

[Processing process] Temperature Time Color development 34.7±0.3℃ 30 seconds, 50 seconds, 9
0 seconds bleach fixing 34.7±0.5℃ 50 seconds stabilization
Dry at 30-34℃ for 90 seconds 60-80℃ for 60 seconds E color developer [AI1 Pure water
800 Beta Ethylene Glycol
l0JN, N-diethylhydroxylamine potassium chloride 2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30 g optical brightener (4.4'-
Add 1 g of diaminostilbendisulfonic acid (i% conductor) to bring the total volume to 11, and adjust the pH to 10.08.

(bleach-fix solution) Ferric ethylenediaminetetraacetate Ammonium dihydrate salt 60.

Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% it) 100ml Ammonium sulfite 7A (40% dissolved IL) 27.5ml
Adjust p)1 to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1.1-diphosphonic acid 2g Water was added to bring the pH to 11, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. 0
Adjust to.

After the treatment was completed, sensitometric measurements were performed using PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.).

Table 1 shows the minimum density (D win>) and relative sensitivity (sensitivity at 90 seconds for each sample at 100 seconds) at each development time.
It is expressed as relative sensitivity when ) is shown.

[BF solution contamination variability evaluation]
, 0.2 ml/1 of each color developing solution [Bl, [CI to li! Adjustment, color developer [A]
- [Processed using C1 according to the color development processing step. However, the color development time was 50 seconds.

After the treatment, sensitometric measurements were performed using a PDA-65 type densitometer. Table 1 shows AI8 and ΔγC.

Here, ΔγB and AI0 are color developing solution [Bl or [C
This is the difference between γ when processed with I and color developer [γ when processed with AI, and the larger this value is, the worse the variability of BP liquid contamination is.

γ: Value indicating the gradation obtained by the reciprocal of the difference in the logarithms of the respective exposure amounts to obtain densities of 0.8 and 1.8. The results are shown in Table 1.

The method for evaluating pressure characteristics is as follows.

[Drying Pressure Characteristics 1 A ball point needle with a spherical diameter of 0.1 mff1 was placed vertically on the sample surface, and while the sample surface was moved in parallel at a speed of 1 am/sec, a load was applied to the ball point needle at the same time.

Thereafter, each sample was subjected to stepwise exposure to white light using a sensitometer (Model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and processed according to the processing steps described above to achieve a color density of 0.
The color density of the area where pressure was applied and the area where pressure was not applied around 3 was measured using a Sakura Microdensity F meter (PDM-5), and the following evaluations were made. In this case, the smaller the ΔDD value, the better the pressure resistance.

ΔD')=(density in the area where pressure was applied)-(density in the area where no pressure was applied) However, the color development processing time was 50 seconds.

From the results shown in Table 1, it is clear that when silver chloride particles are used, the development speed is high, but fogging is likely to occur, and B
Fluid F contamination variability is poor. When high silver chloride grains are used, which have a high silver bromide phase in the outermost shell of silver halide, but no sensitizing dye is added at the time of silver halide grain formation, fogging occurs. Although the variability of BF liquid contamination is improved, 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 BF liquid contamination variability and pressure resistance are also excellent.

Furthermore, the effects of the present invention can be further improved by treating the grains with hydrogen peroxide after finishing the silver halide grains.

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

(Example 2) Same as EM-C except that in Example 1, A-24 was changed to the sensitizing dye listed in Table 2 (thus, EM-F-
Created J.

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

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 effects of the present invention can be similarly obtained.

(Example 3) A multilayer silver halide photographic material was prepared by sequentially coating the following seven layers on polyethylene resin-coated paper. Note that the amounts added below are per 1/2 unless otherwise specified.

1st layer: 1.2 g of gelatin, 0.35 g (metallic silver equivalent, below) of blue-sensitive silver chlorobromide emulsion (average grain size 0)
．． 8 μl11), and 0.9 g of yellow coupler YC
-1 and 0,015t+ 2,5-dioctylhydroquinone (hereinafter referred to as HQ-1) is dissolved in a layer containing t-dioctyl 7-talate (hereinafter referred to as DOP).

2nd layer...0.7g gelatin and 0.06H HQ
A layer containing DOP in which -1 is dissolved.

Third layer...1.25. of gelatin, 0.35 g of green-sensitive silver chlorobromide emulsion (average grain size 0.5 μm), and 0.5 g of green-sensitive silver chlorobromide emulsion (average grain size 0.5 μm)
3g magenta coupler MC-1 and 0.015gHQ-
A layer containing DOP 1 dissolved therein.

4th layer...1.3g gelatin, 0.08g HQ-
1 and 0.5g of ultraviolet absorber (UV-1) dissolved in D
Layer containing OP.

5th layer: 1.4g gelatin, 0.3g red-sensitive silver chlorobromide emulsion (average grain size 0.5μl11), and 0.5g
cyan coupler CC-1 and 0.02. A layer containing DOP in which HQ-1 is dissolved.

6th layer...1.08 gelatin, 0.032gf)H
0.14g of glue in which Q1 and 0.2g of UV-1 were dissolved.

A layer containing P.

7th layer: layer containing 0.5 g of gelatin.

Sample No. 11 was created as described above.

2,4- G, 03g per 1g of gelatin as a hardening agent
Dichloro-6-hydroxy-s-triazine sodium salt was added. However, as the blue-sensitive silver chlorobromide emulsion of the first layer, an emulsion of EM-C sensitized with sulfur according to the method described in Example-1 was used.

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

As the red-sensitive silver chlorobromide emulsion for the fifth layer, silver halide grains with an average grain size of 0.5μ were prepared in the same manner as EM-I, and sulfur sensitized by the method described in Example-1. An emulsion prepared using the following methods was used.

Next, the following sample No. 12 was prepared.

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

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

The red-sensitive silver chlorobromide emulsion in the fifth layer was a red-sensitive silver chloride emulsion (average grain size: 0.5 μl11).

Sample No. 11.12 was evaluated by the method described in Example-1.

The results are shown in Table-3.

YC-1 Mo-1 (1σ IC-1 (UV-i)) From the results shown in Table 3, it is clear that the effects of the present invention can be obtained even when applied to multilayer silver halide photographic materials.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (method) % formula % 2. Name of the invention Silver halide photographic light-sensitive material with improved pressure resistance 3. Relationship with the person making the amendment Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Utter: Keio 4, Agent: 102 Address: Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone: 263-9524 (Delivery date) June 24, 1988 6. Procedures subject to amendment? mm Endorsement (Jiri September 6, 1986 Commissioner of the Japan Patent Office Black 111 Akira No. 2, Name of the invention Silver halide photographic light-sensitive material with improved pressure resistance 3, Relationship with the amended person case Patent application Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo@Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
1st move: Keio 4, Agent 102 Address: Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone: 263-9524 6. Contents of amendment [I] Part 12 of the specification, Scope of claims. Correct as shown in the attached sheet.

[I] The column [3. Detailed description of the invention] in the description is amended as follows.

(1) Specification box 10, lines 7 to 11: ``...high silver chloride grains with a silver chloride content of 80 to 99 mol%, and the grains have a high silver bromide silver halide phase at the top of the grains. It has in the outer shell part,
Silver halide grains having a sensitizing dye inside the high silver bromide silver halide phase in the outermost shell...''"Silver halide grains with a silver chloride content of 80 to 99 mol %, which are formed by forming a high silver bromide phase on a silver set..." is corrected.

(2) On page 11, lines 7-8 of the specification, the statement [...Silver halide grains made of silver chloride...] was changed to [...Silver halide in a high silver chloride phase made of silver chloride] "Particles..." I corrected myself.

(3) Page 17 of the specification box, lines 1 to 3 [...A sensitizing dye is contained inside the high silver bromide silver halide phase in the outermost shell of the grain. ] is written in the presence of a sensitizing dye. ” he corrected.

(4) On page 47, lines 8 to 10 of the specification, the statement [...it may be added so as to be inside the high silver bromide silver halide phase of the outermost shell portion] is deleted.

2 (Attachment) Claims In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a sensitizing dye. In the presence of
1. A silver halide photographic material comprising silver halide grains having a silver chloride content of 80 to 99 mol %, in which a high silver bromide phase is formed on a high silver chloride set.

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a silver chloride content of 80 to 80.
99 mol % high silver chloride grains, and the grains have a high silver bromide silver halide phase in the outermost shell of the grain, and a sensitizing dye is further provided inside the high silver bromide silver halide phase in the outermost shell. 1. A silver halide photographic material comprising silver halide grains having the following properties.