JPH0611782A - Silver halide photographic emulsion and photographic sensitive material using same - Google Patents

Abstract

PURPOSE:To maintain appropriate gradation to reduce fog and to enhance sensitivity. CONSTITUTION:The silver halide grains are formed by abruptly releasing iodide ions with the iodide ion releasing agent represented by the formula of R-I, and the grains are chemically sensitized to form the silver halide emulsion and the silver halide photographic sensitive material containing this emulsion. In the formula of R-I, R is a univalent organic residue releasing an iodidine I element in the form of ion by reaction with a base and/or a nucleophilic reagent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion and a photographic light-sensitive material containing the emulsion. More specifically, it relates to a silver halide photographic emulsion having low fog and high sensitivity, and a photographic light-sensitive material containing this emulsion.

[0002]

2. Description of the Related Art A silver halide emulsion used in a silver halide photographic light-sensitive material is usually chemically sensitized by using various chemical substances in order to obtain desired sensitivity, gradation and the like. As typical methods thereof, sulfur sensitization, selenium sensitization, sensitization of precious metals such as gold, and various sensitization methods using combinations thereof are known.

In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, and rapid processing for accelerating the progress of development. It has been done.

Among the above-mentioned sensitizing methods, the selenium sensitizing method is described in US Pat. Nos. 1,574,944 and 1,602.
No. 592, No. 1,623,499, No. 3,29
No. 7,446, No. 3,297,447, No. 3,3
No. 20,069, No. 3,408,196, No. 3,
No. 408,197, No. 3,442,653, No. 3,420,670, No. 3,591,385, French Patent No. 2,093,038, No. 2,093,
209, Japanese Examined Patent Publication Nos. 52-34491 and 52-344.
92, 53-295, 57-22090, JP-A-59-180536, 59-185330,
59-181337, 59-187338, 59-192241, 60-150046 and 6-15.
0-151637, 61-246738, JP-A-3-111838, 3-148648, British Patents 255,846, 861,984, and H.M.
E. Spencer et al., Journal of Ph
Otographic Science, Vol. 31, 1
58 to 169 (1983) and the like.

On the other hand, in order to increase the sensitivity of silver halide grains, it is preferable that the content of silver iodide (iodide ion) in each grain be uniform in terms of chemical sensitization and uniform developability. It is considered.

Japanese Unexamined Patent Publication No. 2-68538 (Japanese Patent Application No. 63-22)
No. 0187), the use of a halogen ion sustained-release agent or silver halide fine particles as a halogen ion supply source in place of the conventional aqueous solution of a halogen salt in the formation of silver halide grains results in a non-uniform distribution of halides in and between grains. A technique of eliminating the problem is disclosed.

However, it has not been reported that the formation of silver halide grains while rapidly forming iodide ions is important for producing an emulsion having high sensitivity and low fog.

In general, selenium sensitization has a greater sensitizing effect than sulfur sensitization which is usually carried out in the art, but it often causes fogging and tends to be easily softened. Although many of the above-mentioned known patents improve these drawbacks, they have still obtained insufficient results, and in particular, a basic improvement for suppressing the occurrence of fogging has been eagerly desired.

[0009] Further, particularly when sulfur sensitization or selenium sensitization is used in combination with gold sensitization, a marked increase in sensitivity can be obtained, but at the same time, fog also increases. Compared with gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog, and there has been a strong demand for technological development for suppressing the occurrence of fog.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-sensitivity silver halide photographic emulsion having proper gradation and less fog, and a light-sensitive material using the same.

[0011]

[Means for Solving the Problems] The above-mentioned object is as follows (1)
It is achieved by the means of (6) to (6), and the present invention makes it possible to fully utilize the sensitizing effect of selenium sensitization, which has been difficult with the prior art.

(1) A silver halide grain formed while rapidly generating iodide ions, characterized in that the silver halide grain is chemically sensitized with a selenium sensitizer. Silver halide photographic emulsion.

(2) Use an iodide ion-releasing agent such that 100 to 50% of the iodide ion-releasing agent present in the reaction vessel substantially completes the release of iodide ion within 180 consecutive seconds. The silver halide photographic emulsion as described in (1) above.

(3) The silver halide photographic emulsion according to (1) above, which is a silver halide grain formed by rapidly generating iodide ions using an iodide ion releasing agent and an iodide ion release controlling agent. .

(4) The reaction that rapidly produces iodide ions is a secondary reaction that is substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration, and part 2
The next reaction rate constant is 1000 to 5 × 10 ⁻³ (M ⁻¹ · s
The silver halide photographic emulsion according to (1) above, which uses an iodide ion-releasing agent of ec ^-1 ).

(5) The silver halide photographic emulsion as described in (1) above, which uses an iodide ion-releasing agent represented by the formula (I) shown in Chemical formula 2 below.

[0017]

[Chemical 2] In formula (I), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile.

(6) A photographic light-sensitive material containing the silver halide photographic emulsion described in any one of (1) to (5) above.

The present invention will be described in more detail below.

The iodide ion-releasing agent represented by the formula (I) of the present invention is used in order to make the halogen composition uniform within and between individual silver halide grains in the above-mentioned JP-A-2-68538. Partial overlap with the compound used.

However, by forming iodide ions rapidly in the presence of the iodide ion-releasing agent represented by the formula (I) to form silver halide grains, the fog is low and the silver halide has high sensitivity. It was unexpected that the present inventors found that an emulsion could be obtained.

The iodide ion-releasing agent represented by the following formula (I) shown in Chemical formula 3 of the present invention will be described in detail.

[0023]

[Chemical 3] In formula (I), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile.

The compound represented by formula (I) will be described in more detail. R represents, for example, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 to 2 carbon atoms.
3 alkynyl group, C 6-30 aryl group, C 7-30 aralkyl group, C 4-30 heterocyclic group, C 1-30 acyl group, carbamoyl group, C 2-30 Is preferably an alkyl or aryloxycarbonyl group, an alkyl or arylsulfonyl group having 1 to 30 carbon atoms, or a sulfamoyl group. R is preferably the above group having 20 or less carbon atoms, and particularly preferably the above group having 12 or less carbon atoms. The number of carbon atoms is preferably within the above range in terms of solubility and addition amount.

Further, R is preferably substituted, and preferable substituents include the following.
The substituent may be further substituted with another substituent. For example, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), an alkenyl group (eg, allyl). , 2-butenyl, 3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group ( For example, pyridyl, furyl, imidazolyl, piperidyl, morpholyl), alkoxy group (eg, methoxy, ethoxy, butoxy), aryloxy group (eg, phenoxy, naphthoxy), amino group (eg, unsubstituted amino, dimethylamino, ethylamino) ,
Anilino), acylamino group (eg acetylamino, benzoylamino), ureido group (eg unsubstituted ureido, N-methylureido, N-phenylureido), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino), sulfonyl Amino group (eg, methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (eg, carbamoyl,
Diethylcarbamoyl, phenylcarbamoyl), sulfonyl group (eg, methylsulfonyl, benzenesulfonyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group ( For example, phenoxycarbonyl), acyl group (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy group (eg, acetoxy, benzoyloxy), phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide), alkylthio group (Eg, methylthio, ethylthio), arylthio group (eg, phenylthio group), cyano group, sulfo group, carboxyl group, hydroxy group, phosphono group, nitro group.

Further preferred substituents for R are halogen atoms, alkyl groups, aryl groups, 5- or 6-membered heterocyclic groups containing at least one O, N or S, alkoxy groups,
An aryloxy group, an acylamino group, a sulfamoyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryloxycarbonyl group, an acyl group, a sulfo group, a carboxyl group, a hydroxy group and a nitro group. A particularly preferred substituent of R is a hydroxy group, a carbamoyl group, a lower alkylsulfonyl group or a sulfo group (including a salt thereof) when substituting an alkylene group, and a sulfo group (including a salt thereof) when substituting a phenylene group. Including).

The compound of the formula (I) of the present invention is preferably the compound of the formula (II) or the formula (II) shown below.
It is a compound represented by I).

The compound represented by the formula (II) shown in Chemical formula 4 of the present invention will be explained.

[0029]

[Chemical 4] In the formula (II), R21 represents an electron withdrawing group, and R22 represents a hydrogen atom or a substitutable group.

N2 represents an integer of 1 to 6, and n2 is 1 to
An integer of 3 is preferable, and 1 or 2 is particularly preferable.

The electron-withdrawing group represented by R21 is preferably an organic group having a Hammett's σ _p or σ _m or σ _I value of greater than 0.

The Hammett's σ _p value or σ _m value is “Structure-activity relationship of drug” (published by Nankodo), page 96 (1979).
Also, the σ _I value is described on page 105 of the same, and can be selected based on this table.

R21 is preferably, for example, a halogen atom (eg, fluorine, chlorine, bromine, etc.), trichloromethyl group, cyano group, formyl group, carboxylic acid group, sulfonic acid group, carbamoyl group (eg, unsubstituted carbamoyl). , Diethylcarbamoyl), an acyl group (eg, acetyl group, benzoyl group), an oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group),
Sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonyloxy group (eg, methanesulfonyl group), carbonyloxy group (eg, acetoxy group), sulfamoyl group (eg, unsubstituted sulfamoyl group, dimethylsulfamoyl group) ), A heterocyclic group (for example, a 2-thienyl group, a 2-benzoxazolyl group, 2
-Benzothiazolyl group, 1-methyl-2-benzimidazolyl group, 1-tetrazolyl group, 2-quinolyl group). The carbon-containing group of R21 preferably contains 1 to 20 carbons.

As the examples of the substitutable group represented by R22, those enumerated as the substituents of R are directly applicable. Plural R22s in the molecule may be the same or different.

It is preferable that more than half of R22 contained in the compound of the formula (II) are hydrogen atoms.

R21 and R22 may be further substituted, and preferable substituents include those enumerated as the substituents of R.

R21 and R22, or two or more R
22 may combine with each other to form a ring.

Next, the compound represented by the formula (III) shown in Chemical formula 5 of the present invention will be explained.

[0039]

[Chemical 5] In the formula (III), R31 is R33 O-group, R33 S-group, (R3
3) ₂ N-group, (R33) ₂ P- group or phenyl, wherein R33 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 3 carbon atoms. Represents an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and a heterocyclic group having 4 to 30 carbon atoms. The number of carbon atoms is preferably within the above range in terms of solubility and addition amount.

R31 is a (R33) ₂ N-group, (R33) ₂ P-
When representing groups, each two R33 groups may be the same or different.

R32 and n3 have the same meanings as R22 in formula (II), and a plurality of R32 may be the same or different.

As the examples of the substitutable group represented by R 32, those enumerated as the substituents of R are directly applicable.

It is particularly preferable that n3 is 1, 2, 4 or 5.

R31 and R32 may be further substituted, and preferable substituents include those enumerated as the substituents of R.

In addition, R31 and R32, or two or more R
32 may combine with each other to form a ring.

Specific examples of the compounds represented by the formulas (I), (II) and (III) of the present invention are shown below, but the compounds of the present invention are not limited to these.

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12] The iodide ion-releasing agent of the present invention can be synthesized according to the following synthetic method.

J. Am. Chem. Soc. , 76 , 3
227-8 (1954), J. Org. Chem. , 1
6 , 798 (1951), Chem. Ber. , 97 ,
390 (1964), Org. Synth. , V, 47
8 (1973), J. Am. Chem. Soc. , 1951 ,
1851, J.M. Org. Chem. , 19 , 1571
(1954), J. Chem. Soc. , 1952 , 1
42, J. Chem. Soc. , 1955 , 1383,
Angew, Chem. , Int. Ed. , 11 , 22
9 (1972), Chem. Commu. , 1971 ,
1112.

The iodide ion-releasing agent of the present invention releases iodide ions by reaction with an iodide ion-releasing regulator (base and / or nucleophile), and the nucleophile used at this time is preferably The following chemical species are listed.

For example, hydroxide ion, sulfite ion,
Hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, alcohols, ureas,
Examples thereof include thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines and sulfides.

In the present invention, the concentrations of bases and nucleophiles,
By controlling the addition method and the temperature of the reaction solution, the release rate and timing of iodide ions can be controlled. The base is preferably alkali hydroxide.

The preferred concentration range of the iodide ion-releasing agent and the iodide ion-releasing agent used for rapidly producing iodide ions is 1 × 10 ^{-7 to} 20 M, more preferably 1 × 10 ^-5 〜. 10M, more preferably 1 × 1
It is 0 ^{-4 to 5} M, particularly preferably 1 x 10 ^{-3 to 2} M.
If the concentration exceeds 20 M, the iodide ion-releasing agent having a large molecular weight and the added amount of the iodide ion-releasing agent become too large with respect to the capacity of the grain forming container, which is not preferable.

On the other hand, if it is less than 1 × 10 ^-7 M, the reaction rate of iodide ion-releasing reaction becomes slow, and it becomes difficult to rapidly generate the iodide ion-releasing agent, which is not preferable.

The preferred temperature range is 30-80 ° C.
More preferably 35 to 75 ° C, particularly preferably 35 to 6
It is 0 ° C. When the temperature is higher than 80 ° C., the reaction rate of iodide ion release is generally extremely high, and when the temperature is lower than 30 ° C., the reaction rate of iodide ion release is generally extremely slow. In the present invention, when a base is used for releasing iodide ions, a change in liquid pH may be used. At this time, a preferable pH range for controlling the iodide ion release rate and timing is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably the adjusted pH is 7. .5 to 10.0. Even under neutral conditions of pH 7, the hydroxide ion determined by the ionic product acts as a regulator.

Further, a nucleophile and a base may be used in combination,
At this time, the pH may be controlled within the above range to control the iodide ion release rate and timing.

A preferable range of the amount of iodide ions released from the iodide ion releasing agent is 0.1 to 20 mol% with respect to the total amount of silver halide, and more preferably 0.3 to.
15 mol%, particularly preferably 1 to 10 mol%,
You can choose according to your purpose.

If it exceeds 20 mol%, the developing rate is generally delayed, which is not preferable.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or some of them may remain without being decomposed.

The iodide ion releasing rate from the iodide ion releasing agent will be specifically described with reference to examples.

In the present invention, for example, in the process of introducing dislocations into tabular grains, the formation of silver halide phase containing silver iodide at the edges of the grains while rapidly generating iodide ions means that dislocations are densely formed. It is preferable for the introduction.

If the supply rate of iodide ions is too slow, that is, the time for forming the silver halide phase containing silver iodide is too long, the silver halide phase containing silver iodide is redissolved during that period. The dislocation density will decrease.

On the other hand, it is preferable to slowly supply the iodide ions in order to form grains so that the dislocation amount distribution does not become nonuniform among grains.

Therefore, it is important to generate iodide ions rapidly without causing locality (non-uniform distribution).

A region where iodide ion has a high locality is formed when an iodide ion-releasing agent or an iodide ion-releasing regulator used in combination with the iodide ion-releasing agent is added to the reaction solution in the grain forming container. This is because the iodide ion-releasing reaction is too fast with respect to the locality of the local concentration of the additive generated near the mouth.

The time for the released iodide ions to deposit on the host grains is extremely fast, and since grain growth occurs in the region near the addition port where the iodide ion has a high locality, uneven grain growth between grains occurs. Occur.

Therefore, it is necessary to select an iodide ion release rate that does not cause iodide ion locality.

In the conventional method (for example, adding an aqueous potassium iodide solution), the iodide ion is added in a free state even if the aqueous potassium iodide solution is diluted and added. There are limits to trying to reduce locality.

That is, it has been difficult to form particles without nonuniformity by the conventional method.

However, according to the present invention capable of controlling the iodide ion release rate, the locality of iodide ions can be reduced as compared with the conventional method.

In the above example, according to the present invention in which grain formation is performed while iodide ions are rapidly generated without causing locality, dislocations are introduced between the grains more uniformly and with higher density than in the conventional method. It has become possible.

In the present invention, the iodide ion-releasing rate can be determined by controlling the temperature and the concentrations of the iodide ion-releasing agent and the iodide ion-releasing agent as described above, and may be selected according to the purpose.

In the present invention, the preferred iodide ion release rate is 100 to 50% of the total weight of the iodide ion releasing agent present in the reaction solution in the grain forming container, which is continuous.
It is a rate of completing the release of iodide ions within 0 seconds and 1 second or more, more preferably within 120 seconds, and particularly preferably within 60 seconds.

In the present invention, "within 180 consecutive seconds"
Is 180 during the continuous iodide ion release reaction.
It is within seconds, and the iodide ion release time may be measured by counting from any point during the continuous reaction.

When the iodide ion releasing reaction period is divided into two or more times, it is calculated from any time point of the first iodide ion releasing reaction period or any time point of the second and subsequent iodide ion releasing reaction periods. Then, the iodide ion releasing rate from the iodide ion releasing agent present in the reaction solution at that time may be determined.

If it exceeds 180 seconds, the release rate is generally slow, and if it is less than 1 second, it is too fast, and the use conditions are limited.
The same is true even if it is less than 50%.

Further, 100 to 70% of the iodide ion-releasing agent present in the reaction solution in the grain forming container is continuously 1
The rate of completing the release of iodide ions within 80 seconds is more preferable, still more preferably 100 to 80%, and particularly preferably 100 to 90% at the rate of completing the release of iodide ions within 180 seconds. is there. .

When the reaction for rapidly producing iodide ions is represented by a secondary reaction which is substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration (40 ° C. in water), In the present invention, the second-order reaction rate constant is preferably 1000 to 5 × 10 ⁻³ (M ⁻¹ · sec ⁻¹ ).
And more preferably 100 to 5 × 10 ^-2 (M ^-1
* Sec ^-1 ), particularly preferably 10 to 0.1
(M ^-1 · sec ^-1 ).

The term "substantially second-order reaction" means that the correlation coefficient is 1.0 to 0.8. When the concentration of the iodide ion-releasing agent is 10 ^-4 to 10 ^-5 M and the concentration of the iodide ion-releasing agent is 10 ^-1 to 10 ^-4 M, in water,
A typical second-order reaction rate constant k (M ⁻¹ · se measured under conditions that can be regarded as a pseudo first-order reaction at 40 ° C.)
c ^-1 ) is as follows. Compound number Iodide ion release regulator k 11 Hydroxide ion 1.3 1 Sulfite ion 1 × 10 ⁻³ or less 2 Ibid 0.29 58 Ibid 0.49 63 Ibid 1.5 22 Hydroxide ion 720 k is 1000 If it exceeds 5, the release will be too fast to control, and if it is 5 × 10 ⁻³ or less, it will be too slow to obtain the effect of the present invention.

The following method is preferable for controlling the release of iodide ions in the present invention. That is, by changing the pH, the concentration of the nucleophilic substance, the temperature, etc., from the already uniformly distributed iodide ion-releasing agent added to the reaction solution in the grain forming container, it is usually possible to change the pH from low to high. It is a method of releasing the iodide ion while controlling it uniformly throughout the reaction solution.

It is preferable that the alkali for increasing the pH at the time of releasing iodide ions and the nucleophilic substance used in combination are added in a state in which the iodide ion releasing agent is uniformly distributed throughout. More specifically, the present invention produces silver iodide-containing silver halide (eg, silver iodide, silver iodobromide, silver chloroiodobromide, silver chloroiodide) grains by Iodide ions that react with ions are rapidly generated in the reaction system. Most commonly, the iodide ion of the present invention is added to a reaction system in which a silver ion is already present, for example, by the addition of silver nitrate, or an aqueous gelatin solution containing, for example, silver halide grains of silver iodobromide is used as a reaction medium. Releasing agent, if necessary, other halogen ion source (eg KBr)
Is added together with and uniformly distributed in the system (for example, by stirring). At this time, the pH of the reaction system is usually weakly acidic. In this state, the iodide ion-releasing agent does not rapidly release iodide ions.

Next, the pH of the reaction system is adjusted to the alkaline side (preferably 7.5 to 10) by adding an alkali (eg sodium hydroxide, sodium sulfite) as an iodide ion release regulator to the reaction system. ) To. With the addition of this alkali, iodide ions start to be rapidly released from the iodide ion-releasing agent, which reacts with silver ions or is converted into a halogen with silver halide grains to form a region of silver halide grains containing silver iodide. To generate.

As mentioned above, the reaction temperature is 30 to 80 ° C., which is usually used for producing silver halide, more preferably 35 to 75 ° C., further preferably 35 to 60 ° C. ℃. The release of iodide ions from the iodide ion-releasing agent is usually within 180 seconds continuously from immediately after the addition of the alkali within 1 second or more.
00 to 50% by weight is allowed to complete the release of iodide ions. For that purpose, the combination of the iodide ion-releasing agent and the iodide ion-releasing regulator and their use concentrations are selected in light of the above-mentioned second-order reaction constant.

The alkali may be added while vigorously stirring the reaction system in order to uniformly distribute the alkali in the reaction system (that is, in order to uniformly produce silver iodide). Preferred (eg by controlled double jet method).

The emulsion grains of the present invention will be described below.

The emulsion grains of the present invention are silver halide containing silver iodide.

The emulsion grains of the present invention contain at least one of a silver iodide phase, a silver iodobromide phase, a silver chloroiodobromide phase and a silver chloroiodide phase.

Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The preferable silver iodide content of the emulsion grains of the present invention is 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, and particularly preferably 1 to 10 mol%. , You can choose according to your purpose. . If it exceeds 20 mol%, the developing rate is generally delayed, which is not preferable.

The emulsion grains of the present invention preferably have a structure based on a halogen composition. (1) In the case of a particle having one or more coating shells for a base particle, a double structure, a triple structure, a quadruple structure, a quintuple structure, ... It is preferably formed by using an iodide ion releasing method.

(2) In the case of particles in which one or more layers that do not completely cover the base particles are deposited: two-layer structure, three-layer structure, four-layer structure, five-layer structure, ... The outermost layer is preferably formed by using the iodide ion releasing method of the present invention.

(3) In the case of grains epitaxially grown at selective sites of the base grain: The apex of the grain, the peripheral portion of the grain, and the epitaxial portion of the main plane portion of the grain are formed using the iodide ion releasing method of the present invention. It is preferable.

The composition of the coating shell of silver halide containing silver iodide, the deposition layer and the epitaxial portion formed by using the method of releasing iodide ions of the present invention preferably has a high silver iodide content.

The silver halide phase may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but is preferably silver iodide or silver iodobromide. It is more preferably silver halide.

In the case of silver iodobromide, the silver iodide (iodide ion) content is preferably 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 45 mol%. .

When it is less than 1 mol%, it is difficult to obtain effects such as enhancement of adsorption of dye, increase of intrinsic sensitivity, and formation of misfit necessary for introducing dislocation lines, which is not preferable. 45 mol% is the solid solution limit of silver iodobromide.

It is preferred to prepare silver halide grains containing dislocations using the iodide ion releasing method of the present invention.

The dislocation is a linear lattice defect on the slip plane of the crystal, which exists at the boundary between the already slipped region and the non-slip region.

Regarding dislocations of silver halide crystals, 1)
C. R. Berry, J .; Appl. Phys. , 2
7,636 (1956), 2) C.I. R. Berry,
D. C. Skillman, J .; Appl. Phys. ，
35, 2165 (1964), 3) J. F. Hamil
ton, Photo. Sci. Eng. , 11, 57 (1
967), 4) T.I. Shiozawa, J .; Soc. P
hot. Sci. Jap. , 34, 16 (1971),
5) T. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35, 213 (1972) and the like, which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.

When observing dislocations directly using a transmission electron microscope, be careful not to apply pressure to the grains so that the dislocations are generated, and place the silver halide grains taken out from the emulsion on a mesh for electron microscope observation. In order to prevent damage (for example, printout) by the electron beam, the sample is cooled and observed by the transmission method.

In this case, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is better to use a voltage type (200 kV or more for a thickness of 0.25 μm) electron microscope for clearer observation. You can

On the other hand, as the influence of dislocations on the photographic performance, G. C. Farnell, R.M. B. Flint,
J. B. Chapter, J. Photo. Sci. , 1
3, 25 (1965), it is shown that in a large size high aspect ratio tabular silver halide grain, the place where the latent image nucleus is formed and the defect in the grain have a close relation. There is.

JP-A-63-220238 and JP-A-1-
No. 201649 discloses tabular silver halide grains in which dislocations are intentionally introduced.

It is shown in these patent applications that tabular grains having dislocation lines introduced therein are superior in photographic characteristics such as sensitivity and reciprocity law to tabular grains having no dislocation lines.

Here, a method for introducing dislocations into silver halide grains will be described.

In the present invention, it is preferable to introduce dislocation into the inside of the silver halide grain as follows.

That is, a silver halide grain serving as a base is prepared, and a silver halide phase containing silver iodide (the above-mentioned silver halide coating shell, a deposition layer, and epitaxial growth) is formed on the base grain.

As described above, the higher the silver iodide content of these silver halide phases, the more preferable. The silver iodide content of the base grains is preferably 0 to 15 mol%, more preferably 0 to 12 mol%, and particularly preferably 0 to 10 mol%.
However, it may be selected according to the purpose. If it exceeds 15 mol%, the developing rate is generally delayed, which is not preferable.

The amount of halogen added to form this high silver iodide content phase on the base grain is 2 times the silver amount of the base grain.
-15 mol% is preferable, 2-10 mol% is more preferable, and 2-5 mol% is particularly preferable, but it may be selected according to the purpose.

If it is less than 2 mol%, dislocation lines are hardly introduced, which is not preferable. When it exceeds 15 mol%, the developing rate is delayed, which is not preferable.

At this time, the high silver iodide content phase is preferably present in the range of 5 to 80 mol%, more preferably 10 to 70 mol%, and particularly preferably 20 to 10 mol% based on the total silver amount of the grains. It is present within the range of 60 mol%.

If the amount is less than 5 mol% or more than 80 mol%, it is difficult to obtain high sensitization by introducing dislocation lines, which is not preferable.

The high silver iodide content phase may be formed on the base grains at any place, and the base grains may be covered or may be formed only on a specific portion, but a specific portion is epitaxially grown. It is therefore preferable to control the position of dislocations within the grain.

At that time, the composition of the halogen to be added, the method of addition, the temperature of the reaction solution, pAg, the solvent concentration, the gelatin concentration,
The ionic strength and the like may be freely selected and used.

Dislocations can then be introduced by forming a silver halide shell outside these phases.

The composition of this silver halide shell is silver bromide,
Either silver iodobromide or silver chloroiodobromide may be used, but silver bromide or silver iodobromide is preferred.

In the case of silver iodobromide, the silver iodide content is preferably 0.1 to 12 mol%, more preferably 0.1.
It is -10 mol%, most preferably 0.1-3 mol%.

If it is less than 0.1 mol%, it is not preferable because effects such as enhancement of dye adsorption and development acceleration cannot be obtained. 12 mol%
If it exceeds, the developing speed is delayed, which is not preferable.

The preferred temperature in the above dislocation introduction process is 30 to 80 ° C, more preferably 35 to 75 ° C.
It is particularly preferably 35 to 60 ° C.

In order to control the temperature at a low temperature of less than 30 ° C. or a high temperature of more than 80 ° C., a high-capacity manufacturing apparatus is required, which is not preferable in manufacturing.

The preferred pAg is 6.4 to 10.5.
Is.

In the case of tabular grains, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be obtained from the photograph of the grain taken by using an electron microscope as described above. .

The dislocation lines may or may not be visible depending on the tilt angle of the sample with respect to the electron beam. Therefore, in order to observe the dislocation lines without omission, the particle photographs at the same sample tilt angle as much as possible should be observed. It is necessary to find the position of the dislocation line.

In the present invention, it is preferable to determine the existence position and the number of dislocation lines by using a high-voltage electron microscope and changing the tilt angle in 5 ° steps with respect to the same grain, and taking five types of grain photographs.

When dislocations are introduced into the tabular grains in the present invention, the positions thereof can be selected from, for example, limiting to the apex portion and the fringe portion of the grain, or introducing into the entire main plane portion. It is particularly preferable to limit to the fringe portion.

The fringe portion in the present invention refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content is the first point seen from the side. The rate is outside the point where the rate exceeds or falls below the average silver iodide content of the entire grain.

In the present invention, it is preferable to introduce dislocations into the silver halide grains at a high density.

When dislocations are introduced into the tabular grains, tabular grains having 10 or more dislocation lines per grain in the grain fringe portion are preferable when the number of dislocation lines is counted by the above-mentioned method using an electron microscope. It is preferably 30 or more, and particularly preferably 50 or more.

When the dislocation lines are densely present, or when the dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted.

However, even in these cases, the number can be counted to about 10, 20, or 30.

It is desirable that the distribution of dislocation amounts among silver halide grains be uniform.

When dislocations are introduced into the tabular grains in the present invention, it is preferable that tabular grains having 10 or more dislocation lines per grain in the fringe portion account for 100 to 50% (number) of all grains. It preferably constitutes 100 to 70%, particularly preferably 100 to 90%.

If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the proportion of grains containing dislocations and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains, more preferably 200 grains or more, and particularly preferably 300 grains. Observe and obtain the above.

The tabular grains of the present invention are silver halide grains having two parallel main planes facing each other.

The tabular grains of the present invention have one twin plane or two or more parallel twin planes. What is twin plane (11
1) This is the (111) plane when the ions at all lattice points on both sides of the plane have a mirror image relationship.

When viewed from above, the tabular grains have a triangular shape, a hexagonal shape or a rounded circular shape, and have outer surfaces parallel to each other.

The equivalent-circle diameter of the tabular grains of the present invention is preferably 0.3 to 10 μm, more preferably 0.4 to 5 μm, and particularly preferably 0.5 to 4 μm.

If it is less than 0.3 μm, the merit of tabular grains cannot be fully utilized, which is not preferable. When it exceeds 10 μm, the pressure property is deteriorated, which is not preferable.

The grain thickness of the tabular grain of the present invention is 0.
The thickness is preferably 05 to 1.0 μm, more preferably 0.08 to 0.5 μm, and particularly preferably 0.08 to
It is 0.3 μm.

If it is less than 0.05 μm, the pressure property is deteriorated, which is not preferable. When it exceeds 1.0 μm, the merit of tabular grains cannot be fully utilized, which is not preferable.

The tabular grain of the present invention preferably has an aspect ratio of 2 to 30, more preferably 3 to 2.
5, particularly preferably 5 to 25.

If it is less than 2, the advantages of tabular grains cannot be fully utilized, which is not preferable. When it exceeds 30, the pressure property is deteriorated, which is not preferable.

The aspect ratio is a value obtained by dividing the circle-equivalent diameter of the projected area of a silver halide grain by the grain thickness.

As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and determining the equivalent circle diameter and thickness of the projected area of each grain.

In this case, the thickness is calculated from the length of the shadow of the replica.

In the present invention, hexagonal tabular grains having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 to 1 are projected on all grains in the emulsion. It is preferable to occupy 100 to 50% of the area, more preferably 100 to 70%, particularly preferably 10%.
It occupies 0 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

The emulsion of the present invention is preferably monodisperse.

The variation coefficient of the grain size distribution of all silver halide grains of the present invention is preferably 20% to 3%, more preferably 15% to 3%, particularly preferably 10%.
To 3%. If it exceeds 20%, it is not preferable in terms of homogeneity between particles.

It is a value obtained by dividing the variation coefficient of the particle size distribution and the standard deviation of the particle size distribution of the particles by the average particle size.

Further, it is preferable to form the outermost shell near the surface of the silver halide grain uniformly within and between grains by using the iodide ion releasing method of the present invention.

Forming a silver halide phase containing silver iodide in the vicinity of the grain surface is important from the viewpoint of enhancing the dye adsorbing power and controlling the developing speed.

In the present invention, the particle surface means 5 from the surface.
A region to a depth of about 0 angstrom.

The halogen composition in such a region is XPS.
It can be measured by a surface analysis method such as (X-ray photoelectron spectroscopy) method or ISS (ion scattering spectroscopy) method.

In the present invention, a silver halide grain having a silver iodide content of 0.1 to 15 mol% in the silver halide phase on the grain surface of the emulsion grain measured by these surface analysis methods is preferable, and more preferably 0. 0.3 to 12 mol%, particularly preferably 1 to
It is 10 mol%, most preferably 3 to 8 mol%. 0.
If it is less than 1 mol%, it is difficult to obtain enhanced sensitization due to enhanced dye adsorption and development, which is not preferable. When it exceeds 15 mol%, the developing rate is delayed, which is not preferable.

In the present invention, it is preferable that the halogen composition among the emulsion grains is uniform.

In the emulsion of the present invention, the variation coefficient of the silver iodide content distribution of individual grains is preferably 20% to 3%, more preferably 15% to 3%, particularly preferably 10% to 3%. Is.

If it exceeds 20%, it is not preferable in terms of homogeneity between particles.

The silver iodide content of each grain can be measured by analyzing the composition of each grain with an X-ray microanalyzer.

The variation coefficient of the silver iodide content distribution is a value obtained by dividing the variation (standard deviation) of the silver iodide content of each grain by the average silver iodide content.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-25832 and JP-A-4-109240 are preferably used. Specific examples of the unstable selenium sensitizer include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, Two
-Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. can give.

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-unstable selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-3449.
The compounds described in No. 2 and No. 52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles,
Examples thereof include quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, the following formulas (IV) and (V) are preferable.

Formula (IV)

[0171]

[Chemical 13] In formula (IV), Z ₁ and Z ₂ may be the same or different, and an alkyl group (for example, methyl, ethyl,
t-butyl, adamantyl, t-octyl), alkenyl group (eg vinyl, propenyl), aralkyl group (eg benzyl, phenethyl), aryl group (eg phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl). , 4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group (eg, pyridyl, thienyl, furyl, imidazolyl), —NR ₁
(R _2), - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ .

However, R ₁ and R ₂ are each a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) may be used.

In formula (IV), preferably Z ₁ represents an alkyl group, an aryl group or --NR ₁ (R ₂ ), and Z ₂ represents --NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R ₆
May be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

In formula (IV), more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-N '.
-Acyl selenoureas, tetraalkyl selenoureas, N,
Represents N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

Formula (V)

[0177]

[Chemical 14] In the formula (V), Z ₃ , Z ₄ and Z ₅ may be the same or different, and are each an aliphatic group, an aromatic group, a heterocyclic group,
-OR ₇ , -NR ₈ (R ₉ ), -SR ₁₀ , -SeR ₁₁ ,
X represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the formula (V), Z ₃ , Z ₄ , Z ₅ and R
_The aliphatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkyl group, aralkyl group (for example, methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3
-Pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the formula (V), Z ₃ , Z ₄ , Z ₅ and R
_The aromatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl). , 4-methylphenyl).

In the formula (V), Z ₃ , Z ₄ , Z ₅ and R
_The heterocyclic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom ( For example, pyridine, thienyl, furyl, thiazolyl,
Imidazolyl, benzimidazolyl).

In the formula (V), R ₇ , R ₁₀ and R ₁₁
The cation represented by represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In formula (V), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇
Represents an aliphatic group or an aromatic group.

In formula (V), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

Specific examples of the selenium compounds represented by the formulas (IV) and (V) are shown below, but the invention is not limited thereto.

[0186]

[Chemical 15]

[0187]

[Chemical 16]

[0188]

[Chemical 17]

[0189]

[Chemical 18]

[0190]

[Chemical 19]

[0191]

[Chemical 20]

[0192]

[Chemical 21]

[0193]

[Chemical formula 22] These selenium sensitizers include water or, for example, methanol,
Dissolved in an organic solvent such as ethanol alone or in a mixed solvent, or disclosed in JP-A-4-140738 and JP-A-4-14
No. 0739 is added at the time of chemical sensitization.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-5 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

It is more effective to carry out the selenium sensitization in the presence of a silver halide solvent.

The silver halide solvent usable in the present invention is, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A Nos. 54-1019 and 54-158917.
(A) Organic thioethers described in JP-A No. 1993-54,
3-82408, 55-77737, 55-2
982, etc., (b) thiourea derivative, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) Thiocyanate.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 × per mol of silver halide.
It is 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually performed by adding a sulfur sensitizer at high temperature,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

Known sulfur sensitizers can be used for the above-mentioned sulfur sensitization. For example, thiosulfate, thioureas, allyl isothiocyanate, cystine, p-
Toluene thiosulfonate and Rhodanine are mentioned.
Other US Pat. Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501,313, No. 3,
656,955, German Patent 1,422,869,
Sulfur sensitizers described in JP-B-56-24937 and JP-A-55-45016 can also be used.
The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, size of silver halide grains, etc., but is 1 × 1 per mol of silver halide.
It is preferably 0 ⁻⁷ mol or more and 5 × 10 ⁻⁴ mol or less.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include, for example, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 and not more than 5 × 10 ⁻⁴ mol.

In chemical ripening, there is no particular limitation on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. It is not necessary to provide it, and the above compounds can be added at the same time, or at different addition points, during the initial (preferably) or during the progress of chemical ripening. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone and added.

The following is a description of the emulsion of the present invention and the emulsions other than the present invention which are used in combination therewith.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as Rhodan silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The silver halide emulsion of the present invention has a distribution or structure with respect to the halogen composition in its grains.
Typical examples thereof are JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, and JP-A-6-222845.
It is a core-shell type or double structure type grain having a halogen composition in which the inside of the grain is different from the surface layer as disclosed in JP-A No. 0-14331 and JP-A No. 61-75337. Further, it is not a simple double structure, but is disclosed in JP-A-60-22.
It is possible to form a triple structure as disclosed in No. 2844 or a multilayer structure of more than that, or to thin the silver halide having a different composition on the surface of the grain of the core-shell double structure.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59
-133540, 58-108526, European Patent 199,290A2, JP-B-58-24772,
It is disclosed in JP-A-59-16254. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other. However, for example, a silver salt compound not having a rock salt structure such as silver rhodan or silver carbonate may be combined with silver halide to form a junction structure. it can. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible.

In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable.
Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment.

In the case of silver halide grains in which two or more silver halides exist as crystals or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion in which grain size is a function of halogen composition. For example, there is a correlation in which larger size grains have a higher iodide content, while smaller size grains have a lower iodide content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, (100) plane and (1
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain 11), or on one of the main plane and the side surface of the tabular grain.

The silver halide grains used in the emulsion of the present invention and the emulsions other than the present invention which are used in combination with the emulsion of the present invention, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photographs (Corona). Company, P. 163, eg, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, JP-B-55-42737, and JP-A-60-
The dodecahedron grains having the (110) plane disclosed in No. 222842 can be used. Furthermore, Jou
rnal of ImagingScience 30
Volume 247 as reported in 1986 (2
(H11) plane particles represented by (11), (hh1) plane particles represented by (331), (hk0) plane particles represented by (210) plane, and (321) plane represented by (hk).
1) The surface particles also require a devised preparation method, but can be selected and used according to the purpose. A tetrahedral particle in which the (100) plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist. Particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

The value obtained by dividing the equivalent circle diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of more than 1 can be used in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography Theo).
ry and Practice (1930)), 13
Page 1: Gatov, Photographic Science and Engineering (Gutoff, Photogr
apic Science and Engineer
Ring), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
No. 4,310, No. 4,433,048, No. 4,4
It can be prepared by the method described in 39,520 and British Patent 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitizing efficiency by a sensitizing dye, which are described in detail in US Pat. No. 4,434,226 cited above. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. A triangle, a hexagon, a circle or the like can be selected as the shape of the average particle. U.S. Pat. No. 4,797,35
A regular hexagon having six sides of approximately the same length as described in No. 4 is a preferred form.

A circle-equivalent diameter of a projected area is often used as a grain size of tabular grains.
The average diameter as described in No. 8,106 is 0.6
Particles having a size of μm or less are preferable for improving image quality. An emulsion having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 is also preferable. It is preferable to increase the sharpness by limiting the grain thickness of the tabular grains to 0.5 μm to 0.05 μm, and more preferably 0.3 μm to 0.05 μm. Furthermore, an emulsion having a high uniformity of thickness with a variation coefficient of grain thickness of 30% to 3% is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a grain containing no dislocation lines, a grain containing several dislocation lines, or a grain containing many dislocation lines according to the purpose. It is also possible to select a dislocation line or a curved dislocation line that is linearly introduced with respect to a specific direction of the crystal orientation of the particle, or it can be introduced throughout the particle or only in a specific part of the particle. For example, the dislocation line can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. Issue, JP-A-6
The surface may be modified as disclosed in 0-221320.

Generally, the structure is such that the particle surface is flat.
It is sometimes preferable to intentionally form the unevenness.
JP-A-58-106532, JP-A-60-22132
Part of the crystals described in US Pat. No. 0, for example, a method of drilling holes in the centers of vertices or planes, or US Pat.
Raffle particles described in 643,966 are examples.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less, and coarse particles having a diameter of more than 10 μm. It is preferable to use grains of 0.1 μm or more and 3 μm or less as photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% to 3%, more preferably 20% to 3%, still more preferably 15% to 3%.

A monodisperse emulsion is used within 80% to 100% of all grains within ± 30% of the average grain size in terms of number of grains or weight.
In some cases, it is defined as a particle size distribution containing%.
In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. It can be applied in multiple layers. 2 more
It is also possible to use more than one kind of polydisperse silver halide emulsion or a combination of a monodisperse emulsion and a polydisperse emulsion as a mixture or a multilayer.

The emulsion of the present invention and the photographic emulsion used in combination therewith are described in "Physics and Chemistry of Photography" by Graphkide, published by P. Montefler (P. Glafkides, Ghimie et.
Physique Photographique
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Fmulsion
Chemistry (Focal Press, 19
66), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like. That is, the acidic method, the neutral method,
Any method such as the ammonia method may be used, and the method of reacting the soluble silver salt and the soluble halogen salt is a one-sided mixing method,
Any of the simultaneous mixing method and the combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

A method of adding silver halide grains which have been formed in advance to a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Are optionally preferred. These can be used as seed crystals, and are effectively supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method may be selected from total addition at once, addition in plural times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method of converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,582 and 4,1.
42,900, European Patents 273,429, 2nd
73,430, West German Laid-Open Patent No. 3,819,241, etc., and is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from methods such as converting at once, changing by dividing into multiple times, or converting continuously.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in the above-mentioned No. 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
No. 3, ibid. 3,342, 605, ibid. 3, 415, 65
No. 0, No. 3,785,777, West German Published Patent No. 2,
It can be selected and used from the methods described in Nos. 556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. All of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts,
It is also possible to add halide salts, silver salts or peptizers and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently during the silver halide salt and silver salt addition steps.

As the ripening agent, for example, ammonia, thiocyanate, (for example, rhodan potassium, rhodan ammonium), organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,021,215, No. 3,057,724, No. 3,038,805,
No. 4,276,374, No. 4,297,439
No. 3,704,130, No. 4,782,01
No. 3, compounds described in JP-A-57-104926. ), A thione compound (for example, JP-A-53-8240).
No. 8, 55-77737, U.S. Pat. No. 4,221,
Tetrasubstituted thioureas described in Japanese Patent No. 863, etc., and compounds described in JP-A No. 53-144319)
And a mercapto compound and an amine compound capable of promoting the growth of silver halide grains described in JP-A-57-202531 (for example, JP-A-54-100717).
Can be given.

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate and starch derivatives. Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
A variety of synthetic hydrophilic polymeric substances such as single or copolymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No.16. The enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 ° to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. For example, Mg, Ca, Sr, Ba,
Al, Sc, Y, La, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Ti, In, S
n, Pb and Bi can be used. These metals may be in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates or hexacoordinated complex salts, tetracoordinated complex salts, which can be dissolved during grain formation. Can be added. For example, CdBr ₂ , CdCl ₂ , C
d (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl
₆ and K ₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

The metal compound is preferably added by dissolving it in water or a suitable organic solvent such as methanol or acetone. Aqueous hydrogen halide solution (eg HCl, HBr) or alkali halide (eg KCl, NaCl, KBr, Na) to stabilize the solution.
A method of adding Br) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (for example, AgNO
₃ ) or an aqueous alkali halide solution (eg Na
Cl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods. US Pat. No. 3,77
The method of adding a chalcogenide compound as described in No. 2,031 during emulsion preparation may also be useful.
In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salt,
Known are ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions formed here may form a sparingly water-soluble silver salt such as silver halide, silver sulfide or silver selenide, or a silver salt easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO _{2
· H 2 O 2 · 3H 2} O, 2NaCO 3 · 3H 2 O 2, N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
.2H ₂ O), peroxy acid salts (eg K ₂ S
₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3
_{H 2 O, 4K 2 SO 4} · Ti (O 2) OH · SO 4 · 2
H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] ・ 6H
₂ O), permanganates (eg KMnO ₄ ), chromates (eg K ₂ Cr ₂ O ₇ ) oxyacid salts,
There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high molecular weight metals (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, for example, p
Examples thereof include quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B).

Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidants, and quinones organic oxidants.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), many compounds known as antifoggants or stabilizers such as pentaazaindenes can be added. For example, US Pat.
Those described in 954,474, 3,982,947 and JP-B-52-28660 can be used. One of the preferable compounds is JP-A-63-21293.
There are compounds described in No. 2. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, i.e. indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinoline nuclei are applicable. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5-6 membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus, or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928, that spectral sensitization is carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started before the completion of silver halide grain precipitation. Furthermore, it is possible to add these said compounds separately, as taught in U.S. Pat. No. 4,255,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 × 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The above-mentioned various additives are used in the light-sensitive material of the present invention. In addition to them, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (December 1979).
Mon) and Item 308119 (December 1989)
Month), and the relevant parts are summarized in Table 1 below.

[0250]

[Table 1] The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler and a DIR compound as described in JP-A-61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be arranged in this order.

Also, as described in JP-B-55-34932, the blue-sensitive layer /
It can also be arranged in the order of GH / RH / GL / RL.
Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, there may be mentioned an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. In the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four layers or more, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table 2 below.

[0261]

[Table 2] In order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is used as a light-sensitive material. It is preferable to add.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 0479, a dye dispersed by the method described in JP-A-1-502912 or EP 317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, section VII-F and ibid. 307105, VII-
Patents described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154,234, 60-184,248, 63-37,346, 63-37,350, and U.S. Pat.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , RD. No. 1
1449, 24241, and bleaching accelerator releasing couplers described in JP-A No. 61-201247, U.S. Pat.
55,477, etc., a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-tert-amylphenyl)
Phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2-ethylhexylbenzoate) , Dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate); amides (eg, N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (for example, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (for example, bis (2- Ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg N, N-dibutyl-2-butoxy-).
5-tert-octylaniline); hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) can be exemplified. The auxiliary solvent has, for example, a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of not less than about 160 ° C. and not more than about 160 ° C. can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
No. 274 and No. 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248 and JP-A No. 1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2 −
It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Representative examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention can be particularly preferably used for a film for color duplication.

Suitable supports usable in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, for example, A. Green et al., Photography Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. In addition, T _1/2 is a color developing solution of 30
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
0% is defined as the saturated film thickness, which is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in 2
It is also possible to use together more than one species.

The color developer contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-.
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal processing is carried out, black and white development is usually carried out before color development. This black-and-white developer contains, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-, for example.
Known black-and-white developing agents of aminophenols such as p-aminophenol can be used alone or in combination.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also
When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, the movable lid described in JP-A-1-82033 is used. And the slit development processing method described in JP-A-63-216050. Reducing the aperture ratio is preferably applied not only in both the color development and black and white development steps but also in the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The time of color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. .

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching treatment after the bleach-fixing treatment can be arbitrarily carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids (in particular, sodium persulfate is suitable for color negative films for motion pictures), quinones, and nitro compounds are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Complex salts of can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 51-140129, a thiazolidine derivative described in JP-A No. 51-140129;
832, 53-32735, and U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561, West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, JP-A-49-59644,
53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95630 are preferred. Further, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specific examples thereof include acetic acid, propionic acid and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Also, with thiosulfate, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 2
The sulfinic acid compounds described in No. 94,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methyl. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as imidazole.

The total time for the desilvering step is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or a stirring means using a rotating means in JP-A-62-183461 is used. There are ways to increase the effect. Furthermore, a method of further improving the stirring effect by moving the photosensitive material while making the emulsion surface contact with the wiper blade provided in the solution and making the emulsion surface turbulent, and increasing the circulation flow rate of the entire processing solution There is a method of making it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the agitation improving means is more effective when a bleaching accelerator is used, and the accelerating effect can be remarkably increased, and the fixing inhibiting effect can be eliminated by the bleaching accelerator.

Automatic developing machines used for developing the light-sensitive material of the present invention are disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to various conditions such as a replenishment method such as counterflow and forward flow. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
the Society of Motion Pi
movie and Television Engi
neers Vol. 64, p. 248-253 (1955
May issue).

According to the multi-stage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, bacteria are propagated due to an increase in the residence time of water in the tank, and the resulting suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Sanitary Technology "Sterilization, sterilization and antifungal technology of microorganisms" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal It is also possible to use the fungicide described in "Molding Encyclopedia" (1986).

P of washing water in processing the light-sensitive material of the present invention
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on, for example, the characteristics of the light-sensitive material and the use, but generally 15 to 45 ° C. and 20 seconds to 1
A range of 0 minutes, preferably 25 to 40 ° C. and 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used.

In addition, subsequent to the water washing treatment, a stabilizing treatment may be performed. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic processor,
When each of the above treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

A color developing agent may be incorporated in the silver halide color photographic light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, such as Research Disclosure No. 3,342,599. 14, 850 and the same No.
Schiff base type compounds described in Nos. 15 and 159, No. 1
Aldol compounds described in US Pat.
Metal salt complexes described in JP 719,492, JP-A-53-1.
The urethane compound described in No. 35628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention comprises
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380.
No. 56, European Patent No. 210,660A2 and the like can be applied to the photothermographic material.

The silver halide color photographic light-sensitive materials of the present invention are described in JP-B-2-32615 and JP-B-3-397.
When applied to the lens-equipped film unit described in No. 84 etc., it is more effective and more effective.

[0309]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Tabular silver iodobromide emulsion (1) Preparation of emulsion Tabular silver iodobromide core emulsion 1-A Aqueous solution 1 containing 6.2 g of gelatin and 6.4 g of KBr.
Stirring while keeping 200 cc at 60 ° C., A of 1.9M
gNO ₃ aqueous solution 8 cc and 1.7 M KBr aqueous solution 9.6
cc was added with a double jet for 45 seconds. Gelatin 3
After adding 8 g, the temperature was raised to 75 ° C., and 2% was added in the presence of NH _3.
Aged for 0 minutes. After neutralization with HNO ₃ , 1.9M AgN
An aqueous solution of 405 cc of O ₃ and an aqueous KBr solution containing 1 M% of KI were added for 87 minutes while accelerating the flow rate while keeping the pAg at 8.22 (the flow rate at the end is 10 times that at the start). Thereafter, this emulsion was cooled to 35 ° C. and desalted by a conventional flocculation method. The obtained silver iodobromide emulsion was a tabular grain having an average equivalent circle diameter of 2.0 μm, an average thickness of 0.25 μm and an average aspect ratio of 8.

Tabular Silver Iodobromide Emulsion 1-B (Comparative Emulsion) Emulsion 1 containing silver iodobromide equivalent to 164 g of AgNO _3.
-A was added to 1950 cc of water, temperature was 55 ° C, pAg
Was maintained at 8.9 and pH at 5.0. Then 0.32M
KI aqueous solution of 1.9M AgN
206 cc of O ₃ aqueous solution and 2.0 M of KBr aqueous solution are pA
g was added over 36 minutes to keep 8.9. After this,
It was desalted by a conventional flocculation method. The obtained silver iodobromide emulsion has an average equivalent circle diameter of 2.1 μm and an average thickness of 0.3.
The tabular grains had a thickness of 0 μm and an average aspect ratio of 7. The same applies to the following emulsions 1-C to 1-H.

Tabular Silver Iodobromide Emulsion 1-C (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following.

Instead of adding the KI aqueous solution, a silver iodide fine grain emulsion having an average grain size of 0.02 μm corresponding to AgNO ₃ (6.8 g) prepared separately was added and completely dissolved in 10 minutes.

Tabular Silver Iodobromide Emulsion 1-D (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following.

After adding an aqueous solution of iodoacetic acid (7.5 g) instead of adding the aqueous solution of KI, an aqueous solution of NaOH was added and the pH was raised to 10.5 and maintained for 15 minutes to gradually release iodide ions. , Back to 5.0.

Tabular Silver Iodobromide Emulsion 1-E (Emulsion of the Invention) The same procedure as emulsion 1-B was carried out except the following.

Instead of adding the KI aqueous solution, 2-iodoethanol (3.1 cc) was added, and then the NaOH aqueous solution was added to raise the pH to 9.5 and kept for 10 minutes to rapidly generate iodide ions. And then back to 5.0.

Tabular Silver Iodobromide Emulsion 1-F (Emulsion of the Invention) The same procedure as emulsion 1-E was carried out except the following.

After adding 2-iodoethanol (3.1 cc), an aqueous NaOH solution was added to raise the pH to 10.5 and kept for 4 minutes to rapidly generate iodide ions, and then returned to 5.0. It was

Tabular Silver Iodobromide Emulsion 1-G (Emulsion of the Invention) It was prepared in the same manner as Emulsion 1-B except for the following.

Instead of keeping the temperature at 55 ° C, it was kept at 40 ° C.

Instead of adding an aqueous KI solution, sodium P-iodoacetamidobenzenesulfonate (15.
3 g) After adding an aqueous solution, a 0.80 M sodium sulfite aqueous solution (75 cc) was added, and a NaOH aqueous solution was added to raise the pH to 9.0 and hold for 10 minutes to rapidly generate iodide ions. Returned to 5.0.

Tabular Silver Iodobromide Emulsion 1-H (Emulsion of the Invention) The same procedure as emulsion 1-B was carried out except the following.

Instead of adding an aqueous solution of KI, sodium P-iodoacetamidobenzenesulfonate (15.
3 g) aqueous solution, then 0.80 M sodium sulfite aqueous solution (60 cc) was added, NaOH aqueous solution was added to raise pH to 9.0 and held for 8 minutes to rapidly generate iodide ions, Returned to 5.0.

Tabular Silver Iodobromide Emulsion 1-I (Emulsion of the Invention) The same procedure as emulsion 1-G was carried out except the following. 40 ℃
Instead of keeping it at 55 ° C.

Tabular silver iodobromide core emulsion 2-A was prepared in the same manner as emulsion 1-A except for the following. 60 ℃
Instead of keeping at 30 ℃, 1.9M AgNO ₃ aqueous solution 8
cc and 1.7 M KBr aqueous solution 9.6 cc in 45 seconds instead of adding 0.1 M AgNO ₃ aqueous solution 48 cc
25 cc of 0.2 M KBr aqueous solution was added over 10 seconds. 2 NH ₃ without instead of aging in the presence of NH ₃
Physically aged for 0 minutes. The obtained silver iodobromide emulsion was a tabular grain having an average equivalent circle diameter of 2.6 μm, an average thickness of 0.14 μm and an average aspect ratio of 19.

Tabular Silver Iodobromide Emulsion 2-B (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following. Emulsion 2-A was used instead of Emulsion 1-A. The obtained silver iodobromide emulsion was tabular grains having an average equivalent circle diameter of 2.7 μm, an average thickness of 0.18 μm and an average aspect ratio of 15. Emulsion 2 below
The same applies to -C.

Tabular Silver Iodobromide Emulsion 2-C (Emulsion of the Invention) The same procedure as emulsion 1-I was carried out except the following. Emulsion 2-A was used instead of Emulsion 1-A. (2) Chemical sensitization Emulsions 1-B to 1-I, 2-B and 2-C were subjected to gold-sulfur sensitization as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
xS-1 is 2.4 × 10 ⁻⁴ mol / mol Ag, ExS-2
1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 3.5.
× 10 ^-4 mol / mol Ag, sodium thiosulfate 9.0 ×
10 ⁻⁶ mol / mol Ag, potassium thiocyanate 1.9 ×
10 ^-3 mol / mol Ag, chloroauric acid 1.0 × 10 ^-6 mol /
Optimal chemical sensitization was performed by adding mol Ag. Here, "optimally perform chemical sensitization" means chemical sensitization that maximizes the sensitivity when exposed for 1/100 second.

Emulsions 1-B to 1-I, 2-B, 2-C
Was subjected to gold-sulfur-selenium sensitization as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described later was added.
xS-1 is 2.4 × 10 ⁻⁴ mol / mol Ag, ExS-2
1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 3.5.
× 10 ^-4 mol / mol Ag, sodium thiosulfate 7.4 ×
10 ^-6 mol / mol Ag, chloroauric acid 1.9 × 10 ^-6 mol /
Molar Ag, potassium thiocyanate 1.9 × 10 ⁻³ mol /
Molar Ag, N, N-dimethylselenourea 1.5 × 10
^-6 mol / mol Ag was added for optimum chemical sensitization. (3) Preparation of coated samples and evaluation thereof Coating emulsions 1 and 20 were prepared by coating the emulsion and the protective layer on a cellulose triacetate film support having an undercoat layer in coating amounts shown in Table 3 below. did. Table 3 Emulsion coating conditions (1) Emulsion layer ・ Emulsion …… Various emulsions (Silver 3.6 × 10 ^-2 mol / m ² ) ・ Coupler shown in the following chemical formula 23 (1.5 × 10 ^-3 mol / m ² ).

[0332]

[Chemical formula 23] -Tricresyl phosphate (1.10 g / m < ² >)-Gelatin (2.30 g / m < ² >) (2) Protective layer-2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.08 g /) m ² ) ・ Gelatine (1.80 g / m ² ) These samples were placed under the conditions of 40 ° C. and 70% relative humidity for 14 days.
After standing for a time, the film was exposed through a continuous wedge for 1/100 second, and color development shown in Table 4 below was performed. The treated sample was measured for density with a green filter.

Table 4 Process Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleach fixing 2 minutes 00 seconds 40 ° C Water washing (1) 20 seconds 35 ° C Water washing (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Dry Drying 50 seconds 65 ° C. Next, the composition of the treatment liquid is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxyamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethylamino] 4.5-2-methylaniline sulfate Water was added to 1.0 liter pH 10.05 (bleach-fixing solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid sodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach accelerator shown in 24 0.01 mol

[0334]

[Chemical formula 24] 1.0 liter pH 6.0 (water washing liquid) was added water, and tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) packed with a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by sodium diisocyanurate dichloride 2
0 mg / liter and 1.5 g / liter of sodium sulfate were added.

The pH of this liquid is in the range of 6.5-7.5. (Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added 1. 0 liter pH 5.0-8.0 Sensitivity was expressed as the relative value of the logarithm of the reciprocal of the exposure dose expressed in lux · sec which gives a density of 0.2 on fog. Gamma was obtained as the slope of a straight line connecting the point of fog +0.2 and the point of fog +1.2. The results obtained are shown in Table 5 below.

[0336]

[Table 5] As is clear from Table 5, the above-mentioned constitution of the present invention made it possible to obtain an emulsion having a low fog, a high sensitivity and a large gamma value. Example 2 Emulsion 1-B, 1-H, 1-J, 1-prepared in Example 1
K was subjected to gold-sulfur-selenium sensitization as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
xS-4 was 4.7 × 10 ⁻⁵ mol / mol Ag, ExS-5
1.1 × 10 ⁻⁴ mol / mol Ag and ExS-6 4.0
× 10 ^-4 mol / mol Ag, sodium thiosulfate 7.4 ×
10 ⁻⁶ mol / mol Ag, potassium thiocyanate 1.9 ×
10 ⁻³ mol / mol Ag, chloroauric acid 1.9 × 10 ⁻⁶ mol /
Molar Ag, N, N-dimethylceriurea 2.3 × 10 ⁻⁶
Mol / mol Ag was added for optimum chemical sensitization.

On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers, and samples 101 to 104, which are multilayer color light-sensitive materials, were coated.
Was produced. (Photosensitive layer composition) The main materials used for the multilayer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Samples 101 to 104) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS- 2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ^{− 5} ExS-3 3.1 × 10 ⁻⁴ ExC-1 0.17 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0.87 4th layer ( Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.20 ExC -0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 5th layer (high Sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.097 ExC- 2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) Cpd-1 0.040 HBS-1 0. 020 Gelatin 0.80 7th layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0. ^{0 ExS-4 2.6 × 10 -5} ExS-5 1.8 × 10 -4 ExS-6 6.9 × 10 -4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY -1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (medium-speed green emulsion layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS- 5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion (Emulsion 1-B, 1-I, 2-B, 2-C) Silver 1.55 ExC-1 0.015 ExM -1 0.013 ExM-4 0.065 ExM-5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95 11th layer (low sensitivity blue emulsion layer) Emulsion C Silver 0.18 ExS-7 8.0 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1.10 12th layer (medium sensitivity blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.15 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) ) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ⁻⁴ ExY-2 0.20 HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) Emulsion G 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5. 0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0 .10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, in each layer, storability, processability, pressure resistance, anti-mold and
W-1 for improving antibacterial property, antistatic property and coating property
To W-3, B-4 to B-6, F-1 to F-
17 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Contains rhodium salt. The emulsions represented by the above abbreviations are shown in Table 6 below, and the compounds are shown in Chemical formulas 25 to 37 below.
Are shown respectively.

[0339]

[Table 6] In Table 6, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to F are described in JP-A-3-23745.
According to the Example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate.

(3) Preparation of tabular grains is described in JP-A-1-1.
Low molecular weight gelatin is used according to the Example of 58426.

(4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0343]

[Chemical 25]

[0344]

[Chemical formula 26]

[0345]

[Chemical 27]

[0346]

[Chemical 28]

[0347]

[Chemical 29]

[0348]

[Chemical 30]

[0349]

[Chemical 31]

[0350]

[Chemical 32]

[0351]

[Chemical 33]

[0352]

[Chemical 34]

[0353]

[Chemical 35]

[0354]

[Chemical 36]

[0355]

[Chemical 37] The samples 101 to 104 thus obtained were exposed and then processed by the method described below.

Processing method Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching fixing 3 minutes 15 seconds 38 ° C water washing (1) 40 seconds 35 ° C water washing (2) 1 minute 00 Sec. 35 ° C. stable 40 sec. 38 ° C. dry 1 min. 15 sec. 55 ° C. Next, the composition of the treatment liquid is described. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,13.0-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N-β 4.5 -hydroxyethylamino] -2-methylaniline sulfate Water was added to 1.0 liter pH 10.05 (bleaching solution) ( Unit g) ethylenediaminetetraacetic acid 120.0 ferric ammonium dihydrate diethylenediaminetetraacetic acid disodium salt 10.0 ammonium bromide 100.0 ammonium nitrate 10.0 bleaching accelerator 0.005 mol ((CH ₃ ) N-CH ₂ -CH ₂ -S-) ₂ · 2HCl aqueous ammonia (27%) was added to 15.0ml water 1.0 liters PH 6.3 (bleach-fixing solution) (unit g) ethylenediaminetetraacetic acid ferric acid 50.0 ammonium dihydrate ethylenediaminetetraacetic acid disodium salt 5.0 sodium sulfite 12.0 ammonium thiosulfate aqueous solution (70%) 240. 0 ml Ammonia water (27%) 6.0 ml Water was added to 1.0 liter pH 7.2 (Washing liquid) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by sodium diisocyanurate dichloride 20
mg / l and 0.15 g / l sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5. (Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p 0.3 -monononyl phenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to the mixture 1. Regarding the characteristic curve of 0 liter pH 5.0-8.0 magenta dye, the sensitivity was shown by the relative value of the fog density and the reciprocal of the exposure amount giving a density 0.1 higher than the fog density. Gamma was obtained as the slope of a straight line connecting the point of fog +0.1 and the point of fog +0.6.

The results obtained are shown in Table 7 below.

[0358]

[Table 7] From Table 7, the emulsion of the present invention had a low fog, high sensitivity and a large gamma value, and the effect of the present invention was remarkable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroyuki Kawamoto, 210, Nakanuma, Minamiashigara-shi, Kanagawa, Fuji Photo Film Co., Ltd. (72) Morio Yagihara, 210, Nakanuma, Minamiashigara, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (6)

[Claims] 1. A silver halide grain formed while rapidly generating iodide ions, wherein the silver halide grain is chemically sensitized with a selenium sensitizer. Silver photographic emulsion. 2. An iodide ion-releasing agent is used such that 100 to 50% of the iodide ion-releasing agent present in the reaction vessel substantially completes the release of iodide ion within 180 consecutive seconds. The silver halide photographic emulsion according to claim 1. 3. The silver halide photographic emulsion according to claim 1, which is a silver halide grain formed by rapidly generating iodide ions using an iodide ion releasing agent and an iodide ion release controlling agent. 4. A reaction for rapidly generating iodide ions is a second-order reaction substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration, and its second-order reaction rate constant is 1000. To 5 × 10 ^-3 (M ^-1 · sec
^The silver halide photographic emulsion according to claim 1, wherein the iodide ion-releasing agent which is ^-1 ) is used. 5. A silver halide photographic emulsion according to claim 1, wherein an iodide ion-releasing agent represented by the formula (I) shown below is used. [Chemical 1] In formula (I), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. 6. A photographic light-sensitive material containing the silver halide photographic emulsion according to claim 1.