JPH05323485A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain a high sensitive silver halide emulsion suppressed in fogging by containing a silver halide particle arranged by epitaxial growing silver halide as a guest on a host particle which is a normal crystalline silver halide particle having transition in the inner part of the particle. CONSTITUTION:The host particle is the normal crystalline silver halide particle having transition in the particle and the silver halide particle arranged by epitaxial growing silver halide on the host particle is contained as the guest. And before epitaxial growing, a photosensitizing dyestuff is added. The surface of the normal crystalline silver halide particle is composed of (100) plane. Furthermore, coefficient of variation of particle size distribution is <=20%, the average silver iodide content of the host particle is <=10mol% and halogen composition of the host is composed substantially of silver bromide. The epitaxial growing position of the guest is regulated to be the vertex of the host particle.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive silver halide photographic emulsion having excellent photographic sensitivity.

[0002]

2. Description of the Related Art In recent years, the demands on the performance of silver halide emulsions for photography have become more and more strict, and in particular, high standards have been demanded for high sensitivity. Since conventional silver halide emulsions are not sufficient to meet this demand, further improvement in performance has been desired.

Regarding the observation of dislocation of silver halide grains, (1) CRBerry, J. Appl. Phys., 27, 636 (195)
6) (2) CRBerry, DCSkilman, J.Appl.Phys., 35, 21
65 (1964) (3) JF Hamilton, J.Phot.Sci.Eng., 11, 57 (19)
67) (4) T. Shiozawa, J. Soc. Phot. Sci. Jap., 34, 16 (1)
971) (4) T. Shiozawa, J.Soc.Phot.Sci.Jap., 35, 213.
(1972) and the like, it is possible to observe dislocations in the crystal by X-ray diffraction or low-temperature transmission electron microscopy, and by intentionally giving strain to the crystal, It is described that various dislocations occur.

The silver halide grains in these documents do not have dislocations intentionally introduced during the formation of photographic emulsions, but silver halide grains having positively introduced dislocations are disclosed in JP-A-63-220238, It is described in JP-A-1-201649. According to these patents, tabular grains having dislocation lines introduced to some extent have excellent photographic characteristics such as sensitivity and reciprocity law as compared with tabular grains having no dislocation lines, and sharpness when these are used in a light-sensitive material. Although it has been shown to have excellent graininess, it is still unsatisfactory due to problems such as high fog.

No case has been reported so far in which dislocations are positively introduced into normal crystal grains. A technique for improving the sensitivity of a silver halide grain by depositing a silver salt having a composition different from that of the silver halide on the silver halide host grain is described in European Patent Application No. 00199.
No. 17 (announced on December 10, 1980) and Tokkyo 3-4
Although disclosed in 5809 etc., it is not yet satisfactory in terms of the effect on particles having higher sensitivity.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having high sensitivity and suppressed fog.

[0007]

The objects of the present invention are as follows.
It is achieved by (1) to (10).

(1) A feature is that a normal crystal silver halide grain having a dislocation inside the grain is used as a host grain, and a silver halide grain in which silver halide is arranged as a guest by epitaxial growth is contained on the host grain. A silver halide photographic emulsion.

(2) The silver halide photographic emulsion as described in (1), characterized in that a spectral sensitizing dye is added before the epitaxial growth.

(3) The silver halide photographic emulsion according to (1), characterized in that the surface of the normal crystal silver halide grains is mainly composed of (100) faces.

(4) The silver halide photographic emulsion as described in (1), which has a variation coefficient of grain size distribution of 20% or less.

(5) The average silver iodide content of the host grains is 10
The silver halide photographic emulsion as described in (1) above, wherein the content is mol% or less.

(6) The silver halide photographic emulsion according to (1), wherein the halogen composition of the guest is substantially silver bromide.

(7) The silver halide photographic emulsion according to (1), wherein the epitaxial growth site of the guest is the apex of the host grain.

(8) The silver halide photographic emulsion according to (1), wherein at least 30% or more of the grains have 10 or more dislocation lines per grain.

(9) The silver halide photographic emulsion according to (1), wherein the amount of silver in the guest portion is 0.001 to 20 mol% with respect to the amount of silver in the host grains.

(10) The silver halide photographic emulsion according to (1), wherein the number of grains in which silver halide is arranged as a guest by epitaxial growth is 50% or more of the total number of grains.

The present invention will be described in more detail below.

The emulsion in the silver halide photographic light-sensitive material of the present invention is preferably a negative type silver halide grain having a regular crystal form such as a cube, octahedron, dodecahedron or tetrahedron. It is preferable that the particles are particles (normal crystal particles).

In the above emulsion, the surface of the grains is preferably composed mainly of (100) faces. The fact that the surface of the particle is mainly composed of the (100) plane is defined by the fact that the ratio P (%) of the area of the (100) plane to the total surface area of the particle shows a value of 70% or more. More preferably, the value is 80% or more. The above P (%) is T. Tani, Journal of Ima
Ging Science 29 165 (1985).

Usually, when the shape of the particles, the surface of which is mainly composed of the (100) plane, is observed with an electron microscope, the particles are cubic particles. Therefore, the shape of the emulsion grains in the present invention is preferably cubic.

The diameter of the normal crystal grain is 0.05 to
The thickness is preferably 5.0 μm, more preferably 0.
It is 1 to 2.0 μm. Coefficient of variation of size distribution is 20%
It is preferably not more than 15%, more preferably not more than 15%.

The silver halide grain in the present invention has dislocations inside the grain. The dislocations of silver halide grains are
For example JF Hamilton.Phot.Sci.Eng., 11, 57,
(1967) and T. Shiozawa, J.Soc.Phot.Sci.Japan, 3
5, 213 (1972), it can be observed by a direct method using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample is placed to prevent damage (printout etc.) due to electron beam. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough.
It is possible to observe more clearly by using an electron microscope of 200 kV or more for particles having a thickness of. The position and number of dislocations can be determined from the photograph of the particles obtained by such a method.

In the present invention, at least 30% or more of the grains have dislocation lines inside the grains. Preferably, at least 30% or more of particles are 10 per particle.
More than one dislocation line, and particularly preferably at least 80
% Or more of the grains have 10 or more dislocation lines per grain.

The halogen composition of the host silver halide grains in the present invention is silver iodobromide, silver bromide or silver chloroiodobromide.
The average silver iodide content of the host grains is preferably 10 mol% or less. The structure of the halogen composition inside the grain may be a uniform type, a double structure type, or a multiple structure type,
The high silver iodide phase may be present inside the grain, on the grain surface, or in the intermediate portion. Further, it may have a halogen-converted silver halochloride layer, a silver thiocyanate layer or a silver citrate layer inside the grain.

In the present invention, in order to introduce dislocations into the silver halide grains, silver halide having a high silver iodide content is grown on the host grains, or once the silver iodide content is increased. After growing high silver halide grains on the host grains, the growth is continued. In this case, the silver halide having a high silver iodide content is a silver halide containing 30 mol% or more of silver iodide, and preferably pure silver iodide.

A method for joining silver iodide on host grains having a face-centered cubic rock salt crystal structure by epitaxial growth is disclosed in JP-A-59-162540. According to this method, it is described that the deposition by epitaxial growth can be performed by selecting a silver salt that is non-isomorphic to the host grain crystal structure. This allows dislocations to be introduced into the silver halide by epitaxially growing silver iodide on the host grains or by growing the grains again after the epitaxial growth.

There is also a method of introducing dislocations into silver halide grains without using silver iodide. For example, it is possible to use a method in which a large number of minute projection-shaped silver chloride particles are formed on host grains, physically ripened, and if necessary, silver chloride is converted to silver chloride to remove chlorine.

According to the above method, first, silver chloride micro epitaxial is formed on the host grains. At this time, the temperature is preferably lower, and is preferably 60 ° C to 30 ° C. Moreover, pAg is preferably 6.0 to 7.2. Then, physical ripening is performed. At this time, the temperature is preferably 40 ° C
That is all. A silver halide solvent can be added if necessary. As the silver halide solvent, for example, thiocyanate, ammonia, thioether, thioureas can be used.

Specific examples thereof include thiocyanates (for example, US Pat. Nos. 2,222,264 and 2,44).
No. 8,534, No. 3,320,069), ammonia, thioether compounds (for example, US Pat. No. 3,27).
No. 1,157, No. 3,574,628, No. 3,7
04,130, 4,297,439, 4,
276,347) and thione compounds (see, for example, JP-A No.
No. 3-144319, No. 53-82408, No. 55-
77737), amine compounds (see, for example, JP-A-54-54).
No. 100717) thiourea derivative (for example, JP-A-55)
No. 2982) imidazoles (for example, JP-A-54-
No. 100717) and substituted mercaptotetrazole (for example, JP-A-57-202531).

Furthermore, if necessary, potassium bromide can be added to remove silver chloride by halogen conversion.
The amount of potassium bromide is 100 to 400%, preferably 100 to 200%, in terms of molar ratio with respect to the silver required for forming silver chloride microepitaxial.

Using such grains as host grains, silver halide is epitaxially grown as a guest. The guest composition includes silver chloride, silver bromide, silver iodide, or a mixture thereof, but is preferably substantially silver bromide. The term "substantially" as used herein means that a small amount of silver iodide or silver chloride contained in the base may be contained in the silver bromide epitaxial. This is because a part of the silver halide forming the base grains usually enters the growth solution during the epitaxial growth and is contained in the silver bromide epitaxial. Xmo is silver halide other than silver bromide
When it is contained in an amount of 1%, if it is x / 3 mol% or less, even if it is included in the silver bromide epitaxial layer, the effect of the silver bromide epitaxial layer is not impaired. JP-A-58-108526 or JP-B-3-45809 describes that silver chloride or silver thiocyanate has a high solubility and is more preferable for epitaxial deposition. However, these silver salts have problems in storage stability and reproducibility. By substantially forming a silver bromide epitaxial film, the problems of storage stability and reproducibility can be solved.

The amount of silver nitrate and halogen added at this time is preferably 0.01 to 20 mol% of the base grain, more preferably 0.01 to 5 mol%, and more preferably 0.1.
~ 5 mol%. The pAg at the time of addition is preferably 7 to 12, and more preferably 7 to 10. Addition temperature is 40
-70 degreeC is preferable and 40-55 degreeC is more preferable. In some cases, it is preferable to add the dye before the epitaxial growth, and the amount of the dye added at that time is 4 × 10 ⁻⁶ to 8 ×.
10 ⁻³ mol / mol Ag is preferable, 1 × 10 ^{−5 to} 5 × 1
0 ⁻³ mol / mol Ag is more preferable, and further 8 × 10
^{-5 to} 2 × 10 ^-3 mol / mol Ag is most preferable. The silver halide epitaxial deposition can be carried out by conventional precipitation techniques or Ostwald ripening techniques.

In the present invention, the number of epitaxial grains preferably accounts for 50% or more, more preferably 65% or more, and more preferably 80% of all grains.
It is most preferable to occupy the above. Further, it is more preferable that the epitaxial growth site is the apex of the host grain.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Gl.
afkides, Chimie et Physique Photograhique Paul Mon
(Tel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsio
n Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al, Making and Coating Photograph
ic Emulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good. 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.

The method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994. Is more preferable. These can be used as seed crystals and are also effective when 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 can be selected from total addition at once, divided addition in a plurality of times or continuous addition.

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,
The particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. 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. Further, 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.
Issue 3, Issue 3,342,605, Issue 3,415,650
No. 3,785,777, West German Published Patent No. 2,55
It can be selected and used from the methods described in 6,885 and 2,555,364.

The silver halide solvent described above 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. Also, other ripening agents can be used.
The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding the silver and halide salts, and the halide salt, silver salt or peptizer can be added in the reactor as well. Can also be introduced into. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. You can

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
16, enzyme-treated gelatin as described in p. 30, p30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate 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 ° C 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,
The method can be selected from the centrifugal separation method, coagulation sedimentation method and 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,
During the desalting process and chemical sensitization, the metal ion salt is present before coating.
It is preferable to do so according to the purpose. Dope particles
In some cases, during grain formation, grain surface modification or chemical sensitization
When used as an agent, added after grain formation and before chemical sensitization
Preferably. Doping the entire particle and the particle
Core part only, shell part only, or epi
Dope only in the axial part or only in the base particles
You can also choose how to do it. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals are ammoniu
Salts, acetates, nitrates, sulphates, phosphates, hydrates or
Is a hexacoordinated complex salt, a tetracoordinated complex salt, etc., and is dissolved when particles are formed.
Any salt form can be added. For example, CdB
r₂, CdCl₂, Cd (NO₃)₂, Pb (NO₃)₂,
Pb (CH₃COO)₂, K ₃[Fe (CN)₆], (N
H_Four)_Four[Fe (CN)₆], K₃IrCl₆, (NH_Four) ₃
RhCl₆, K_FourRu (CN)₆Etc. Coordination
Halo, aco, cyano, cyanene as ligands for compounds
G, thiocyanate, nitrosyl, thionitrosyl, o
You can choose from Kiso and Carbonyl. these
May use only one type of metal compound, but two types or
You may use it in combination of 3 or more types.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
1, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acid or alkali may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. It is also possible to add it to a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, KI) and continuously add it during the formation of silver halide grains. Furthermore, 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.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate,
Phosphate and acetate may be present.

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization in any step of the silver halide emulsion production process. Can be applied with. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded in the grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which chemically sensitized nuclei are formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected according to the purpose, but it is generally preferable that at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention
One is chalcogenide sensitization and noble metal sensitization, either alone or in combination.
And, The Photographer by James (T.H. James)
Fick Process, 4th edition, published by Macmillan, 197
7 years (T.H. James, The Theory of the Photographic P
rocess, 4th ed, Macmillan, 1977) 67-76.
Can be done with active gelatin as described
RUSSHI, Research Disclosure Volume 120, 1
April 974, 12008; Research Disclosure
Jar, Vol. 34, June 1975, 13452, USA
Patent Nos. 2,642,361 and 3,297,446
Issue 3,772,031, Issue 3,857,711
Issue 3, Issue 3,901,714, Issue 4,266,018
No. 3,904,415 and British Patent No.
PAg5-1 as described in No. 1,315,755.
Sulfur at 0, pH 5-8 and temperature 30-80 ° C,
Selenium, tellurium, gold, platinum, palladium, iridium or
Alternatively, a combination of a plurality of these sensitizers can be used.
In noble metal sensitization, gold, platinum, palladium, iridium
Precious metal salts such as um can be used.
Sensitivity, palladium sensitization and a combination of both are preferred. Money increase
In case of feeling, chloroauric acid, potassium chloroaurate,
Potassium aurithiocyanate, gold sulfide, gold selenide
Known compounds such as can be used. Palladium
The compound means a divalent or tetravalent salt of palladium. Good
Rare palladium compounds₂PdX₆Or R₂P
dX_FourIt is represented by. Here, R is a hydrogen atom, alkali gold
Represents a genus atom or an ammonium group. X is a halogen source
Represents a child, and represents a chlorine, bromine or iodine atom. Concrete
Specifically, K₂PdCl_Four, (NH_Four)₂PdCl₆, Na
₂PdCl_Four, (NH_Four)₂PdCl_Four, Li₂PdCl
_Four, Na₂PdCl₆Or K₂PdBr _FourIs preferred
Yes. Thiocyanates for gold and palladium compounds
Alternatively, it is preferably used in combination with selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,05
The sulfur-containing compounds described in 4,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,
411,914, 3,554,757, JP-A-5
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mol of silver halide.
It is 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1
It is ^{x10 -5 to} 5 x 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both. The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, 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. Known reduction sensitizers include stannous salt, 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, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount.
A range of 0 ^-7 to 10 ^-3 mol is suitable.

The reduction sensitizer is dissolved in water or a 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. In addition, it is also a preferable method to add the solution of the reduction sensitizer in several times with the grain growth or to continuously add the solution for a long time.

Acid for silver during the manufacturing process of the emulsion of the present invention.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are silver halide, silver sulfide, and selenium.
It may form a sparingly soluble silver salt such as silver halide, or silver nitrate.
A silver salt that is easily soluble in water may be formed. Oxidation for silver
The agent may be an inorganic substance or an organic substance. inorganic
Ozone, hydrogen peroxide and its addition as oxidizing agents
Thing (eg NaBO₂, H₂O₂・ 3H ₂O, 2Na
CO₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂Two
Na₂SO _Four・ H₂O₂・ 2H₂O), peroxy acid salt
(Eg K₂S₂O₈, K₂C₂O ₆, K₂P
₂O₈), Peroxy complex compounds (eg, K₂[Ti
(O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na ₃[VO (O₂)
(C₂H_Four)₂・ 6H₂O), permanganate (eg,
KMnO _Four), Chromates (eg, K₂Cr₂O₇)
Which oxyacid salts, halogen elements such as iodine and bromine, perhalo
Genates (eg potassium periodate) of high valence metals
Salts (eg potassium hexacyanoferrate) and thi
Osulfonate and the like.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B). The preferred oxidant of the present invention is ozone,
Hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidants and quinones organic oxidants. It is a preferred embodiment that the reduction sensitization described above and the oxidizing agent for silver are used in combination. The method 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 selected and used in both 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 fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. .. That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
Nos. 47 and 52-28660 can be used. Japanese Patent Application Sho 6
There are compounds described in 2-47225. 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. Addition during emulsion preparation to exert the original antifogging and stabilizing effect, in addition to controlling the crystal wall of the grain, reducing the grain size, reducing the solubility of the grain, controlling chemical sensitization, 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, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5- or 6-membered heterocyclic nucleus such as a 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 especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12,375, and Japanese Patent Laid-Open No. 52-375. -110,618 and 52-109,925.

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 timing of adding the sensitizing dye to the emulsion may be 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. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 8-969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, it is possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, ie to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains including the method disclosed in US Pat. No. 4,183,756. The addition amount is 4 × 10 ^-6 to 1 mol of silver halide.
Although it can be used in an amount of 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective for a more preferable silver halide grain size of 0.2 to 1.2 μm.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. 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. In the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-
The couplers and DIR compounds as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are 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 installed in order. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in Japanese Patent No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also be arranged in the order of / GH / RH.

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. Another example is 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. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, they 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 configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used according to the purpose. These additives are
For more details, Research Disclosure Item 1764
3 (December 1978), Item 18716 (1979)
November) and Item 307105 (November 1989)
Month), and the relevant parts are summarized in the following table.

[0068]

[Table 1]

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat. Nos. 4,470,454 and 4,788,132.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C-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
1,432, 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-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 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.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are 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 and the like.

As couplers in which the color forming dye has an appropriate diffusibility, 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. Research Disclosure No. is a colored coupler for correcting unnecessary absorption of color forming dye.
17643, Item VII-G, ibid. VII-307-
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 releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,093
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.
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. 173,302A and 313,308A R.K. D. No.
11449, 24241, JP-A-61-201247.
Bleach accelerator releasing couplers described in U.S. Pat.
Examples thereof include ligand releasing couplers described in US Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, couplers releasing a fluorescent dye described in US Pat. No. 4,774,181, and the like. To be

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. 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 (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-)
Octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical 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.

Suitable supports which can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid. 18
716, right column, page 647 to left column, page 648, and ibid.
307105, page 879.

In the photographic 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 means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A. Green
Photographic Science and Engineering (Photogr.Sci.Eng.), Volume 19, Issue 2, 1
Serometer of the type described on pages 24 to 129 (swelling meter)
Can be measured, and T _1/2 is 90% of the maximum swollen film thickness reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer, and the saturated film thickness is defined as 1/2 of the saturated film thickness. It is defined as the time to reach.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The photographic 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. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid. 18
716, 651 left column to right column, and the same No. 307105
It can be developed by a usual method described on pages 880-881.

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-
Examples thereof include 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. Two or more kinds of these compounds can be used in combination depending on the purpose.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination.

The pH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The color development processing time 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 the color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, aminopolycarboxylic acid irons such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
(III) Complex salt 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 the bleaching solution or the 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: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. 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 photographing.

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 preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically, acetic acid,
Propionic acid and the like are preferred.

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. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and 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, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2 for adjusting the pH. It is preferable to add 0.1 to 10 mol / l of imidazoles such as methylimidazole.

The total time of the desilvering process 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 process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. 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 above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, 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 process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers Volume 64, P.248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably 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 stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, there is a case where a stabilizing treatment is further carried out after the above-mentioned water washing treatment. As an example, a stabilizing treatment containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is given. You can mention the bath. 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 other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure
No. 14,850 and the same No. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

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 disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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 is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2 and the like.

[0110]

EXAMPLES The present invention will be further described below with reference to examples. Example 1 (1) Preparation of emulsion A. Preparation of host particles a. Preparation of emulsion A-1 (seed emulsion)

An aqueous solution containing 0.94 mol of silver nitrate and potassium bromide was added to 1.5 liter of an aqueous solution containing 0.2 g / liter of potassium bromide and 30 g / liter of gelatin by the double jet method while maintaining the temperature at 45 ° C. A 0.94 mol / liter aqueous solution was added while keeping the pAg at 7.3 to prepare an emulsion A-1 composed of silver bromide cubic grains having a sphere-equivalent diameter of 0.2 μm. b. Preparation of Emulsion A-2 (octahedral host grains)

The seed emulsion A- in which the amount of silver atom is 0.1 mol.
1 and 1 g of an aqueous solution containing 30 g of gelatin, while maintaining the temperature at 70 ° C., add a 1.6 mol / liter aqueous solution of silver nitrate and a 1.6 mol / liter aqueous solution of potassium bromide while keeping the pAg9. did. The silver nitrate used was 0.9 mol. It was desalted by the usual flocculation method. Obtained emulsion A-
No. 2 consisted of octahedral grains having a sphere-equivalent diameter of 0.4 μm. c. Preparation of Emulsion A-3 (cubic host grains)

Emulsion A-3 was prepared by changing pAg during grain formation to 7.3 in the method of preparing emulsion A-2. The resulting emulsion A-3 consisted of cubic grains having a spherical equivalent diameter of 0.4 μm. B. Preparation of particles with dislocations a. Preparation of Emulsion B-2 (octahedral grains with dislocations)

Emulsion A-2 (0.5 mol silver) 500 g
And 350 cc of distilled water were mixed, the temperature was raised to 76 ° C., and the mixture was sufficiently stirred. Then, 0.04 mol / liter silver nitrate aqueous solution and 0.04 mol / liter potassium iodide aqueous solution were added over 5 minutes. The addition amounts of silver nitrate and potassium iodide corresponded to 3 mol% with respect to the silver amount of the host grains. Thereafter, an amount of silver nitrate and potassium bromide in an amount corresponding to 50 mol% with respect to the silver amount of the host particles was added as an aqueous solution of 1.6 mol / liter while keeping pAg at 9 and added for 60 minutes. Then, it was desalted by a usual flocculation method. The resulting emulsion B-2 had a sphere equivalent diameter of 0.46 μm.
m octahedral grains. b. Preparation of Emulsion B-3 (cubic grains having dislocations)

In the preparation method of Emulsion B-2, Emulsion B-3 was prepared by changing the host grain to A-3 and changing the pAg when adding silver nitrate and potassium bromide to 7.0.
The resulting emulsion B-3 consisted of cubic grains having a sphere-equivalent diameter of 0.46 μm. C. Preparation of dislocation-free particles a. Preparation of C-2 (Dislocation-Free Octahedral Grains) Emulsion C-2 was prepared by removing the step of forming silver iodide from the method of preparing emulsion B-2. The resulting emulsion C-2 consisted of octahedral grains. b. Preparation of C-3 (Dislocation-Free Cubic Grain) Emulsion C-3 was prepared by removing the step of forming silver iodide from the preparation method of emulsion B-3. The resulting emulsion C-3 consisted of cubic grains. (2) Observation of particle dislocation

Emulsions B-2, B-3, C-2, C-3
Were observed directly using a transmission electron microscope. It was observed at an acceleration voltage of 200 kV or more and a temperature of -120 ° C.

Dislocation lines were observed in Emulsions B-2 and B-3. In Emulsions B-2 and B-3, random dislocations were indiscriminately present in the silver halide grains. The proportion of grains having dislocations was obviously 80% or more.

(3) Spectral sensitization Emulsions B-2, B-3, C-2 and C-3 were sensitized as follows.
Sensitizing agent 8.0 × 10 ^-Fourmol / mol Ag was added.

[0119]

[Chemical 1]

(4) Preparation of grains in which silver halide was arranged as a guest by epitaxial growth For the spectrally sensitized emulsions B-2, B-3, C-2 and C-3, host grains of A silver nitrate solution (concentration: 1.17 mol / l) and a potassium bromide solution (concentration: 1.68 mol / l) in an amount corresponding to 2.1 mol% based on the silver amount were added by the double jet method over 1 minute. The particles having the epitaxial growth sites thus obtained are referred to as D-2, D-3, E-2, and E-3 with respect to B-2, B-3, C-2, and C-3.

(5) Chemical Sensitization Emulsion B-2, B-3, C-2, C-3, D-2, D-
Sodium thiosulfate, potassium thiocyanate, and chloroauric acid were added to 3, E-2, and E-3 so that the highest sensitivity would be obtained when exposed for 1/100 second, and the mixture was aged at 60 ° C. for 60 minutes.

(6) Preparation of coating sample and evaluation thereof Each emulsion prepared as described above was coated on a cellulose triacetate film support having an undercoat layer by coating the emulsion and the protective layer in the following coating amounts. Samples 101 to 108 were prepared.

(1) Emulsion layer ・ Emulsion ... Various emulsions (silver 3.6 × 10 ^-2 mol / m ² ) ・ Coupler (1.5 × 10 ^-2 mol / m ² ).

[0124]

[Chemical 2]

[0125] - tricresyl phosphate (1.10 g / m ²⁾ · Gelatin ^{(2.30g / m 2) (2} ) protective layer, 2,4-dichloro-6-hydroxy -s- thoria Jin sodium salt ( 0.08 g / m ² ). Gelatin (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 processing was performed according to the following steps. The density of the treated sample was measured with a green filter. Next, the composition of the treatment liquid used will be 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 Hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleach-fix solution (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator represented by the following chemical formula 3 0.01 mol

[0126]

[Chemical 3]

1.0 L with addition of water pH 6.0 (aqueous solution)

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) was passed through 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 sodium sulfate 1.5 g / liter were added. The pH of this solution is in the range 6.5-7.5. (Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1 0.0 liter pH 5.0-8.0

The sensitivity was represented by the relative value of the reciprocal of the exposure amount expressed in lux · sec which gives a density of 0.2 on the fog.
(The sensitivity of Sample 1 one day after application was set to 100.) The above results are shown in Table 1.

[0130]

[Table 2]

As is apparent from Table 1, the emulsions D-2 and D-3 according to the present invention have remarkably high sensitivity as compared with the other comparative examples, and remarkably suppress high fog caused by dislocation introduction. Recognize.

Comparing the emulsions D-2 and B-2 obtained by epitaxially growing the emulsion B-2, it is found that high sensitivity is realized by the epitaxial formation.

The same can be said by comparing the emulsions E-2 and C-2 obtained by epitaxially growing the emulsion C-2.

Further, for example, emulsions B-2, D-2, C-
From the comparison of 2 and E-2, it is understood that the effect of increasing the sensitivity and the effect of suppressing fogging by the epitaxial formation are larger in the particles having dislocation lines.

Emulsions B-2, B-3 and D-2, D-
As compared with No. 3, cubic grains have a larger effect of epitaxial formation in a normal crystal having dislocation lines inside grains. This effect was larger than the difference expected from the effect of epitaxial formation in a normal crystal having no dislocation line inside the grain, which was suggested by comparison between C-2, C-3 and E-2, E-3.

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in multiple layers to prepare samples 201 to 208 which are multilayer color light-sensitive materials. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount 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.

(Sample 201) 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 (First 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

Fourth Layer (Second 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-2 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

Fifth Layer (Third 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

Sixth Layer (Intermediate Layer) Cpd-1 0.040 HBS-1 0.020 Gelatin 0.80

Seventh Layer (First Green Sensitive Emulsion Layer) Emulsion C Silver 0.30 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 (Second Green Sensitive Emulsion Layer) Emulsion of the present invention (B-2, B-3, C-2, C-3, D-2, D-3, E-2 of Example 1) , E-3) Silver 0.55 ExS- ⁴ 2.2x10 ^-5 ExS-5 1.5x10 ^-4 ExS-6 5.8x10 ^-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

Ninth Layer (Third Green Sensitive Emulsion Layer) Emulsion E Silver 1.55 ExS-4 4.6 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.9 × 10 ⁻⁴ 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 Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95

Eleventh Layer (First Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1 .10

Twelfth Layer (Second Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.15 HBS-10 0.050 gelatin 0.78

Thirteenth Layer (Third 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

Fourteenth Layer (First Protective Layer) Emulsion G Silver 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-30 .10 S-1 0.20 Gelatin 1.20

Further, each layer has storability, processability, pressure resistance,
W-1, W-2, W-3, B-4, B-5, B- for improving antifungal / antibacterial properties, antistatic properties and coating properties.
6, F-1, F-2, F-3, F-4, F-5, F-
6, F-7, F-8, F-9, F-10, F-11, F
-12, F-13, F-14, F-15, F-16, F
-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

[0153]

[Table 3]

In Table 2, (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 were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) Low molecular weight gelatin was used in the preparation of tabular grains according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0155]

[Chemical 4]

[0156]

[Chemical 5]

[0157]

[Chemical 6]

[0158]

[Chemical 7]

[0159]

[Chemical 8]

[0160]

[Chemical 9]

[0161]

[Chemical 10]

[0162]

[Chemical 11]

[0163]

[Chemical formula 12]

[0164]

[Chemical 13]

[0165]

[Chemical 14]

[0166]

[Chemical 15]

[0167]

[Chemical 16]

Emulsion B- of Example 1 was used as the eighth layer emulsion.
2, B-3, C-2, C-3, D-2, D-3, E-
Sample 201-
208 was produced. Sample 201 thus obtained
~ 208 were exposed to light and developed in the same manner as in Example 1. For each sample after exposure, the sensitivity was evaluated by the reciprocal of the exposure amount that gave a density 1.0 higher than the minimum density of magenta measured with a green filter. The results are shown in Table 3 below.

[0169]

[Table 4]

Third, Samples 205, 206 according to the present invention
Indicates that the feeling is significantly higher than that of the comparative example, and the effect of suppressing fogging is also large.

[0171]

According to the present invention, it is possible to obtain a silver halide emulsion having high sensitivity and suppressed fog.

Claims (10)

[Claims] 1. A normal crystal silver halide grain having a dislocation inside the grain is used as a host grain, and the silver halide grain is arranged on the host grain as a guest and silver halide is arranged by epitaxial growth. Silver halide photographic emulsion. 2. The silver halide photographic emulsion according to claim 1, wherein a spectral sensitizing dye is added before the epitaxial growth. 3. The surface of the normal crystal silver halide grains is mainly composed of (100) planes.
The described silver halide photographic emulsion. 4. The silver halide photographic emulsion according to claim 1, wherein the variation coefficient of grain size distribution is 20% or less. 5. The average silver iodide content of the host grains is 10 mo.
The silver halide photographic emulsion according to claim 1, which is 1% or less. 6. A silver halide photographic emulsion according to claim 1, wherein the halogen composition of the guest consists essentially of silver bromide. 7. The silver halide photographic emulsion according to claim 1, wherein the epitaxial growth site of the guest is the apex of the host grain. 8. At least 30% or more of particles are 1
The silver halide photographic emulsion according to claim 1, which has 10 or more dislocation lines per grain. 9. The silver halide photographic emulsion according to claim 1, wherein the amount of silver in the guest portion is 0.001 to 20 mol% with respect to the amount of silver in the host grains. 10. The silver halide photographic emulsion according to claim 1, wherein the number of grains in which silver halide is arranged as a guest by epitaxial growth is 50% or more of the total number of grains.