JPS58139137A - Photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a photographic silver halide emulsion having a wide latitude of exposure by dispersing dispersible particles contg. a development inhibitor releasing compound and a colored coupler and dispersible particles contg. a colorless coupler in a silver halide emulsion. CONSTITUTION:This photographic silver halide emulsion is obtd. by dispersing dispersible particles contg. a development inhibitor releasing compound and dispersible particles contg. a colorless coupler in a silver halide emulsion. The particles contg. the development inhibitor releasing compound contain a colored coupler, and the particles contg. the colorless coupler may contain a colored coupler but do not contain a development inhibitor relesing compound. A benzoylacetoanilide compound or a pivaloylacetoanilide compound is preferably used as the colorless coupler. The amount of the colorless and colored couplers to be used is 2/10<3>-3/10mol, preferably 5/10<3>-3/10mol per 1mol silver in the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic emulsion KsI, and more particularly to a silver halide photographic emulsion having excellent storage stability.

A photographic light-sensitive material prepared by coating a hecoupler in a tin halide emulsion on a support is developed with a developer containing an aromatic amine 1IllI form to form a suitable formulation-releasing compound (hereinafter referred to as p-R compound). Silver halide photographic emulsions containing at the same time the above emulsions are known, and it has been expected that the emulsions can be coated to improve photographic properties such as film quality and exposure latitude of photographic light-sensitive materials. Examples of this include British Patent No. 1゜269.037 and British Patent No. 1,26.
No. 1.061 and British Patent No. 1,269,075. However, it is also well known in the art that when coating solutions of silver halide photographic emulsions containing such couplers are stored at high temperatures, photographic properties such as quality and exposure latitude deteriorate. Improvements were desired.

An object of the present invention is to provide a silver halide photographic emulsion having a wide exposure latitude.

Another object of the present invention is to provide a silver halide photographic emulsion in which deterioration in photographic performance is improved when a coating solution of a photographic emulsion containing a coupler is stored at a high concentration.

The above object of the present invention v4 was achieved by discovering a silver halide photographic emulsion having the following characteristics.

In a silver halide photographic emulsion formed by dispersing dispersed grains containing a development inhibitor-releasing compound and dispersed grains containing a colorless coupler, the dispersed grains containing a development inhibitor-releasing compound contain at least A silver halide photographic emulsion (hereinafter referred to as "flK") is characterized in that it contains a kind of colored coupler, and the dispersed grains containing a colorless coupler may contain a colored coupler but do not contain a development inhibitor-releasing compound. (referred to as such silver halide photographic emulsion).

The original I! The colorless coupler, colored coupler and DIR compound used in the silver halide photographic emulsion according to jIK can be arbitrarily selected from conventionally known compounds.

As the colorless coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include US 51411 No. 2.875,057, US 3,408,194, US 3.551,155, US II 3,582,322, and US 3. .894,875, West German Patent Publication No. 1.547.868, West German Patent Application (
OLS) No. 2,213,461, fjll No. 2,261
,361! , 1iiJII2.263.875! , No. 2.414,006, etc.

Specific examples of the colorless yellow coupler used in the tlA of the present invention are described below.

-1 α-(4-ruboxyphenoxy)-α-biparyl 2
-chloro5-(r-(2,4-di-t-amylphenoxy)butyramide)acetanilide-2
t-Amylphenoxy)butylamidocoacetanilide-3 α-benzoyl-2-curo-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetoanilide F-4 α-(4-carboxyphenoxy)-α- Viparilu 2
-Claw 5-[α-(3-pentadecylphenoxy)
butylamide]acetanilide-5 α-(l-benzyl-2,4-dioxo-3-imidazolidinyl)-α-pivalyl-2-chloro5-[r-(
2,4-di-t-amylphenoxy)butyramide]acetanilide-6 α-(4-(,1-benzyl-2-7enyl-3゜5-
dioxo-1,2,4-triaziridinyl)]-]α-
biparyl-2-chloro-5(r-(2,4-di-t-
amylphenoxy)butyramide]acetanilide-7 α-acetoxy-α-13-[α-(2,4-di-t-
amylphenoxy)butyramide]benzoyl)-2-
Methoxyacetanilide-p α-(3-[α-(2,4-di-t-amylphenoxy)butyramide]benzoyl)-2-methoxyacetanilide-9 α-[:4-(4-hensyloxy7-ethylsulfoyl)phenoxy] -α-Biparyl 2-Kurota-5-(r-
(2,4-di-t-amylphenoxy)butyramide core heptaanilide! -10 α-Hibiparyl α-4,5-dikuan-3(2H)-
pyridazol-2-yl)-2-chloro* -5-[(hexyloxycarbonyl)methoxycarbonyl]acetanilide-11 α-piparyl α-(4-(p-0ax diphenyl)-
5-Oxo-Δ3-tetrazoline-1-i,ru)-2-
pa milo-(α-(dodecyloxycarbonyl A/)ethoxycarl-nyl)acetanilito! -12 α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-Vivalyl 2-ripro5-[
α-(2,4-di-t-amylphenoxy)butyramide]acetanilide-13 α-piparyl α-(4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-)riazolidinyl )
]-2-riaa-5-(r-(2,4-di-1-amylphenoxy)butyramide)acetanilide-14 α-vivalyl α-(4-(p-ethylphenyl)-5
-oxo-Δ3-tetrazolin-1-yl]-2-chloro*-5-(r-(2,4-di-t-amylphenoxy)
Butylacetanilide-15 α-(4'-methoxypency)-α-pyrazolyl-
2-Chloro-5-dodecyloxycarbonylacetanilide colorless magenta couplers mainly use 5-pyrazolone compounds, but indazone compounds and cyanoacetyl compounds are also used, examples of which are disclosed in U.S. Pat. No. 2,600,788. No. 3゜062.6! ! No. 3,
Same No. 3,127,269, Same No. 3゜311.476, Same No. 3,419,391, Same No. 3゜519.429
No. 3,558,319, No. 3゜582.32
No. 2, No. 3,615,506, West German Patent No. L810
, No. 464, West German Patent Application (O12) 2゜408.66
No. 5, No. 2,418,959, No. 2゜424.4
No. 67, patent l! No. 14O-6031, No. 44-201
This is described in No. 6, etc.

Specific examples of the colorless magenta coupler used in the present invention are described below.

-1 1-(2,4,6-)lichloroWphenyl)-3-(3-
(2,4-di-t-7-milphenoxyacetamide)penzami)")-5-pyrazoline-2 1-(2,4,@-)ritarotetraphenyl)-3-(3-
dodecylsuccinimidobenzamide)-5-pyrazoline-3 4,4'-methylenebis(1-(2,4,6-)riftaniphenyl)-3-(3-(2,4-di-t-7milf) enoxyacetamido)benzamide-5-bilazonitone) -4 1-(2,4,1-)ritalolophenyl)-3-(2-
Chlo-a-5-octadecylsuccinimide/)
-5-pyrazolone-5 1-(2-riaa-4,@-dimethylphenyl)-3-
43-(α-(3-pentadecylphenoxy)butyramide]penzamide)-5-pyrazolonto' 1-(2,4,6-)wakuI2tetraphenyl)-3-(2
-Chloro-5-octadecylcarno (moylanilino)
-5-Pyrazolone-7 1-(2,4,6-)Ricprofuel)-3-(3-
(2,j-di-t-amylphenoxy to chizyruad)
Penzamide]-5-Virazonitone-8 3-Ethoxy-1-(4-(α-(3-pentadecylphenoxy)phthylamido]phenyl)-5-pyrazolonto] 1-(2,4,6-)rita ν Lofuel)-3-(2-
Yushia -5-tetradecanamide anilino)-5-pyrazolone -10 1-(2,4,6-)rifaa7x=x)-3-(2-
Chlo-a-5-(α-(3-t-butyl-4-and-do-4-oxyphenoxy)tetradecanamideanilino)-5-pyrazolone-11 1-(2,4,6-)lichlorophenyl)-3- (3-
(2,4-di-t-amylphenoxyacetamide)benzamide]-4-acetoxy-5-vilazon
' -12 1-(2,4,6-)ritarotetraphenyl)-3-(3-
(2,4-di-t-amylphenoxyacetamide)penzamide)-4-ethoxycarbonyloxy-5゛-
Pyrazolone -13 1-(2,4,@-)lichlorophenyl)-3-(3
-(2,4-di-t-amylphenoxyacedo(do))
Penzamide)-4-(4-chlorocinnamoyloxy)-5-pyrazolone-14 1-(2,4,11-tric04phenyl)-3-43
-(4-n-dodecylbenzenesulfonamide)penzamide)-5-bilazoline-15 4,4'-penzyldenby(1-(2,4,6-)lichloraphenyl)-3-(2-chloro -5-[r-(2
,4-di-t-amylphenoxy)butyramide]anilino)-5-pyrazolone] -16 4,4'-benzyldenbis(t (2,L4- L
6-pentachlorophenyl)-3-(2-ri44-5
-(r-(2,4-di-t-amylphenoxy)butyl-anilino)-5-pyrazolone] -17 4,4'-(2-riaa)penzyldenbis(1-(2
,4,6-)lichlorophenyl)-3-(2-talo a
-5-dodecylsuccinimidoanilino)-5-pyrazolone] -18 4,4'-methylenebis(1-(2,4,6-)riftetraphenyl)-3-(3-(α-(2,4- monoamylphenoxy) butylbenzamide) -5-
[Pyrazolone] In the colored magenta caprate used in the present invention, a compound substituted with arylazo at the coupling position of the general colorless magenta caprate is used,
For example, Kawa II Patent No. 2,801゜171;
, No. 983,608, No. 3,005,712, @
No. 8,684,514, British Patent No. 937°621,
Examples include chemical compounds described in JP-A-49-123625 and JP-A-49-31448. Furthermore, a type of colored magenta coupler, such as that disclosed in U.S. FFL Patent No. 3,419,3911, in which the dye flows out into the processing solution by reaction with the oxidized material on the main surface of the original can also be used. . Specific representative examples are listed below.

0M-1 1-(2,4,6-)rif 4-day phenyl)-4-(4-
Methoxyphenylazo-3-(3-(2,4-di-t-
Penzamide -5
-Virazoquan 0M-2 1(L4@@-trichlorophenyl)-4-(l-naphthylazo)-3-(2-ri-5-octadecenylsuccinimidoanilino)-5-pyrazolone 0to4 l-(2,4,6-)lichlophenyl)-4-(4-
Hydroxy-3-methylphenylazo)-3-(2-chloro-5-tetradecanamideanilino)-5-virazo, pn0M-4 1-(2,4,6-)rifa a y : c = tv
) -4-(4-hydroxy-3-methylphenylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone M-5 1-(2,4,6-) lift t1 lift el) -3-(2
-Chloro-5-[α-(4-human taki-3-t-butylphenoxy)tetradecanamide anilino)-4-(
1-naphthylazo)-5-pyrazolone 0M-6 1-(2,4,6-)rifa vx y x x-l)
-3-(2-chloro-5-[α-(2,4-di-t-
amylphenoxy)butyramide]aelino) −,
4-(4-methodiphenylazo)-5-virazolone 0
M-7 1-(2,4,@-)likuprophenyl)-3-(tomi-
riaa-5-[r(L4-di-t-amylphenoxy)
butyramide]anilino) -'4-(4-hydroxyphenylazo)-5-vilazopone0M-8 1-(2,3,4,5,@-pentachlorotetraphenyl)-
3-(2-Krylo5-(r-(2,4-di-t-amylphenoxy)butyramide]anilino)-4-(4-
Phenol or naphthol derivatives are mainly used as colorless cyan couplers. A specific example is AIM Permit No. 2,369,9291. Same No. 2.474, 2
No. 93, No. 2.521.9011, No. 2, 811
S, sgg issue, f111113,034,892,
Same No. 3.386,830, Same No. 3.4!58.31 91. 3.471$, 563, 118,583
, No. 971, No. 3, No. 591.383, II#II 1977-7890! ! There are some listed in the issue.

Specific examples of colorless cyan couplers used in Honjitsu@ are described below.

-1 1-human tetraxydoCa-(2,4-di-t-amylphenoxy)butyl-2-naphthamide-2 1-human dixy-N-(r-(L4-di-t-amylphenoxy)butyl) -2-naphthamide -3 2,4-dichloroa -3-methyl-6-(2,4-di't-amylphenoxyacedo(do)phenol) -4 2,4-dichlorovx-3-methyl-6 −[α−(2,4
-di-t-amylphenoxy)butyramide] °phenol □ ・・ -5 2-perfluorinated butylacetl'-5-(α-(2,
4-Di-t-amylphenoxy)hexylphenol-6 1-hydroxy-4-(octadecyl-(do)-toethyl-3',r;-dicarboxy-2-naphthamide-7 1- Hydroxy-4-anilinocarbonyl oxide-
(J-(2,4-di-t@rt-amylphenoxy)butyl-2-naphthamide-8 1,2-bis-(4-hydoxy-3-[K-(J-
(2,4-di-t@rt-amylphenoxy)butyl]
Carbamoyl]-1-naphthyloxycarba())ethane-5 1- and droxy-4-(ethoxycarbonylmethoxy)
-w-(J-(2,4-di-t@rt-alkyl)butyl-2-naphthamide -10 1- and dolxy-4-[β-methoxyethylaminocarbonylmethoxy)-N -(a-(2 ,4-G t r
t-amylphenoxy)butyl]-2-naphthoa(do-11 2-chloro-3-methyl-4-carboxymethoxy-6
-[β-(2,4-di-t@rt-amylphenoxy)
Butyroylaminoco-phenol-12 1-hydroxy-4-methoxycarbonyloxy-N
-dodecyl-2-su7tamide-13 1-hydroxy-4-(4-toluenesulfonamide)
-輯-(-(-(2,4-di@rt-a,milphenoxy)butyl)-2-naphtho--14 1-hydroxy-+'-'<i=<7-tylaminocarl-nyloxy)- Kenichi (a-(2,4-diw-amylphenoxy)butyl]-2-naphthamide 0-15 1-hydroxy-4-[α-(β-methoxyethoxycarbonyl)ethoxy)-N-(δ-( 2゜4-Gt@
rt-amylphenoxy)butyl-2-naphtho-16 1-hydroxy-4-(4-(β-carboxypamide)-phenoxy"l-2-(N-(J-(2,4
-Gt@rt-amylphenoxy)butyl acetate])
Naphthoic acid amide-17 1-Hydroxy-4-(β-methanesulfonylmethoxy)-2-(N-hexadecyl)-naphthoic acid Tsukidomotoji-IjI The colored cyan coupler used in IjI is phenol or naphthol S* form. For example, U.S. Patent No. 2,521,
No. 908, same No. 35034.8928. English l1III
Patent No. 1.255,111, Japanese Patent Application Publication No. 48-22028, Oka No. 50-123341, No. 5o-totss,
It is described in U.S. Patent No. 3,476.563 and the like as the Kinsei method.

Specific examples of colored cyan couplers used in this study are as follows.

0-1 l-hydroxy-4-(2-a7tylphenylazo)
-N-(J-(2,4-di-t-amylphenoxy)butyl-2-natutoad0-2 1-hydroxy-4-(2-(β-phenylpropionyl)phenylazo) -Yanichi [a ( L4-G-t-
amylphenoxy)butyl]-2-naphthamide 0-5 1-heatroxy4-funinylazo-4'-(4-t
-f tylphenoxy)-2-naphthanilide 0-4 1- and nitrogen and -4-(4-(-1-hydroxy-8-
acetamido-3,6-disulfo-2-naphthylazo)
, phenoxycode-(J-(2,4-di-t-amylphenoxy)phthyl)-2-naphthoric disodium salt 0-5 1- and do-4-(4-(2-hydroxy) -3,6
-disulfo-1-naphthylazo)phenylcarbamoyloxy]-N-(J-(2,4-di-t-amylphenoxy)butyl]-2-su7toadode e disodium 0-6 1-and do axy-4-(2-ethoxycarbonylphenylazo)-ze-[-1(2,4-di-monoamylphenoxy)butyl]-2-su7 toamide Honsha@ Usage amount of colorless and colored couplers is generally 2x10 to 5 moles per mole of silver in the silver halide photographic emulsion.
×10 mol, preferably 5×10 mol to 3×10 mol
The p-R compounds used in the molar comparison include those represented by the following general formula (I) or (9).

General formula [! ] Mu T engineering Mml-! S general formula (If
) Mu-2 Specific examples of TIME include intramolecular substitution reaction as described in JP-A-54-145135, and electron reaction along the conjugated chain as described in JP-A-55-17644. It may be due to movement, in short, it may be caused by movement at the beginning.
Any compound may be used as long as the bond of TIMI is broken to release a group to TIMI-, and then the bond of 〒IMI-1 is broken to release 2.

ZK is Research Disclosure (R・1・aroh
Disolosurs) Volume 176 A17643 D@
A, 1978 (hereinafter referred to as Document 1) ms inhibitors such as those described in K.A. Included are mercaptobenzimidazole, selenopenzidazole, benzotriazole, benzodiazole, and their S derivatives.

Hereinafter, examples of variants of the DIR compound having the timing group used in the present FIA, that is, containing the above general formula (INK) will be described.

-1 ? -2 ONOHOOOO14N.

! -4! -6! -14! -18 -19! -Y%W, m and R1 in the addition formula are as follows.

Compound AY'W Zen?
-31N? -35 Metal compound A Z T-31 ethylthiomercaptotetrazole? -32n
-Butylthiomercaptotetrazole T-33sikvhexylthiomercaptotetrazole! -34N-hezothylmerkabutotetrazolte-35
5,6-1 diktalopenzotriazole Synthesis normal of Dxl compound having a timing group used in the present invention 41N
It is described in No. 54-145135, Tokuho No. 55-17644, etc.

Examples of DIR compounds having no timing group include U.S. Pat. Nos. 3,227,554 and 3.773°20.
No. 1, British Patent No. 2,010,818, Mlls.

No. 958.993, F [3,961,959! , same $
13゜938.996 specification, JP-A [l5G-14
No. 7716, No. 5G-152731, 1jls1-1
05819Jf! F, Publication No. 51-6724, Patent Application @
No. 50-123025, U.S. Patent No. 3,928,041
No. 3,632,345, Tokumaro 50-1252
No. 02 specification etc. Klc! The synthetic methods are also described in these specifications.

Specific examples of I)II compounds that do not have a timing group, ie, those included in the general formula (I) used in Honjitsu Wi4, will be described below.

N=N 01H6 D-10 o1m@ 1- -19 -21 D- is D-a Ri-9 blasphemy 0 town N11° D-320H” Oh.

D-audience D-a el=N D-42 D-46 -49 N D tone car mackerel 1-61 -62 -72 -82 − Oll.

The amount of DIR compound used in this article 11 is general i1c
/”t 1.OX per mole of silver in a silver halide photographic emulsion
10-' mol to S, OX 10-' mol, preferably l, oxio-' to 10X10 mol.

Examples of the fIII medium for the dispersed particles of the present invention include high boiling point organic port mediums having a latex polymer 1 boiling point of 175° C. or higher, and low boiling point solvents. Specific examples of latex polymers include styrene, ethyl atelylate, otori-butyl atelylate, h-butyl methacrylate, 2-7cetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammoniummethacrylate), 3-(
methacryloyloxy)pan-1-sulfonate, sodium sulfonate, N-(
2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylp4-tetrapanesulfonic acid, and the like.

Specific examples of high-boiling point solvents include Hirotri-talesyl phosphate, trihexyl phosphate, dioctyl butyl phosphate, di-butyl phthalate, diethyl laurylamide, 2,4-diallylphenol, and octyl benzoate.

Specific examples of low boiling point solvents include ethyl acetate, butyl nitrogen pionate, and the like.

Various methods can be used to disperse the curlless coupler, colored coupler, and Dll compounds according to the present invention, such as the so-called latex dispersion method and oil-in-water emulsification dispersion method. It can be selected as appropriate depending on the situation.

In this case, the latex dispersion method and the oil-in-water emulsification dispersion method are particularly effective. These dispersion methods are well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open No. 49-74538, Oka No. 51-59943,
No. 54-32552, Research Disclosure (R*s*aroh Disclosure), 1
Recorded in August 976, 4148sO, pp. 77-79.
For the L''Ci & oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be used.

That is, after dissolving in a single or mixed solvent of a high-boiling point solvent and/or a low-boiling point organic solvent, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed with a high-speed rotating mixer or a colloidal scupper. A silver halide photographic emulsion is added directly to the silver halide emulsion, or after a low boiling point solvent is added to the emulsified dispersion by a known method, this is added to the silver halide photographic emulsion according to Halogenated Chain Manuscript Example 1111. Silver halide used in emulsions includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver iodobromide, which are commonly used in photographic silver halide emulsions. Anything is included.

The grains of this Q-genide silver may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these helogenated pot particles may be normal crystals or twin crystals, and any ratio of (Zoo) plane to (111) can be used.

Further, the crystal structure of these hetyl silver grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside.

Further, these silver halide may be of a moat type, which forms a latent image mainly on the surface, or of a pool type, which forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art.

The silver halide photographic emulsion according to the present invention is preferably free of rotatable cracks, but those without the breakage removed can also be used. It is also possible to use a mixture of two or more silver halide photographic emulsions prepared separately.

The silver 0genide photographic emulsion according to Honjitsu No. 11 may contain K11l photodye for spectral sensitization, etc., and any one can be used depending on the purpose. For example, O, M, ][, J-s,
With T.H. and James “The Theory of the...
Photographic Puta Seth” (3rd edition), 1966
Miyako Makuran Oo, N, Y, pp. 198-112
Examples include cyanine dyes, meliciaene dyes, and xanthine dyes described on page 2g.

Binders that can be used in the silver halide photographic emulsion according to this gIAwAK include gelatin, colloidal alpine, agar, gum arabic, alkynic acid, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, methyl Cellulose S conductor and combination jlE/(Ingu,
For example, polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly N, N-dimethylacrylic acid, poly I-vinylbitetraridone, water-soluble polymers, phenylcarbamylated gelatin, acylated gelatin, heptalized gelatin. Examples include gelatin S conductors such as gelatin, acrylic acid (ester), methacrylic acid (ester), acrylonitrile, and other monomers having polymerizable ethylene groups, and gelatin copolymerized with duraft. Two or more of these binders can be used as compatible mixtures if desired.

A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitization using noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers can be advantageously used in combination with the silver hesigenide photographic emulsion according to the present invention.

The silver halide photographic emulsion according to the present invention may contain a stabilizing element. The following turtles can be mentioned as stable stiffnesses that are useful in real WR.

One of the effective methods is nitrogen-containing ms compounds.

For example, 4-oxo-6-thiono-4,5,6,7-tetrahydro-1-thia-3,5,7-)riazaindene, 2-substituted benzoi (dazole, benzotriazole,
Substituted 1,2,3-) riazole, urazole, pyrazole, tetrazole compounds, polyvinyl bitetraridone, and the like. It is particularly useful in polyvinyl pyrrolidone Minoru Hiromoto.

In addition, quaternary ammonium destruction is also useful in real ljI. For example, thiazolinium compounds and biryllium compounds are useful. Among them, benzothiazolium compounds are particularly effective.

Mercapto compounds are also useful as well. Example if 5
- yuniru 1-mercaptotetrazole, 2-mercapto-benzothiazole, 2-mercaptothiazole, mercaptobenraikuda, zole, mercaptooxadiazole, mercaptothiadiazole, thioshega,
4-thiouracil and the like are effective. Among these, 5-phenyl-1-mercaptotetrazole and 2-mercaptobenzothiazole are particularly useful.

It is also used for polyhydroxybenzene compound tflllllKl. For example, 1,2-dihydro-oxybenzene metals, gallic acid esters (eg, isoamyl gallate, dodecyl gallate, 2-furkyl-8-tetraquinone containing tetravir gallate) are effective.

Also useful are thione compounds, such as thiazoline-2-thione compounds. Similarly, salts such as zinc and cadmium are
It is for use.

Also, for example, 4-hydroxy-6-methyl-1,3゜3a
, 7-tetrazaindene, 4-methyl-6-hydroxy-1,3, 7-tetrazuindene, 4-human gastric acid 5.6-dimethyl-1.3.3m, 7-tetrazuindene rumored Tetrazaindene compounds are also useful.

Contained in the silver halide photographic emulsion according to the present invention 1
Although the above-mentioned useful stabilizers are listed above, for example, they can be used in combination to achieve a more favorable stabilizing effect.

The silver halide photographic emulsion related to this book *@ was prepared according to the usual method.
l1 [I can do it. The hardeners used are conventional photographic hardeners, such as formaldehyde, glyoxal, aldehyde compounds such as glutaraldehyde, and derivative compounds thereof such as acetals or sodium bisulfite adducts; methanesulfonic acid. Ester compounds; mucochloride or mucoherogen acid compounds; epoxy compounds; aziridine compounds; active halogen compounds; maleic acid imide compounds; active vinyl compounds; carboxylic compounds; isoxazole Systemized metals, N-methylol compounds; isocyanate compounds;
Non-folding agents such as laminate bread, zirconium sulfate, etc. can be mentioned.

The silver halide photographic emulsion according to Honjitsu@ may contain a surfactant alone or in combination.

The silver halide photographic emulsion according to the present invention may also contain an antistatic agent, a hazy agent, a fluorescent whitening agent, a development accelerator, an air fog inhibitor, a toning agent, and the like.

Furthermore, various photographic additives other than those mentioned above may optionally be added to the silver halide photographic emulsion KFi according to Honjitsu WAK.

The present invention is applicable to a variety of color or black and white silver halide photographic emulsions. Applicable photographic emulsions include color, black and white, positive emulsions, color or black and white,
Emulsion for paper, color or black and white/negative emulsion, color! Emulsion for black and white reversal (may contain a fogger),
Examples include emulsions for photographic materials for plate making (for example, gravure films, etc.), emulsions for use in light-sensitive materials for cathode ray tube displays, emulsions for use in light-sensitive materials for xII printing, and the like.

Hereinafter, the present invention will be explained in more detail by giving examples, but the technical scope of the present invention is not limited in any way by the following practical examples, and various implementations are possible. be.

Practical Example Each of the following dispersions was prepared and mixed with the following silver halide photographic emulsion in the combination shown in the table at a ratio such that the exposure amount required to obtain a clearness of Capri +0.1 was constant. . The obtained emulsion was divided into two parts, one part was immediately dusted, and the remaining part was left at 60°C for 8 hours with stirring, and then coated on a subbed cellulose triacetate base in a silver amount M 20qz/d.
It was painted so that

These samples were exposed to wedge light, and color development Jig1 was performed at 38°C for 3 minutes using a color developer with the following composition, and bleaching and
After fixing, it was washed with water.

(Color developer) 4-amino-3-methyl-doethyl-(β- and droxyethyl)-aniline sulfate 4.7
51i Anhydrous sodium sulfite 4.21 Hydroxylua <4 sulfate 2.0 Ii Anhydrous potassium chloride 37.5 & Sodium bromide 1.3 #Nitriloacetic acid.
3 Sodium jm (monohydrate) 2.5 Potassium monohydroxide 1.0 Add N water to 1
1, and adjust f[10, OK using 1 lium hydroxide).

(Dispersion) Colorless coupler 15j was dissolved in ethyl acetate 30- and dibutyl phthalate) 15mK, and this was dissolved in alkanol m (alkylnaphthalene sulfonate, Tubon I).
It was mixed with the 1051 water solution 2011j of I) and the 5-layer gelatin aqueous solution 200-, and emulsified and dispersed using a colloidal gel.

(Dispersion B) Same as dispersion B, but colorless coupler l! Colorless coupler 13.5p and colored coupler 1.51i were added in place of s9.

(Dispersion 0) Same as Dispersion 1, but additionally added the amount of coupler KDIR compound shown in the table.

(Dispersion D) The amount of DIR compound shown in the table was dissolved in ethyl acetate (2IIj) and dibutyl phthalate (1 mK), and this was dissolved in 1 mK of alkanol.
10 water attack solution 1.5- and 5 duck seven latin aqueous solution 15-
and emulsified and dispersed in a colloid cup.

(Dispersion M) Same as dispersion, except that colored couplers 〇 and 5I were further added to the DIR metal.

(Silver halide photographic emulsion) A green-sensitive silver iodobromide emulsion containing L12.0 mol of silver iodide.

M: Red-sensitive silver iodobromide emulsion containing a, O molar amount of silver iodide.

N: Full color orthochromic silver iodobromide emulsion containing 3.0 moles of silver iodide.

The latitude value of the sample coated with Sokuo K11k after emulsion adjustment and the gamma value change (△T) and capri value change (ΔF
og) are shown in the table. The latitude value is expressed by the exposure range (jogllt) of the linear part of the characteristic curve, and as is clear from this table, the silver tetragenide photographic emulsion according to the present invention not only has a wide exposure latitude but also It can be seen that even if the photographic performance is preserved, the deterioration of the photographic performance has been improved. 1982 Patent Application No. 2111011 2 Name of the invention Silver halide photographic emulsion 3 Relationship to famous cases related to supplementary iEt Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name @
, (+27) Roku Konishi Photo Industry Co., Ltd. Representative Director Yoshihiko Kawamoto 4 Agent Address: 191 Address: 1, Sakura-cho, Noichi, Higashi IIt, Tokyo 1 Roku Konishi Handwritten [- within Gyo Co., Ltd. 1 Self-authored 6, Corrections Column 7 of the subject "Detailed Description of the Invention", Contents of Amendment The detailed description of the invention is amended as follows.

Claims (1)

[Claims] In a silver octagenide photographic emulsion formed by dispersing dispersed grains containing a development inhibitor-releasing compound and dispersing grains containing a colorless coupler, the dispersed grains containing a development inhibitor-releasing compound contain at least one type of dispersion. A silver halide photographic emulsion containing a colored coupler, and the dispersed grains containing a colorless coupler may contain a colored coupler but do not contain a development inhibitor-releasing compound.