JPS63264739A - Silver halide photographic sensitive material and its production - Google Patents

Abstract

PURPOSE:To obtain the titled material contg. the emulsion of a silver halide particle which is suitable for spectral sensitization and has a large specific surface area by forming a specified protrusion and by stabilizing the shape of the particle by a particle forming stopping agent before chemically sensitizing the emulsion. CONSTITUTION:The emulsion layer contg. >=50wt.% of the silver halide particle is composed from the silver halide particle which contains the protrusion having <=0.15mum projected area diameter on the surface of the particle in an amount of 10-10,000 numbers/mum<2>. The halogen composite of said protrusion is different from that of the base particle of the silver halide particle. And, the silver halide emulsion is chemically sensitized by a compd. selected from a sulfur compd., a selenium compd. and a gold compd., and is spectrally sensitized by a methine dye. Namely, the protrusion is formed, followed by stabilizing the shape of the particle by the particle forming stopping agent before chemically sensitizing the emulsion. Thus, the titled material contg. the emulsion of the silver halide particle which is suitable for the spectral sensitization and has the large specific surface area, is obtd.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material which is preferable for spectral sensitization by increasing the specific surface area of the silver halide grains. It is.

(Prior Art) Spectral sensitization technology is an extremely important and essential technology for producing photosensitive materials with high sensitivity and excellent color reproducibility. In order to provide highly sensitive light-sensitive materials, various types of spectral sensitizers have been developed, and many technical developments have been made in their use, such as supersensitization methods and addition methods. Sensitizers have the function of absorbing light in a long wavelength range that is not substantially absorbed by silver halide photographic emulsions, and transmitting the light-absorbed electrons and/or light-absorbed energy to silver halide. Therefore, increasing the amount of light captured by a spectral sensitizer is advantageous for increasing photographic sensitivity.

For this reason, not only attempts have been made to develop spectral sensitizers with high light absorption coefficients, but also attempts have been made to increase the amount of light captured by increasing the amount added to silver halide emulsions.

(Problems to be Solved by the Invention) For this reason, attempts have been made to improve and develop an addition method that can increase the amount of spectral enhancer added, and to develop and improve methods for preparing silver halide grain emulsions.

For example, Thomas L.

Penner), B.B. Gilman Jr. (
P. B. Gilman Jr.) Photographic Science and Engineering (Photo
Sci.

Em), 20 (3), 97-106 (1976
), two types of spectral sensitizers with appropriate potential relationships are adsorbed in large amounts on silver halide crystals in a layered manner to increase the amount of light captured by the spectral sensitizers, and to reduce desensitization due to addition of large amounts. Attempts are being made to suppress it.

Attempts have also been made to improve the silver halide grains themselves. One method is to use tabular silver halide with a large specific surface area.
No. 926, No. 58-113927, No. 58-1139
No. 26, No. 58-113930, No. 58-11393
No. 4, No. 5-111934, No. 5B-95337, No. 58-108528, No. 58-108526, etc.

Meanwhile, C.R. Berry and D.C. Skillman
) J, Appf, Phys, 35. 2165-216
9 (1964), an equal atomic equivalent of KC1 solution was added to an aqueous suspension of AgBr crystals, and then a slightly smaller amount of A
The figure shows a grain in which Ag (1!) was epitaxially grown on the silver bromide grain surface by adding gN0sta solution. Also, in JP-A-59-133540, AgCj! was epitaxially grown on the silver bromide grain surface. Particles are shown that were double-jet added and epitaxially grown (non-selectively) at a temperature of 7.2 °C pAg'.

Although these examples are not originally intended to increase the specific surface area, they are one method of increasing the specific surface area.

However, for all of the grains shown in these figures, the protrusions epitaxially grown on the grain surface are large in size and/or the number per unit area is small, and therefore the protrusions are larger than the particles of the same size without protrusions. However, it cannot be expected to sufficiently increase the specific surface area.

The relationship between the size of the protrusions and the specific surface area described above can be easily understood, for example, by the following calculation.

Place protrusions of a triangular pyramid with 100 faces of phase shape per unit area on 111 faces so that the volumes of all protrusions with projected area diameters of 0.2 μm and 0.1 μm are equal.
For example, the number of protrusions is 4 for 0°2 μm and 0.1 μm.
Assuming that there are 32 pieces, the surface area is as follows.

As is clear from the above calculations, small protrusions are more advantageous in terms of specific surface area than large protrusions.

However, as mentioned above, although small protrusions are advantageous in terms of specific surface area, there is a problem in creating small protrusions and making them exist stably, so particles of this type that are suitable for chemical aggravation have not been produced. It wasn't.

(Objective of the Invention) The first object of the present invention is to use an emulsion consisting of silver halide grains with a large specific surface area suitable for spectral sensitization based on a concept completely different from that of tabular grains in silver halide photographic light-sensitive materials. The purpose of the present invention is to provide a silver oxide photographic material.

Second, we provide a method for producing a silver halide photographic material using an emulsion consisting of silver halide grains with a large specific surface area suitable for spectral sensitization, which is based on a concept completely different from that of tabular grains in silver halide photographic materials. It's about doing.

(Disclosure of the Invention) The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
0% or more (heavy ff1) has a projected area diameter of 0.1 on the particle surface.
It consists of silver halide grains in which 10 to ooo pieces/μm of protrusions of 5 μm or less are present, the halogen composition of the protrusions is different from the halogen composition of the grain matrix, and the silver halide emulsion contains sulfur. A silver halide photographic light-sensitive material characterized by being chemically sensitized using a compound selected from a compound, a selenium compound, and a gold compound, and further spectrally sensitized with a methine dye, and the protrusion.
This was achieved by a method for producing a silver halide photographic light-sensitive material, which is formed at a high potential of 0 mV or more, and stabilizes the shape of the grains with a grain formation stopper before chemically sensitizing the emulsion. .

(Specific structure of the invention) The specific configuration of the present invention will be explained in detail below.

The structure of the silver halide grains of the present invention consists of a grain matrix portion and a protrusion portion, and it is necessary that the halogen compositions of the matrix grain and the protrusion portion are different from each other.A preferred halogen composition of the zero grain matrix is AgBr. It is AgBr1. Silver chloride may be mixed into the base grains in small amounts.

The preferred composition of the protrusions is AgBr AgBrC1! A
gC1. Preferably AgBrC1 with C1− of 30 mo1% or more! or AgC1, more preferably (AgBrCA or AgC1 in which l is 75s+o1% or more)
It is. It is better not to include silver iodide as much as possible, but a small amount may be included.

In the combination of the halogen composition of the particle matrix and the halogen composition of the protrusions, the matrix particle has an Agl of 1 (1+oj!% or less)
AgBr1 containing 50s+on% or more of protrusions
Cj! It is preferable that it is AgBrC1 containing.

Particles in which 50% or more of the surface of the entire particle matrix has a surface of <111) are preferable, and more preferably 75% or more of the surface of the particle matrix is (111).
1) The parent shape of the 0-grain, which is a plane grain, is preferably a tabular grain with a high ratio of projected area diameter to grain thickness (aspect ratio) (for example, an aspect ratio of 5 to 20), but tetradecahedral, octahedral, or irregular shapes are preferred. The (111) plane of the twinned particle also has 50
% or more, it can be used as a particle matrix.

Moreover, more preferable results may be obtained by using monodisperse tabular grains.

Tabular grains by Gatsuto Photographic Science
and engineering (Cutoff.

Photographic 5science and
Engineering), Volume 14, 248-25
7 pages (1970); U.S. Patent No. 4,434,226
No. 4,414,310, No. 4,433.048, No. 4,439゜520 and British Patent No. 2.112
, No. 157, JP-A-58-127921, and the like.

Furthermore, the structure and manufacturing method of monodispersed tabular grains were disclosed in a patent application published in 1983.
-299155, but the shape is simply described, 70% or more of the total projected area of the silver halide grains is
A tabular silver halide having a hexagonal shape in which the ratio of the length of the side having the maximum length to the length of the side having the maximum length to the length of the side having the minimum length is 2 or less, and having two parallel surfaces as outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the value obtained by dividing the variation (standard deviation) of the grain size expressed by the circular diameter of its projected area by the average grain size) ] has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

In addition, octahedral, dodecahedral, and irregularly shaped twin grains can be found in "The Theory of Photographic Processes" by Chi. H. James, 4th edition, Macmillan Publishing Co., Ltd.
Theory of the Photography
c Process″4th ed, MacwHIa
It can be easily prepared by referring to the description in Chapter 3 (p, p, 88-104), etc.

The fixation rate of the (111) plane in the particle matrix can be determined by Kubelkamunk's dye adsorption method.
Urnal of Imaging 5science
29 *165-171 (1985), it preferentially adsorbs to either the (111) plane or the (100) plane, and the association state of the dye on the (111) plane and the dye association state on the (100) plane The fixation rate of the (111) plane can be determined by selecting dyes whose association states differ spectrally, adding such dyes to an emulsion, and closely examining the spectra with respect to the amount of dye added.

The grains having protrusions according to the present invention account for at least 50% (heavy N
) Preferably 70% or more (Ii amount), more preferably 9
It is 0% or more (weight).

The protrusion referred to in the present invention is expressed by two constants that define its shape. That is, one is the projected area diameter of 0°15 μm or less, preferably 0.13 μm or less, more preferably 0.11 μm.
m or less. Here, the projected area diameter is expressed as the diameter of a circle having the same area as the projected area from the top of the protrusion.

Another factor is the height of the protrusion. The higher the height of the protrusion, the more effective it is. When a triangular pyramid consisting of (100) planes is a protrusion, the height of the triangular pyramid is 0.55 times the projected area diameter of the triangular pyramid.6 The protrusion described in the present invention is:
The height is 0.4 times or more the diameter of the projected area.

The number of protrusions per unit area (μm2) is l × 10 ~ 1
0', preferably 2 x 10 to 10', more preferably 3
It is XLO~104 pieces.

The main reason why a large number of protrusions are formed on the particle surface as in the present invention is thought to be due to the difference in lattice constant between the particle matrix component and the protrusion component. The lattice constants of a certain silver halide composition are, for example, T and H.

James' The Theory or the
PhotographicProcess” 4
th ad, PP3-4 (1977 MaCsi
If the lattice constant of the 0 particle matrix component and the lattice constant of the protrusion component shown in llansha N, Y) are significantly different,
Growth by the protrusion component progresses until the strain in the lattice structure can no longer be relaxed against the growth in the in-plane direction of the particle matrix, and then or simultaneously grows in directions other than the in-plane direction, resulting in the formation of many protrusions on the particle surface. it is conceivable that. Therefore, the larger the difference between the lattice constant of the particle matrix and the lattice constant of the protrusion component, and more preferably, the more the growth of the protrusion component is promoted in directions other than the plane of the particle matrix, the better the protrusion preparation according to the present invention will be. I can think of it as possible. However, the details will have to wait for future consideration.

The size distribution of the particle matrix may be narrow or wide, but one preferred particle matrix has a narrow size distribution (coefficient of variation of 20%).
(hereinafter) monodisperse emulsion.

The size of the particle base is preferably 0.5 μm or more in average projected area diameter, more preferably 0.7 μm or more, particularly 1°0 μm or more.

The silver halide emulsion in the present invention can be prepared by selecting and combining various methods known in the field of silver halide photographic window optical materials.

Specifically, it is prepared by forming a particle matrix and then forming protrusions on the particle surface.

First, to prepare the particle base, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble root salts and soluble halogen salts can be selected from among the one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another form of the simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble root salt and soluble halogen salt) can also be used. A halogenated IFAR agent such as ureas, 1,000 ethers, amines, etc. may be selected and used. It is desirable to use an emulsion with a narrow particle size distribution of the 0-grain matrix, and the above-mentioned monodisperse grain matrix emulsion is particularly preferred. The halogen composition of individual particles at the particle matrix stage,
In particular, an emulsion with a more uniform iodine content is desirable.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. If the halogen composition of the particle matrix is more uniform, the X-ray diffraction width will be narrower and a sharper peak will be given.

In preparing the silver halide grains in which most of the surface is covered with protrusions according to the present invention, protrusions may be prepared as is after the formation of grains serving as the grain matrix, but the grain matrix may be washed with water for desalting. After that, the protrusions may be prepared.

Preparation of protrusions is preferably carried out by adding a water-soluble silver salt and a water-soluble halogen salt corresponding to the composition of the protrusions.At this time, the rate of addition of water-soluble silver should be as fast as possible without causing re-nucleation. is preferred.

The preparation of the protrusions varies depending on the halogen composition of the protrusions, and/or the temperature, and/or the additives coexisting during the preparation, but the silver potential is at least +1
It is necessary to adjust the tap root potential to 10 mV or more, preferably +120 mV or more, more preferably +130 mV or more.

The value of the silver potential in the present invention is compared to the saturated calomel electrode (S,
Displayed in C, E).

In addition, the temperature during the preparation of the protrusions is preferably lower than 80°C, preferably 70°C or less, although it varies depending on other conditions during the preparation.
The temperature is 0°C or lower, more preferably 65°C or lower.

Although the presence of an additive that becomes a halogenated solvent during the preparation of protrusions is not preferred, it may be used as long as the particle matrix and protrusions do not mix with each other more than necessary.

The silver halide grains of the present invention have a particle size of 10-'mol or more, preferably 5 x 10-'mol or more, more preferably 10-'mol or more per Agmol, for stability of protrusions before chemical sensitization.
X 10-'so1 or more and 5 X +, O-"m
oj! Preferably, it is necessary to add the particle formation stopper in an amount of I x 10-"mol or less. The time of addition of the particle formation stopper is after the formation of protrusions and before chemical sensitization, but especially when the formation of protrusions is After that, it is preferable to do it before the water washing step.

The term "grain formation stopper" used in the present invention refers to materials that strongly adsorb to the silver halide surface and prevent changes in grain shape, such as mercapto compounds, azole compounds, dyes, etc., or combinations thereof. Examples of mercapto compounds and azole compounds include the following.

That is, azoles such as benzothiazolium salts, nitroimidazoles, nitropenzimitatsu-Jl/[
, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitropenzotriazoles, mercaptotetrazoles (especially 1 mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1, 3,3a.

7) Tetraazaindene W4), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can.

It can also contain adenines.

Examples of pigments include: cyanine dye,
Included are 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 commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, pyrroline, oxasoline, thiaso
Phosphorus nucleus, virol nucleus, oxazole nucleus, thiazole nucleus,
selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and after aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benz Indolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

As a particle formation stopper, any of the above-mentioned mercapto compound azoles, dyes, etc. may be used, but dyes such as the dyes mentioned below may be used so that their presence does not interfere with the subsequent chemical sensitization, spectral enhancement, etc. It is particularly preferable to use D-1 to D-45.

Among the dyes, merocyanine dyes are preferred because of their ability to stop particle formation. The merocyanine dye having a high ability to stop particle formation is a compound represented by the general formula (1).

General formula (1) In the formula, Z represents a 5.6-membered heterocyclic ring-forming atomic group.

Examples include heterocyclic atomic groups such as thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, benzoxazole, naphthoxazole, benzimidazole, naphthimidazole, pyridine, quinoline, and pyrrolidine. The 5- and 6-membered heterocycles may be substituted.

Ql, Ql represents a sulfur atom, selenium atom or >NRs, R3 may contain one oxygen atom, sulfur atom or nitrogen atom in the carbon chain, a hydroxy group, a halogen atom, an alkylaminocarbonyl group, an alkoxycarbonyl represents a carbonyl group, an alkyl group having 8 or less carbon atoms which may be substituted with an optionally substituted phenyl group, an optionally substituted jIL ring aryl group, and particularly preferably a hydroxy group or an alkylamino group. A carbonyl group, an alkoxycarbonyl group, an alkyl group having 6 or less carbon atoms which may be substituted with a carboxy group and which may contain an oxygen atom in the carbon chain, or a hydroxy group, an alkyl group, a chloro atom, an alkoxy group, etc. This is a case where it represents an optionally substituted phenyl group or pyridyl group. Y represents a sulfur atom or a selenium atom.

R8 represents a furkyl group having 8 or less carbon atoms which may contain an oxygen atom or a sulfur atom in the carbon chain, or an alkenyl group which may have an tta structure.

Rg R, has the same meaning as R1, and also represents a hydrogen atom or an optionally substituted monocyclic aryl group having 8 or less carbon atoms.

R3 is a hydrogen atom, an optionally substituted phenyl group having 8 or less carbon atoms (examples of substituents include an alkyl group, an alkoxy group, a chloro atom, a carboxy group, a hydroxy group, etc.), or a substituted Represents an alkyl group having 6 or less carbon atoms.

Furthermore, at least two of R, R, and R represent substituents having no sulfo group.

j represents 0 or 1, m represents 0.12 or 3, and n represents 0 or 1.

When m represents 2 or 3, it means that different R1 and R1 can be connected to form a 5.6-membered ring.

Among the compounds represented by the general formula [1], compounds in which m represents 0, 1 or 2 and n represents 0 are even more preferred.

Among the 5- and 6-membered heterocycles substituted in Z, especially preferred fIA groups include chlorine atom, cyano group, alkoxycarbonyl group having 5 or less carbon atoms, and 4 carbon atoms when the heterocycle nucleus is benzimidazole. The following perfluoroalkyl groups, acyl groups having 5 or less carbon atoms (e.g. acetyl group,
(metasulfonyl group, etc.), and in the case other than benzimidazole, an alkyl group that may be substituted with a hydroxy group, a carboxy group, a halogen atom, a phenyl group, an alkoxycarbonyl group, an alkoxy group, etc. having 5 or less carbon atoms, or a carbon A phenyl group, a furyl group, a chenyl group, a pyridyl group, an alkoxy group having a carbon number of 5 or less, which may be substituted with a hydroxy group, a halogen atom, an alkoxy group, an acylamino group, an alkylaminocarbonyl group, a carboxy group, etc., having a number of 8 or less, Particularly preferred substituents include an alkoxycarbonyl group having 5 or less carbon atoms, a hydroxy group, a halogen atom, or a carboxy group.

Preferred examples of substituents for R include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, an optionally substituted phenyl group, a monosaturated monocyclic heterocycle, and the like.

Preferred examples of substituents for R1R4 include alkyl groups, alkoxy groups, chloro atoms, carboxy groups, sulfo groups, or acylamino groups, and preferred examples of aryl groups include phenyl groups, pyridyl groups, furyl groups, and chenyl groups. Examples include groups.

In the present invention, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present in the process of silver halide grain formation or physical ripening. good.

The silver halide emulsions of the present invention are chemically sensitized.

For chemical sensitization, for example, Die H., edited by Frleser.
Grundlagen der Photogra
phischen Prozessesit S
ilberhalogeniden (Akrdem
ischeVerlagsgesellschaft
, 1968), pp. 675-734, can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines), selenium sensitization, reducing substances (e.g., Reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; noble metal compounds (e.g.
In addition to kumquat salts, a noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pt, Ir, and Pd can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
, 574,944, 2.410゜689, 2,278,947, 2゜728.668, 3,656,955, etc., regarding the selenium sensitization method in the United States. Patent No. 1574944, Patent No. 1602592, Patent No. 1
No. 623499. Regarding the reduction sensitization method, U.S. Pat. 419
．． No. 974, US Pat. No. 4.054,458, etc., and US Pat. It is described in.

As a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers,
Although it is preferred to use gelatin, other hydrophilic colloids can also be used.

Examples include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Japa.
Enzyme-treated gelatin such as that described in N, Nl 16, R30 (1966) may be used, and gelatin hydrolysates and enzymatic decomposition products may also be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindene, etc.; benzene-thiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide A number of compounds known as antifoggants or stabilizers can be added, such as. For example, U.S. Patent No. 3,954.474;
982. 947, and those described in Japanese Patent Publication No. 52-28.660 can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
May include urea derivatives, imidazole derivatives, 3-pyrazolidones, etc., e.g., U.S. Pat. No. 2,400,53
No. 2, No. 2,423,549, No. 2,716.062
No. 3,617,280, No. 3,772゜021, No. 3,808.003, British Patent No. 1゜488.99
You can use those listed in No. L.

Examples of documents describing methine dyes used in the present invention include:
The Chemistry of Heterocyclic Compounders by F. M. Rawor.
Chemistry of) Ietero
cyclic compounds)% etc.18t
! The Cyanine Dyesa
nd Re1ated Compounds)j
(A. Edited by Weissberger,
Published by Interscience, New York, 1964)
"The Cyanine Wise and Related Compounder" by SLurmar, D.M.
Dyes and Re1ated Co.
mpounds) j (A, Weisberger Wei
ssberger, E, C.

Taylor IIIA, John Wiley Co.
New York (1977), Research Disclosure (RESEARCH DISCLOSURE);
) 176 @, Magnetic 17643, p, 23-24
(1978), German Patent No. 929.080, U.S. Pat.
No. 912.329, No. 3,656,959, No. 3.
No. 672,897, No. 3,694,217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
No. 2-24844, British Patent No. 584,609, No. 1,
No. 177.429, JP-A-48-85130, JP-A No. 49
-99620, 49-114420, 52-1
No. 08115, U.S. Pat. No. 2,274,752, U.S. Pat. No. 2.533.472, U.S. Pat.
No. 48,187, No. 3,177.078, No. 3,24
7.127, 3,540,887, 3,575
, No. 704, 3. 653. No. 905, 3,71
No. 8,472, No. 4,071゜312, No. 4,070
, No. 352.

These spectral sensitizers may be used alone or in combination, and combinations of spectral sensitizers are often used especially for the purpose of supersensitization, and together with super spectral sensitizers, The emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light but exhibits superchromatic sensitization. For example, aminostilbene compounds substituted with fluorine-containing heterocyclic groups (for example, U.S. Pat. Nos. 2,933,390 and 3,6
35,721), aromatic 81-acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743.51),
0), cadmium salts, azaindene compounds, etc., U.S. Pat.
The combination described in No. 3,635,721 is particularly useful.

Next, typical compounds of dyes used as particle formation stoppers and/or spectral sensitizers in the present invention are shown below.

(CHx)s (CHz)s SOzNa SOx (CHl)! (CHt) 350s K
Sow SOsNa Sow SOs K SOi (CHx)n (CHri3 Sow K SOs C! HS (CHJ4SOi SOs Na SOsD-10 D-11 So, K SOi So, K SOi (CHz)i (CHri3S031'
Ja soiCz Hs
(CHz)sSoi SOJ-N(CJs)s SOstHs SOs K SO! C! I(S
CZ HsCyo H3 蓼(CHz)a Soi C! HsCH,CO
OH Ct Hs (CHz)i■ Oi (CH,)s SOs Na (CH
z)s SOiC, Hs Cz Hs l lCC
Hs CtHs Bn1h CiHs l
lCt Hs Ct Hs 1Ct Hs So, K So, tHs I H3 CH Mushroom C00H C Dew Hs 1 x Hs l C2H4 ow K C4H91 cHt C0OH (CHx)s SOi K IC Tobi Hs SO Ko K C Mushroom Hs Performed below example The present invention will be further explained by referring to the following.

Example 1 Potassium bromide and gelatin were added and dissolved in a solution kept at 70°C, and while stirring, nitric acid was added! I solution and potassium bromide solution were added by double jet method. After addition 3
After lowering the temperature to 5°C and removing soluble salts by the sedimentation method, the temperature was raised to 40°C again and 60g of gelatin was twisted and dissolved.
The host grain emulsion A was prepared by adjusting the H6.8. The obtained base particles were tabular, with an average diameter of 4 μm and a thickness of 0.2 μm.
Met.

Add 900g of emulsion A (equivalent to 70g of AgNOs) and 200mj of water! Add silver nitrate aqueous solution (
AgNOs a, equivalent to 5 g) and sodium chloride aqueous solution at silver potential + 4 Q mV + 100 mV + 160
M/250 300 cc of dye D-13 shown in the text was added by double jet method while maintaining mV or +19'OmV to form protrusions on the base particle surface.
The emulsions 1 to 4 were prepared by adding them, washing with water, and chemically sensitizing them at 50° C. for 20 minutes in a hypo.

When the particle shape was observed using an electron microscope, it was as follows.

1 +40 mV Q Comparative Example 2 +100 mV 5 Comparative Example 3 +160 mV 50 Present Invention 4 +190 mV 140 Micrographs of Emulsions 1 to 4 of the present invention are shown in FIGS. 1 to 4.

Example 2 900g of emulsion A and 200mj of water! In addition, a silver nitrate aqueous solution (equivalent to A g NO 38,5 g) and a sodium chloride aqueous solution were added by a double jet method while keeping the silver potential at +lOOmV or +160mV, respectively, while maintaining the temperature at 50°C to form protrusions on the surface of the base particles. Emulsions 4 and 5 were prepared by washing with water, adding 200 cc of dye D-36 at M/250, and chemically sensitizing it in a hypo at 50°C for 20 minutes. 5
Emulsions 6 and 7 were made in exactly the same manner.

When grains were observed using electron micrographs, emulsion 4.5 had grains similar to emulsion 2.3, but emulsion 6.7 had grains with rounded protrusions.

The amount of dye adsorption was investigated using the reflection spectrum of the emulsion and Kubelker-Munk's equation, and the results were as follows.

4 +100 Before chemical sensitization 115
Comparative example 5+160130 Invention 6+100 After chemical sensitization 105 Comparative example 7 +160 110
Comparative Example Emulsion A --100 *The amount of dye adsorption was estimated based on the adsorption amount of Emulsion A as 100.

As is clear from the above, only Emulsion 5 of the present invention, in which protrusions were formed at a high potential of +11 OmV or more and was stabilized with a dye before chemical sensitization, maintained an increase in adsorption amount.

Example 3 900 g of emulsion A prepared in Example 1 was optimally chemically sensitized using the following chemical sensitizer I at 45°C for 20 minutes.Chemical sensitizer! Emulsion 8 was prepared by adding 300 cc of dye D-9 (M/250).

M/250 300cc of dye D-9 to 900g of emulsion A
After adding chemical sensitizer! Emulsion 9 was prepared by optimally chemically sensitizing the emulsion at 45° C. for 20 minutes.

Add 200ml of water to 900g of Emulsion A! In addition, a silver nitrate aqueous solution (AgNOs, equivalent to 5) and a sodium chloride aqueous solution were added by the double jet method while keeping the silver potential +100 mV at 50°C, and then dye D-9 was added at M/2.
After adding 50.300 cc, emulsion 10 was prepared by optimally chemically sensitizing the emulsion at 45° C. for 20 minutes using chemical sensitizer 1.

Emulsion 11 was prepared in exactly the same manner as Emulsion 10, except that the silver potential was changed from +100 mV to +1.90 mV.

Each emulsion 8.9.
Coating samples 1 to 4 were made by coating 10.11 and a protective layer.

Table 1 Fi+ Emulsion layer 0 Emulsion Each emulsion 8-11 3 g/rdO Dodecylbenzenesulfonic acid sodium salt 0.1 ■/Resistance Q Poly-p-
Styrene sulfonic acid potassium salt 1■/dO gelatin
4.8g/rd(2) Protective layer 0 Gelatin 0.7g/rdON-
Oleoyl-N-methyltaurine sodium salt 0.2■/dO Polymethyl methacrylate fine particles (average particle size 3.17 m) 0.13+ng/
rt (Coated samples 1 to 4 were wedge-exposed in the spectral sensitization region through a sharp cut filter 5C-50 manufactured by Fuji Photo Film Co., Ltd.).

These samples were developed and fixed for 7 minutes at 20°C using the following developer.
After washing with water and drying, the concentration was measured.

Developer Metol 2g Sodium sulfite 100g Hydroquinone
5g Borax・1OH102
g Add water ll! ! Fixer Ammonium thiosulfate 240.0g Sodium sulfite (anhydrous) 15.0g Acetic acid (28%
) 48mj! Sodium metaborate 15g potassium alum
Add 15g water
1. Oj! The results are summarized in Table 2.

As is clear from Table 2, the samples of the present invention were found to have high sensitivity.

Table 2 The photographic sensitivity is expressed as the reciprocal of the exposure amount required to obtain an optical angle of 28 degrees with a fog value of +0.2, but in Table 2, the sensitivity of Sample 3 is expressed relative to 100.

[Brief explanation of the drawing]

Patent applicant: Fuji Photo Film Co., Ltd. 2nd cause Procedural amendment 1933//month/day )death

Claims (1)

[Scope of Claims] 1) In a silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on a support, 50% or more of the silver halide grains present in the emulsion layer ( weight)
consists of silver halide grains having 10 to 10,000 protrusions/μm^2 with a projected area diameter of 0.15 μm or less on the grain surface, and the halogen composition of the protrusions is different from the halogen composition of the grain matrix. and the silver halide emulsion is chemically sensitized using a compound selected from a sulfur compound, a selenium compound, and a gold compound, and further spectrally sensitized with a methine dye. material. 2) Claim 1, characterized in that the grain shape of a silver halide emulsion consisting of silver halide grains having protrusions on the grain surface is stabilized with a grain formation stopper before being chemically sensitized. The silver halide photographic material described in Section 1. 3) In a method for producing a silver halide photographic material having at least one silver halide emulsion layer on a support, 50% (by weight) of the silver halide grains present in the emulsion layer. The above is a silver halide grain in which 10 to 10,000 projections/μm^2 with a projected area diameter of 0.15 μm or less are present on the grain surface, and the halogen composition of the projections is the same as the halogen composition of the grain matrix. are different, and the protrusion is +1
1. A method for producing a silver halide photographic material, which is formed at a high silver potential of 10 mV or more, and the shape of the grains is stabilized with a grain formation stopper before the emulsion is chemically sensitized.