JPS6167845A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To stabilize chemical sensitization and to obtain high sensitivity, low fogging an good shelf life by incorporating a silver halide (AgX) emulsion formed by maturing chemically the specific AgX in the presence of a sensitizer and water soluble salt into at least one AgX emulsion layer. CONSTITUTION:The AgX emulsion obtd. by maturing chemically the monodisperse core/shell type AgX particles having the silver iodide content different near and in the surface in the presence of the chalcogen sensitizer, gold sensitizer and at least one kind of water soluble salt of Rh, Pd, Ir and Pt is incorporated into at least one AgX emulsion layer on a base. The above- mentioned AgX particles are preferably silver iodide particles and the chemical maturation thereof is executed in the presence of the AgX solvent. The water soluble salt of Rh, etc. is the compd. expressed by R2MX4, R2M'X6 (R is H, NH4, alkali metal, M is Pt, Pd, M' is Ir, Rh, X is a halogen atom) and the amt. of said salt to be added is preferably 10:1-100:1 by the mole of the gold sensitizer. The disturbance of the chemical sensitization by gold-gelatinate is thus prevented and the sensitizing stage is simplified.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive phase material with improved photographic properties, which furthermore prevents fogging, achieves high sensitivity, and has good storage stability. The present invention also relates to a silver halide photographic material.

[Conventional technology]

In recent years, demands on silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) have become increasingly strict, and in particular, there is a strong demand for the development of g-light materials with high sensitivity and excellent -1 characteristics.

Conventionally, in order to obtain a silver halide emulsion with high sensitivity, a silver halide emulsion in which the halogen composition is different inside the silver halide grains and near the surface has been actually used.Furthermore, by using a monodisperse emulsion, Quantum efficiency has improved, making it possible to obtain emulsions with high sensitivity and low capri, and it is now expected that sensitization can be achieved efficiently while maintaining a low capri concentration in the chemical sensitization process. Ta.

However, in reality, chemical sensitization is difficult to control when a substantially monodisperse emulsion is chemically sensitized, and not only is it difficult to achieve low capri and high sensitivity as expected, but also undesirable results in terms of shelf life. One of the causes of this, which is often obtained, is a gold-gelatin complex. In other words, the gold ions of the gold sensitizer, which is commonly used as a chemical sensitizer, form a complex (gold-gelatinate) with gelatin and are captured in the gelatin, making it difficult to control chemical sensitization and preventing capture. Gold ions adversely affect the storage stability of photosensitive materials.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned inhibition of chemical sensitization by gold-gelatinate, to achieve stable chemical sensitization, and to provide a photosensitive material that is highly sensitive, has low capri, and has excellent storage stability. 7 [Structure of the Invention] As a result of repeated studies for the above-mentioned purpose, the present inventors have developed a method for producing g-optical materials with high sensitivity, low capri, and excellent storage stability in a far more stable manner than in the past. I found it. That is,
By performing chemical ripening in the presence of a core/shell 15 that is substantially monodisperse and has a different silver iodide content between the grain surface and the inside, gold ions are released from the gold-gelatinate and silver halide is removed. By stably controlling chemical sensitization by promoting the adsorption of gold ions onto the grains, the photosensitive material obtained by coating at least one layer of the emulsion prepared in this way on a support has the above-mentioned characteristics. satisfy the purpose.

In the present invention, substantially monodisperse silver halide grains are dissolved;
When the emulsion is observed using an electron microscope, the shape of each silver halide grain appears to be uniform, the grain size is uniform, and the grain size distribution is defined by the following formula. That is, when the standard deviation S of the grain size distribution is divided by the average grain size Te, the value is 0.20 or more.

Σni −<0.20 The average grain size here refers to the diameter in the case of spherical silver halide grains, or the projection image of the grains with the same area in the case of grains having shapes other than cubic or spherical. 7 is defined by the following formula when the individual particle size is ri and therefore ni.

-Σnmu ri Σni The above particle size can be measured by various methods commonly used in the technical field for the above purpose.A representative method is Loveland's "particle size". Analytical method J A,S.

T, M, Symposium on Light Microscopy, 1955, pp. 94-122, 7+1: [The Theory of Photographic Growth], co-authored by Mies and James, 3rd edition,
It is described in Chapter 2 of Macmillan Publishing (1966). The particle size can be measured using the projected area or approximate diameter of the particle.

If the particles are of substantially uniform shape, the particle size distribution can be expressed accurately as either diameter or projected area.

The silver halide emulsion of the present invention is composed of P-gras 7Kidex (
P, GIafkides) Heat, Shimmy, Technique, Physiic Photographic
iquePhotographique ) (Pa
ul Mante1, 1967);
Photographic Emulsion Chemistry (Pho) by G, F, DuffLn
tographic Emulsion Chemises
try ) (The Focal Press 196
Published in 966, L.
Making and Coating Photographic Emulsion: 17 (
Making and Coa eyes Photogr
aphicEmulsion ) (The Foca
It can be prepared using the method described in 1964, published by I Press.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any of the injection mixing method, simultaneous mixing method, and a combination thereof. One type of simultaneous mixing method that may be used is a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, ie, the so-called Chondrald double jet method.

The core/shell type silver halide grains in the present invention have a grain structure composed of two or more layers having different silver iodide contents, and the iodine in the vicinity of the surface of the two or more layers is It is preferable that the silver oxide content is lower than that in the interior.

Here, the term "near the surface" means that the thickness from the surface is 0.01 to 0.
This refers to the 3 μm portion. It is preferable that the difference between the silver iodide content near the surface and that contained inside the surface is 1 molar or more.

In the present invention, the silver iodide content near the surface is preferably as low as possible, and preferably consists essentially of silver bromide.

Emulsions containing such silver halide grains have high sensitization efficiency and are particularly suitable for obtaining surface layer [house-shaped emulsions].

In the core/shell type silver halide grains of the present invention, the slope due to the difference in content from a layer with a high silver iodide content to a layer with a low silver iodide content may have a sharp boundary; , the boundaries may be continuously changing and not necessarily obvious.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures, as described in the Abstracts of the Annual Canine Society Lectures of the Photographic Society of Japan in 1981. I can do it.

Accordingly, in a preferred embodiment of the silver halide grains of the present invention, 0 to 4 mol of silver iodide is contained near the surface of the grain, and 2 to 15 mol of silver iodide is contained further inside. % of silver halide. In the present invention, the silver halide composition other than the above-mentioned silver iodide is mainly silver bromide, but silver chloride may also be included as long as it does not impair the effects of the present invention, and the limit is less than about 1 molar ratio. preferable.

The silver halide emulsion according to the present invention may contain a mixture of octahedral and tetradecahedral grains.

The silver halide emulsion having core/shell type silver halide grains of the present invention can be produced by using a substantially monodisperse silver halide grain as a core and coating the core with a shell.

In order to produce monodisperse silver halide grains of the core, grains of a desired size can be produced by a double jet method while keeping βAg constant. For example, a monodisperse silver halide emulsion can be produced. For example, a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are mixed into a gelatin aqueous solution containing silver halide seed particles. by varying the rate of addition as a function of time. In this case, the time function of the addition rate, p
By appropriately selecting Hs pJ"gz temperature, etc., highly highly dispersible silver halide grains can be obtained.

Regarding the method for producing the above-mentioned core/shell type silver halide grains, for example, Japanese Patent No. 1.169.290, British Patent No. 1.027,146, and JP-A-57-15
4232 and Japanese Patent Publication No. 51-3417.

In the present invention, for example, cadmium salt, zinc salt, lead salt,
A thallium salt, an iridium salt or a complex salt thereof, a rhodium group or a complex salt thereof, etc. may be coexisting. The chalcogen sensitizer in the present invention is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer. However, for general use, sulfur sensitizers and selenium sensitizers are preferred, and known sulfur sensitizers can be used. , for example, thiosulfate, allylthiocarbide, thiourea,
Examples include allyl isothiocyanate, 7-stin, p-)luenethiosulfonic acid 1fA, and rhodanine. In addition, U.S. Patent No. 1,574.944, U.S. Patent No. 2,410.
No. 689, No. 2,278,947, No. 2, 728
, No. 668, No. 3.501.313, No. 3,656.
No. 955 specifications, West German Application Publication (OLS) 1,42
Sulfur sensitizers described in Japanese Patent Application Publication No. 2.869, Japan B# Publication No. 56-24937, and Japanese Patent Application Publication No. 55-45016 can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This value changes over a considerable range depending on various factors such as the amount of the desired heterocyclic compound added, pH, leakage, and the thickness of the silver halide grains, but as a guide, silver halide 1 A range of about 10-7 moles per mole to 10-' moles is preferred.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include allylisoseleno-anate, aliphatic isoselenocyanates, selenourea, selenoketo, and selenamide. selenides such as selenocarboxylic acids and esters, selenophosphates, diethylsennide, diethylsennide, etc.
;t'' These specific sequences include U.S. Pat. No. 1.574,944, U.S. Pat.
It is described in the specification of 1.623.499.

As with the sulfur sensitizer, the amount added varies over a wide range, but as a guideline, approximately 10%
A range of 1 to 10 −1 moles is preferred.

In the present invention, as the gold sensitizer, a wide variety of compounds can be used, regardless of whether the oxidation number of gold is +1 or +3.6 Typical examples include chloraurate, potassium chloroaurate, auric trichloride, Potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on the regulations, but as a guideline, it is about 10 to 10 moles per mole of silver halide.
A range of up to 1 mol is preferred.

Preferred compounds that release gold ions from gold-gelatinate and promote adsorption of gold ions onto silver halide grains include Rh, Pd, There are water-soluble salts of Ir and Pt, but the salts are not limited thereto.

General formula [■] Between R7 and X4 General formula [■] R3M'X.

In the formula, R represents a hydrogen atom, ammonium, or an alkali metal, M@Pt-4f'cHPd, and M' is Ir.
It represents the trading company Rh. Moreover, X represents a halogen atom.

Specific compounds include (NH4), Pt(J4. (N
H4), PdC14KsIrBr, , (NH,)
, RhC716,12H,0, etc., but particularly preferred are ammonium tetracyanolactate (If) (NH4), PdC71, and the like. The amount added is preferably in the range of 10 to 100 times the stoichiometric ratio (mole ratio) to the gold sensitizer.

The addition time may be at the start of chemical ripening, during ripening, or after the end of ripening, but preferably during chemical ripening, and particularly preferably at the same time as or before or after the addition of the metal sensitizer.

In the present invention, reduction sensitization can also be used in combination. The reducing agent Fi is not particularly limited, but known examples include stannous chloride, thiourea dioxide, hydrazine derivatives, and polyamines.

Reduction sensitization is carried out during the growth of silver chloride grains, but chalcogen sensitization, gold sensitization and Rh, P of the present invention
It is preferable to carry out the sensitization after completion of sensitization using a compound selected from water-soluble salts of d, Ir, and Pt.

Further, the silver halide grains used in the present invention can be chemically ripened in the presence of a silver halide solvent, thereby achieving a significantly higher sensitivity, which is preferable.

The silver halide solvent used in the present invention is Mokuga Tokkei No. +3.271,157, No. +531,289.
No., L574.628 Specifications, JP-A-1983-1
No. 019, Patent Publication No. 54-158917, etc.
No. 55-77737, No. 55-2982, etc. (bl thiourea derivative, JP-A-53-1
(c) described in JP-A No. 44319 is a silver halide solvent having a thiocarbonyl group sandwiched between a sulfur atom and a nitrogen atom; , (e) sulfite, (
f) Thiocyanate and the like.

These specific compounds are shown below.

(al HO(CH,)t s(OH,), 8(CH,)t
0HCH,NHCOCH,CH,C00)1C)(,8
CH, CH, SC,)I.

(cl K180°(f) NH, SCN 8ON Particularly preferred solvents include thiocyanate and tetramethylthiourea.The amount of solvent used varies depending on the type, but for example, in the case of thionanate,
A preferred value is in the range of 51π9 to II per mole of silver halide.

The silver halide emulsion used in the present invention uses various dyes.
can be spectrally sensitized. Dyes used include cyanines, merocyanines, complex cyanines and complex merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), oxonols, hemioxonols,
Volime containing styryl, merostyril and stregtocyanin.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz[
e] Indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacillinium, imidazolium, imidazolinium,
benzoquinacillinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, dihydronaphthothiazolium, pyrylium and imidazopyrazinium quaternary It contains two basic heterocyclic nuclei linked by a methine bond, as derived from the salt.

Merocyanine spectral sensitizing dyes include barbituric acid, 2-
Thiobarbic acid, rhodanine, hydantoin, 2-
Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-inxacillin-5-one, indan-1,3-dione, cyclohexane-1,3-dio/, 1,3-dioxane-4,6 Acidic nuclei and cyanine colors such as those derived from -diones, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione' It includes those in which a complex basic heterocyclic nucleus is bonded through a methine bond.

Spectral sensitizing dyes useful for sensitizing silver halide emulsions are described in British Patent No. 742,112 and US Pat. No. 1.846.
No. 300, No. 1,846.303, No. 1.846.3
No. 02, No. 1,846.303, No. 1.846,30
No. 4, No. 2.078, 233-, No. 2,089.72
No. 9, No. 2.16 Fi, No. 338, No. 2.213.23
No. 8, No. 2,231.6s No. 8, No. 2, 493, 7
No. 47, No. 2,493.748, No. 2.52 Fi, 6
No. 32, No. 2,739,964 (Reissue Patent No. 24, 2
92), 2,778.823, 2.917.5
No. 16, No. 3,352.857, No. 3.411.91
No. 6, No. 3, No. 431, No. 111, No. 2.295.2
No. 76, No. 2,481,698, No. 2.503,77
No. 6, No. 2.688.545, No. 2.704.714
No. 2,921.067, No. 2.945.763, No. 3,282,933, No. 3.397.060,
3,660.102, 3.660.103, 3.335.010, 3.352.680, 3
, No. 384.486, No. 3.397.981, No. 3,
No. 482.978, No. 3,623, 881, No. 3,718,470 and No. 4.025,349. Examples of useful dye combinations, including supersensitizing dye combinations, are described in US Pat. No. 3,506,443 and US Pat. No. 3,672,898. As a supersensitizing combination array consisting of a spectral sensitizing dye and a non-original absorbing additive, thio7anate is used in the process of spectral sensitization as taught in U.S. Pat. No. 2,221.805; Using bis-triazinylaminostilbene as taught by U.S. Pat. U.S. Patent 3,4
No. 57,078, using a mercagut-substituted heterozygote compound as taught in British Patent No. 1,413.826.
and other compounds, including those described in Gilman's Review of Mechanisms of Supersensitization. can be used.

The above-mentioned sensitizing dye may be added at an appropriate time such as at the start of chemical ripening (also called second ripening) of the silver halogenide emulsion, during the course of ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. But it doesn't matter.

In addition, the method for adding the sensitizing dye to the photographic emulsion is as follows:
Various methods that have been proposed so far can be applied. For example, as described in US Pat. No. 3,469.987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. The sensitizing dyes may also be dissolved individually in the same or different solvents and the solutions may be mixed or added separately before being added to the emulsion.

In the present invention, when a sensitizing dye is added to a silver halide photographic emulsion, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone are preferably used as the dye solvent. Addition j11-1 when adding a sensitive dye to a silver halide emulsion,
1 x 10''S moles to 2.0% per mole of silver halide.
5 X 10-1 mol, preferably Fil, OX 10
-':E: l/"lLl, 0x10→mol. The sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers.

The silver halide grains used in the present invention are prevented from fogging during the manufacturing process, storage, or development process.
Alternatively, for the purpose of stabilizing photographic performance, various compounds may be included to complete chemical ripening.

For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, nitrobenzodiazoles, nitrobenzodiazoles, etc. triazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptopyrimidines, thioketo compounds such as oxazolinthione, and benzenethiosulfinic acid, benzenesulfinic acid, benzene. Many compounds known as anti-capri agents or stabilizers can be added, such as sulfonic acid amides, hydroquinone derivatives, amine phenol derivatives, gallic rIR enzyme derivatives, ascorbic acid derivatives and the like.

These compounds are preferably added during chemical ripening or before coating.

Silver halide emulsion according to the invention (Various hydrophilic colloids including gelatin are used as the inder. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes zeditic acid anhydride. , reaction products of gelatin and incyanate, or reaction products of gelatin and a compound having an active halogen atom, etc.Acid anhydrides used in the reaction with gelatin include , for example, maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, conolic anhydride, etc., and as in-7anate compounds, for example, phenylisocyanate, p
-Bromophenyl inocyanate, p-chlorophenylisocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthyl inocyanate, and the like.

Furthermore, as compounds having active halogen atoms, examples include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitropenze/sulfonyl chloride. , m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride), 3-nitro 4-aminobenzenesulfonyl chloride, 2-
Carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-
Amino-5-methylbenzenesulfonyl chloride, phthalyl chloride, p-nitrobenzoyl chloride,
Included are benzoyl chloride, ethyl chlorocarbonate, furoyl chloride and the like.

In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as a hydrophilic colloid to prepare a silver halide emulsion, colloidal albumin, agar, gum arabic, f-xtran, alginic acid, such as acetyl Conductors for cellulose such as cellulose acetate hydrolyzed to a content of 19-26%, polyacrylamide, imidized polyacrylamide, casein, and 90% urethane carboxylic acid group of vinyl alcohol-vinyl cyanoacetate copolymer. cyanoacetyl t
vinyl alcohol polymers containing polyvinyl alcohol-polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with vinyl group-containing heptamers, polyvinyl pyridine, polyvinylamine, polyaminoethyl methacrylate , polyethyleneimine, etc. can also be used.

The hardening treatment of the emulsion is carried out according to conventional methods. O1! The hardeners used are conventional photographic hardeners, such as formaldehyde, glyoxal, aldehyde compounds such as glutaraldehyde, and conductor compounds such as ahital or bisulfite adducts thereof, and methanesulfonic acid esters. compound, epoxy compound, aziridine compound, active halogen compound, maleic acid imide compound, active vinyl compound, carbodiimide compound, inoquinazole compound, N-methylol compound, incyanate compound, or Examples include inorganic hardeners such as chromium clearpan and zirconium sulfate.

The silver halide emulsion of the present invention contains a coating aid, an antistatic agent,
Various known surfactants may be included for various purposes such as improving slickness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, promoting friction, increasing contrast, and increasing g).

i.e. - U.S. Pat. No. 2,240.472, 2.83
1.766, 3,158.484, 3.210
．． No. 191, No. 3,294.540, No. 3.507.
No. 660, British Patent], No. 012.495, 1.0
22.878, 1,179.290, 1.19
8.450, U.S. Pat. No. 2,739i91, U.S. Pat.
No. 23,123, No. 1, No. 179, No. 290, No. 1.
No. 198.450, No. 2,739.891, No. 2.8
No. 23.123, No. 3,068.101, No. 3.41
5,649 thoughts, 3, 666, 478, 3,7
No. 56.828, British Patent No. 1,397.218, No. 3
, 113, No. 816, No. 3, 411, 413, No. 3, 473, 174, No. 3,345.974
No. 3,726.68 Ko No. 3, No. 3,843,368
No. 1, Belgian Patent No. 7: (No. 1,126, British Patent No. 1,1
No. 38,514, No. 1,159.825, No. 1,37
No. 4,780, U.S. Patent No. 2,271.623, U.S. Patent No. 2,
No. 288.226, No. 2,944,900, No. 3,2
No. 35.919, No. 3.671.247, No. 3.77
2, No. 021, No. 3.589.906, No. 3, 6
66, No. 478, No. 3.754.924, OLS No. 1.961.683, specification B4, and Japanese Patent Application Publication No. 117414/1982, No. 59025/1983, Japanese Patent Publication No. 378/1983, 4 U-379, 43-
7'1 described in the 13822 specification publication. There is c. , the list is saponin (steroid type), alkylene oxide 18
4 bodies (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl alkyl aryl ethers, polyethylene glycol esters,
) Ethylene glycol norbitane esters, polyalkylene glycol alkylamines or amides, 71
(Polyethylene oxide adducts of Nocone), glycidol triglyceride (IZIJ: alkenylsuccinic polyglyceride, alkylphenol polyglyceride), fatty acid esters of multi-flexible alcohol, alkyl esters of sugars, urethanes or ethers Nonionic surfactants such as triterpenoid saponins, alkyl carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfones #! salts, alkyl sulfates, alkyl phosphates, N-7sil-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxine group, sulfo group, phosphor group, sulfate ester group, phosphate ester group, amino e-s, aminoalkyl sulfone soaps, aminoalkyl sulfuric acid or phosphorous powder Nisdels, alkyl betaines , amphoteric surfactants such as amine imides and amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, complex quaternary ammonium salts such as pyridium and imidazolium, and aliphatic or heterocyclic Cationic surfactants such as sulfonium or sulfonium salts can be used.

In the silver halide emulsion of the present invention, in addition to the above-mentioned surfactants, the present single-bed accelerator contains
, 002,871, 2,445.611, 2,
It may contain imidazoles, thioethers, selenoethers, etc., which are described in 36 (J, No. 878, British Patent No. 1.352,196 - I!F).

In addition, in order to apply the silver halide emulsion of the present invention to a color photosensitive material, the red-sensitive silver halide emulsion, the silver halide emulsion adjusted to green sensitivity and blue sensitivity according to the present invention V
It is sufficient to apply the methods and materials used for color sensitive materials, such as incorporating a combination of cyan, magenta, and yellow couplers, respectively. Preferably a sexual one. The coupler is 4-equivalent or 2-equivalent to silver ion.
It may be either equivalence, or it may contain a colored coupler having a color correction effect, or a coupler that releases a phenomenon suppressor (so-called DIR coupler) as the color increases. Additionally, the coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethyleno coupler can be used. Among these, benzoylacetanilide-based and piparoylacetanilide-based compounds are advantageous.6 Specific examples of yellow-coloring couplers that can be used include U.S. Pat.
．． No. 408.194, 3. F) No. 51.155, No. 3
．． No. 582.322, No. 3,725.072, No. 3.
No. 891.445, West German patent], No. 547,868,
West German Published Application (OLS) No. 2,213.461, 2
, No. 219,917, No. 2,261,361, No. 2.
No. 414,006, No. 2,263.875, etc.

As the magenta color-forming coupler, pyrazolone compounds, inodacylon compounds, 7-anoacetylated compounds, and 7-anoacetylated compounds can be used, and in particular, pyrazolone-based compounds are used. Specific examples of magenta color-forming couplers that can be used include U.S. Pat. No. 2,600,788, U.S. Pat.
No. 9, No. 3, 314, 476, No. 3, 419
, No. 391, No. 4,519.429, No. 3, 55
8, No. 319, No. 3,582.322, No. 3.61
5. No. 506, No. 3, No. 834, No. 908, No. 3.8
91.445, West German Patent No. 1,810.464, West German Application Publication C, 0L8) 2.468.665, West German Patent No. 2.4
No. 17,945, No. 2,418,959, No. 2.42
4.467, Special Publication No. 40-6031, etc.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples are Kyokoku Patent Nos. 2,369,929 and 2.434.27.
No. 2, No. 2,474,293, No. 2.521,908
No. 2,895.826, No. 3.034.892, No. 3,311,476, No. 3.458.315,
No. 3,476.563, No. 3.583,971, No. 3,591.383, No. 3.767.411, OLS No. 2.414,830, No. 2, 4
Examples of colored couplers include U.S. Pat. No. 3.476.560 and U.S. Pat. No. 2,521.908.
No. 3.034,892, Special Publication No. 44-2016, No. 38-22335, No. 42-11304, No. 4
No. 4-32461, specification of patent application No. 49-98469-
Specification No. 50-118029, West German Application Publication (OLS)
) 2,418.959 can be conveniently used.

As a DIR coupler, for example, US Pat. No. 3.227.
No. 554, same:<, 617, No. 291, same'(,
701, 783, same 3, 790, 384, same'
, 4, 632, 345-'i”f, West German Application Publication (
OLS) No. 2.414,006, 2, 454,
No. 301, 2.454.4 (29 considerations, British Patent No. 953)
．． No. 454, and those described in Tokusho FIO-146570 can be used.

In addition to DIR Kagura, the light-sensitive material may contain a compound that releases a development inhibitor during development, and I+l
J. E. U.S. Pat. No. 3,297,445, 3.379.
No. 529, b'a insect publication (OLS') 2.417.
Those described in No. 914 can be used. Others, JP-A-5
No. 5-85549, No. 57-94752, No. 56-6
No. 5134, No. 56-135841, No. 54-130
No. 716, No. 56-133734, No. 5 fi-1
35841, U.S. Pat.
1980), 190:'43 (] 980),
19146 C1980 Mao, 20525 (198))
, 21728(]-9982) may also be used.

Two or more of the above couplers may be contained in the same layer.

The same compound may be contained in two or more different layers.

The coupler can be introduced into the silver halide emulsion layer using known methods such as the method described in U.S. Pat. No. 2,322,027. ),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic esters (octyl benzoate), alkyl amides (if fed) diethyl laurylamide), or organic solvents with a temperature of about 150°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
After dissolving in butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl selonorub ahitate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and 1 degree boiling point organic bath medium may be used in combination.

A positive and negative Vc coupler having an acid group such as carboxylic acid or sulfonic acid is introduced into the hydrophilic colloid as an alkaline aqueous solution.

These couplers are generally present in an amount of 2 X 10' moles to 5 X 10@ moles, preferably I X iff' moles to 5 X moles, per mole of silver in the silver halide emulsion layer.
10-mol is added.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminephenol derivatives,
It may contain gallic acid derivatives, ascorbic acid derivatives, etc., and specific examples thereof include US Pat. No. 2.360.290,
2,336.327, 2,403.721, 2,418.613, 2, 675, 314,
2,701,197, 2,704,713, 2,728.659, 2,732,300, 2
, No. 735,765, JP-A No. 50-92981 (No. 50-92989, No. 5Q-93928, No. 50-
No. 110337, Japanese Patent Publication No. 50-23813, etc.

As the MN inhibitor, diacetylcellulose, styrene-perfluoroalkylsodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of the agent include polymethyl methacrylate, polystyrene, and alkali-soluble polymers, and it is also possible to use colloidal silicon oxide as a lever. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and monomers having ethylene groups. Examples of the gelatin plasticizer include glycerin/glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer, alkyl vinyl ether-maleic acid copolymer, and the like.

Supports for light-sensitive materials made using the silver halide emulsion prepared as described above include baryta paper, polyethylene-coated paper, polypropylene coated paper, glass paper, cellulose acetate, and cellulose night. Supports include polyurethane, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports may be selected depending on the purpose of use of each photosensitive material.

These supports are subjected to F drawing processing depending on the safety.

The light-sensitive material made using the silver halide emulsion of the present invention can be subjected to one-speed processing by a commonly used known method after being exposed to light. It is an alkaline solution containing current active ingredients such as amine phenol and amine benzene, and can contain other alkali metal salts such as sulfite, carbonate, bisulfite, bromide and iodide. In the case of color, the normally used color development method is used, and in the 7-inversion method, which can be used tax-free, ``First, use Kurosha negative developing solution, and then apply the mortar!''. ! , or treated with a bath containing a fogging agent, and further treated with an alkaline solution containing herbal medicines for color development.

There are no particular restrictions on the processing method, and any processing method can be applied; for example, typical methods include a method in which after color development, bleach-fixing treatment is performed, followed by washing with water and stabilization treatment depending on safety; After drying, it is possible to apply a method in which licking and fixing are performed in separate cans, and further washing with water and stabilization treatment are performed as necessary.

The photosensitive material according to the present invention has high sensitivity, low fog, and good storage stability, so it can be applied to many uses, such as black and white general use, X-ray use, color use, infrared use, micro use, and silver %R. Excellent for various uses such as whitening, reversal, and diffusion transfer methods.

Further, when applied to multilayer color light-sensitive materials, the present invention can be applied to various layer structures well known in the field, including normal layer, reverse layer, and other layer structures.

〔Example〕

The present invention will be specifically explained below with reference to examples, but the present invention is not limited thereto.

The silver iodide content was 2 mol % in the core, 0.5 mol % in the shell, and a tetradecahedral crystal). This emulsion was divided into 6 parts, each emulsion containing sodium thiosulfate, dimethylselenourea, chloroauric acid, ammonium thiocyanate, 4-hydroxy-6-methyl-1,3, :(
a, 7-thitrazaindene and a sensitizing dye (v4 structure) were added, one was added and the mixture was stirred (referred to as emulsion A), and the other was further added with tetrachloropalladium (n) and d-monium as shown in Table 1. After adding varying amounts (emulsion B, C
, I), E, F), chemical sensitization and spectral sensitization at the optimal multiplier [sensitizing dye] Each emulsion (A to F) obtained above was treated with 4 as a stabilizer.
-Hydroxy-6-methyl-1+: 3+3a, 7-f traf indene, 1-phenyl-5-mercagutotetrazole, saponin as a coating aid, as a hardening agent], 2
- Add appropriate amounts of each of bis(vinylsulfonyl)ethane and 3 g of polyvinylpyrrolidone, and then add the following color couplers, doacyl gallate, and tricresyl phosphate-1.
A dispersion of -, j-r-thyl acid, sodium triisopropylnaphthalenesulfonate, and gelatin was added, coated on a triacetate base, and dried to prepare samples (A-F).

[Color coupler]

4J Sensitometry of each of these samples was carried out by the following method. A tungsten bulb (color temperature 5400°K) was used as the light source for exposure, and a U light of 1750 seconds was applied through a filter wedge.

The following treatments were then carried out: Treatment step 8 (38°C) Treatment time Color development gap...
...3 minutes 15 seconds 1 beach white...6 minutes (fund) sand water washing...
...Fix for 3 minutes and 15 seconds Set in water for 6 minutes Washing... Stable bath for 3 minutes and 15 seconds...
...The composition of the processing liquid used in each of the 1-minute blade-sho processing steps was as follows.

[Coloring phenomenon 1 liquid composition] [(Layered white liquid) [Fixing liquid formation] [Stabilizing liquid composition] The results of sensitometry are shown in Table 1 below, and the sensitivity is Emulsion A. The sensitivity is expressed relative to 100.

Table 1 From the results shown in Table 1 above, by adding 10 to 100 equivalent of palladium salt to gold salt in terms of chemical relative ratio,
It is clear that the capri is also low and high sensitivity can be achieved.

The thermal stability of samples and D was investigated and the results are shown in Table 2.

From the above results in Table 2, it can be seen that the samples according to the present invention have the same storage stability at high temperatures, and in particular, the increase in fog is suppressed7).

Using the monodisperse core/shell type silver iodobromide emulsion used in Example ff1J 2, chemical sensitization and photosensitization were carried out under the same conditions as emulsions A and D of Example 1. Run the emulsion in row 1
Similar stabilizers, couplers, coupler dispersants, @! A membrane agent, a coating aid, etc. were added, and the mixture was dried on a support and subjected to sensitometry.

Table 3 shows the results of repeating the above process and comparing the speed of the sensitization process with and without Pd salt. The sensitivity is actually M! i I
:'II The sensitivity of sample A obtained from 7L cutting A of 1 was set to 1.
Relatively expressed as 00 and 7.

From the above results in Table 3, it can be seen that the sensitization process was much stabilized by the addition of Pd salt according to the present invention ~ Monodisperse iodobromide monodecahedron used in Example 3 Crystal emulsion (
A, l)) Polydisperse silver iodobromide twin crystals”
L? jll (average particle size 1.5 μ, S / r =
0.34 silver iodide (equally distributed in the grains at a proportion of 2 mol) was prepared, and chemical sensitization and spectral sensitization were carried out in the same manner as in Example 1. These sensitized emulsions were coated on a support in the same manner as in Example 1, dried, and sample 0
1H) Seven knot measurements were performed. The results are shown in Table 4. Sensitivity A is expressed as a relative value with the sensitivity of the sample person as 100.

As is clear from the fourth cover, monodisperse pores rjl are larger than polydisperse emulsion.
1 (and has a non-uniform silver halide composition structure) has a greater effect of changing the taste due to the addition of Pd salt.

Example 4 Monodisperse core/shell type silver iodobromide emulsion with an average grain size of 0.9 μm (S/γ = 0.10, shell thickness 0.016 μm, silver iodide content 2 mols in the core part, 0 mols in the shell part) %) was prepared. Divide this into two parts, each containing sodium 100sulfate, dimethylselenourea, chloroauric acid, ammonium 100ocyanate, 4
-Hydroxy-6-methyl-1,3,3a,7-chitrazain, -Ribazonama\(emulsion ■),
For the others, tetrachloride and ammonium lobaladate (II) were further added, and after fc <emulsion J), chemical ripening was carried out under the optimum conditions. After aging, the stabilizer used in Example 1, a commonly used hardening agent, and a coating aid were added, and the mixture was coated on polyethylene terephthalate hese and dried. , ÷e well−゛°′
-7 These samples were subjected to sensitometry as fc
, Exposure was performed using tungsten electricity as a light source (color temperature 5.40
σ...K) and exposed for 1750 seconds through an optical wedge. The current test was carried out at 20°C for 10 minutes using the following current sea liquid.

Metol 2.51 Ascorbic acid 10. Oy Sodium metaphorate dihydrate 44I! potassium bromide
1. Add O1 water 1
The results are shown in Table 5.The sensitivity is the sensitivity of sample I 100.
It is expressed as relative sensitivity.

As is clear from Table 5, sample J of the present invention can be used not only at room temperature, but also at room temperature.
It can be seen that the storage stability under high temperature is significantly improved.

Claims (5)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a different silver iodide content near the surface and inside. Substantially monodisperse core/shell silver halide grains are chemically ripened in the presence of a chalcogen sensitizer, a gold sensitizer, and at least one water-soluble salt of Rh, Pd, Ir, or Pt. A silver halide photographic material containing the obtained silver halide emulsion. (2) The silver halide photographic material according to claim 1, wherein the silver halide grains are chemically ripened in the presence of a silver halide solvent. (3) The silver halide photographic light-sensitive material according to claims 1 and 2, wherein the silver halide grains are silver iodobromide grains. (4) Claims 1 and 2, wherein the water-soluble salts of Rh, Pd, Ir, and Pt are compounds represented by the following general formula [I] or [II]. The silver halide photographic material according to item 3. General formula [I] R_2MX_4 General formula [II] R_3M
X_6 [wherein, R represents a hydrogen atom, ammonium, or an alkali metal, M represents Pt or Pd, M' represents Ir or Rh, and X represents a halogen atom. ] (5) The amount of the compound represented by the general formula in the preceding paragraph is 10:1 to 100:1 in stoichiometric ratio (mole ratio) to the gold sensitizer.
The silver halide photographic light-sensitive material according to claims 1, 2, 3, and 4, characterized in that the silver halide photographic material is within the range of.