JPS59181337A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To form an image high in contrast with high sensitivity by aging a silver halide emulsion contg. AgI less concd. in shells than in cores in the presence of an instable type Se compd. CONSTITUTION:An emulsion high in sensitivity contains silver halide grains having 0-4mol% AgI content in shells and 1-15mol% AgI as the total content, and 10-300nm shell thickness. An instable type Se compd., such as tetramethylselenourea is added to this emulsion to age it and to prevent said core-shell type emulsion contg. AgI from lowering in contrast. Further, a solvent of silver halide, such as ammonium thiocyanate, is used in combination to age it chemically and to further enhance a sensitization effect, and moreover, one of phenols represented by the formula shown here in which R1-R5 are each H, halogen, CN, carbamoyl, or the like is incorporated to enhance its contrast to a higher degree. As a result, the obtained photosensitive material is high in sensitivity and gamma value, and low in fog.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and further relates to a silver halide photographic material having a layer containing an emulsion sensitized by a high contrast sensitization method of the light-sensitive material. Regarding photosensitive materials.

(Prior art) Silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material)
Appropriate hardness for high sensitivity and tone reproduction (C gamma-1γ)
has always been a technical problem.

Various chemical sensitization methods are known as means for increasing the sensitivity of silver halide photographic emulsions (hereinafter simply referred to as emulsions), which are the basic elements of photosensitive materials. It is representative.

By the way, among the above-mentioned sensitization methods, the selenium sensitization method is described in U.S. Pat.
゜499, same No. 1.602.592, same No. 2,64
No. 2,361, No. 2,739,060, No. 3,2
No. 97,446, No. 3,420,670, No. 3,
No. 320,069, No. 3.658.54Q, No. 3
, No. 408,196, No. 3,408,197, No. 3,442,653, No. 3,591°385%, British Patent No. 255,846-No. 861,984,
German Patent No. 1,033,510, German Patent No. 1,547,
762, French Patent No. 2,093,038, French Patent No. 2,093,209, Japanese Patent Publication No. 52-34491, French Patent No. 52-34492, French Patent No. 53-295, French Patent No. 52-36
009 No. 1, same! 52-38408 and 57-22
No. 090. However, in general, selenium sensitization has a greater sensitizing effect than sulfur sensitization, which is currently commonly performed in the industry (but is more likely to cause fogging,
In addition, it has the disadvantage that it easily softens the tone, and has been considered difficult to put into practical use.On the other hand, as a method of increasing the elementary sensitivity as a quality of the silver halide grain itself,
For silver bromide or silver chlorobromide, a method is known in which silver iodide is mixed to the extent that a solid solution or a mixed crystal is formed. For example, A and P described in Photographic Journal Vol. 79 (1939) from page 463 onwards.
It is known from the literature by , H., Trivelli and W.F. Smith that when silver iodide is included in silver bromide up to a certain content, the sensitivity increases in accordance with the silver iodide content ffi.

However, silver halide grains mixed with silver iodide have the disadvantage that the tone becomes softer as the silver iodide content increases.

As mentioned above, there are two methods to increase the sensitivity, the selenium sensitization method in j-, and the increase in elementary sensitivity using silver iodide, but it is possible to properly adjust γ, which is another important characteristic of photographic properties. The contrast is becoming softer (lower gamma) without any control, and the way of utilization is closed, and it has become a bottleneck in the development of continuous or hard high-sensitivity photosensitive materials (Objective of the Invention). In view of the above, an object of the present invention is to provide a photosensitive material that is highly sensitive and has an appropriate r or high contrast. It is preferable for the silver iodide distribution in the silver grain to be high in the grain core and low in the surface part in order to obtain the basic sensitivity and appropriate gamma. Therefore, the above requirements can be preferably achieved by the core/shell type, and the iodide Emulsions containing core/shell type grains with silver distribution contain selenium compounds, especially unstable types (labile,
'1abil@) I learned that chemical ripening in the presence of a selenium compound causes non-soft contrast sensitization to become hard contrast.

Furthermore, it has been found that the chemical ripening of the emulsion is effectively promoted by the coexistence of a silver halide solvent. In the present invention, it is preferable to add it to the emulsion after the desalting step and preferably after the physical ripening in a manufacturing method that does not include a desalting step. is obtained by a production method including a desalting step.

Based on the above knowledge, the silver halide grains of the emulsion used in the emulsion layer of the light-sensitive material are substantially core/shell type grains, and regarding the silver iodide distribution, the silver iodide content in the core part is high in the core part and the silver iodide content in the core part is high in the shell part. By selecting a grain structure with a lower O content and subjecting the emulsion to chemical ripening using a selenium compound, especially a labile hexasin compound, high sensitivity, appropriate gamma, or high contrast sensitization can be achieved. It constitutes the main technology for obtaining materials, and further promotes the ripening effect by coexisting with silver halide solvents in chemical ripening.

Furthermore, at least one type of phenolic rust conductor specified by the general formula (■) was added to serve as a complementary technical means for gamma adjustment. Hydrogen atom/halogen atom, hydroxyl group, alkoxy group,
Amino group, acylamino group, acyloxy group, carboxyl group, alkoxycarbonyl group, alkoxycarbonylamino group, aryl group, sulfo crystal (may be in salt form)
, represents a cyan group, an alkyl group, a carbamoyl group or a sulfomyl group, and any two of them are preferably R1 and &
, R2, R8, R3, R4, R4 and Rs may be combined to form a ring (for example, a benzene ring).

Next, the present invention will be explained in more detail.

The core/shell type silver iodide grains according to the present invention consist of at least one sheath/layer part and a core part with different silver iodide contents, and the silver iodide grains in the shell part are The silver iodide content is determined to be lower than the silver iodide content in the core.

In the present invention, the composition is as described above! The silver iodide content in the shell portion of the X silver halide grains is preferably as low as possible, preferably close to 0%, and substantially silver bromide is preferred.

Furthermore, the core portion of the grain may be formed as two or more layers having different silver iodide contents. The difference in content between the layer with a high silver iodide content and the layer with a low silver iodide content in the silver norogenide grains of the present invention may have a sharp boundary, or may vary continuously without necessarily having a clear boundary. It may be something.

The distribution state of silver iodide in the above silver nohalide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated, for example, by measuring luminescence at low temperatures as described in the Abstracts of the 1986 Annual Conference of the Photographic Society of Japan.

The core/shell type halogen according to the present invention (l1 particle is 1
．． It consists of a core part made of silver halide containing silver iodide, and a shell part made of silver halide, which covers the core part and has a lower content of silver iodide than the content in the core part. Preferably, the silver halide grains have a thickness of 0.01 to 03 μm.

4. In a preferred embodiment of the silver halide grains of the present invention, the silver halide composition of the core portion is such that silver iodide is 1.
The shell portion is a silver halide containing 0 to 4 mol% of silver iodide. Further, it is preferable that the difference in silver iodide content between the shell portion and the core portion is 1 mol % or more. In the silver halide grains of the present invention, the silver halide composition other than the above-mentioned silver iodide is preferably mainly silver bromide, but may contain silver chloride as long as the effects of the present invention are not impaired.

The average silver iodide content of the silver halide grains according to the present invention is preferably 0.5%/l/% to 15%/l/%.

The shape of the silver halide grains according to the present invention may be, for example, hexahedral, octahedral, dodecahedral, plate-like, or spherical, or may be a mixture of these various shapes. Particles having a hedral shape or a dodecahedral shape are preferred.

The silver halide grains used in the silver halide emulsion layer according to the present invention include the above-mentioned core/shell type silver halide grains.
It is preferable that all m particles are core/shell type silver halide grains.

The core/shell type silver halide grains according to the present invention can be used alone (- or two or more types of silver halide grains having different average grain sizes can be arbitrarily mixed and used).

Further, two or more kinds of core/shell type silver halide grains having different silver iodide contents, which will be described later, can be preferably used as a mixture.

The method for producing the core/shell type emulsion is as follows: First, a strawberry emulsion having a predetermined silver iodide content and serving as a core portion is prepared, and then a strawberry emulsion is prepared that has a predetermined silver iodide content and is then prepared without dissolving the silver halide grains of the mother's milk. The new silver halide may be precipitated to form a shell portion at a precipitate formation rate such that the surface of the grain becomes the crystal deposition surface of the new silver halide to be precipitated. Whether or not the shell portion can be formed varies depending on the conditions of the breast milk, but the formation conditions can be determined experimentally.

Next, as the selenium compound used in the present invention, among the various selenium sensitizers disclosed in the above-mentioned patents, non-labile selenium compounds (e.g. selenite, selenocyanate) should be avoided. An unstable (labile) selenium compound (hereinafter referred to as a selenium sensitizer) suitable for the core/shell type emulsion having the silver iodide distribution according to the invention is selected and used.

Unstable type (1ablle labile) as used herein
The term has a meaning well known to those skilled in the art, ie, for a substance that produces a silver salt when added to an aqueous solution of silver nitrate.

For example, unstable sulfur compounds yield silver sulfide and unstable selenium compounds yield silver selenide.

The selenium sensitizers used in the present invention include a wide variety of labile selenium compounds, e.g.
U.S. Patent No. 1,623,499, U.S. Patent No. 1,574°9
No. 44 and No. 1,602,592.

Useful selenium sensitizers include colloidal selenium metal, aliphatic inselenocyanates such as allyl isoselenocyanate, and the like. Particularly useful groups of selenium sensitizers include aliphatic selenoureas such as aliphatic groups such as methyl, ethyl, propyl, impropyl\butyl, selenoketones (such as selenoacetone, selenoacetopheno7, etc.) and selenoamides, selenocarboxylic acids, etc. Also useful selenium sensitizers containing O0 include one or more aromatic groups (e.g. phenyl,
Tolyl, etc.) or related selenoureas containing bicyclic groups (e.g. benzothiazolyl, pyridyl, etc.) In addition to the unstable organic selenium compounds mentioned above, other useful selenium containing unstable selenium atoms. Sensitizers may also be used and these include: Namely, tetramethylselenourea, N-(β-carboxyethyl)-NUN'-dimethylselenourea, selenoacetamide, diethylselenide, 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate, e.g. p-) Lyselenophosphate etc.

The amount of selenium sensitizer used varies depending on the specific selenium compound used, the properties of the silver halide, the aging conditions, etc. Generally, the selenium sensitizer per mole of silver halide is 0.01■
From 5. Use OmyPIi degree.

Further, the silver halide grains according to the present invention described above can be chemically ripened in the presence of a silver halide solvent to achieve significantly higher sensitivity.

Silver halide solvents used in the present invention include: U.S. Patent No. 3,271,157, U.S. Patent No. 3,531,289, U.S. Pat. -Organic thioethers described in JP-A-53-82408 and JP-A-55-7
(b) described in No. 7737, No. 55-2982, etc.
Thiourea derivatives, silver halide solvents having (c) an acid complex or a thiocarbonyl group sandwiched between a sulfur atom and a nitrogen atom, described in JP-A-54-100717; In addition to the listed (d) imidazoles, (el sulfites, (f) thousand oceanates, etc.
Examples include silver genide solvents described in JP-A-57-196228.

These specific compounds are shown below.

(S -11 HO-(CH,), -8-(CH,), -8-(CH,
), -0HCHI -NHCOCHl CI(t C
0OHCH, -S -CH2CH,SC,HIl(S-
2) (S-3) (S-4) “ (S-5) K2SO.

(S-6) H45CN (S-7> SCN Particularly preferred solvents include thiocyanate and tetramethylthiourea.Also, the fl of the solvent used varies depending on the type, but for example, in the case of thiocyanate,
The preferred Asahi ranges from 51n9 to 1 g per mole of silver halide.

All of the compounds represented by the general formula +n used in the present invention are known to act as reducing agents, and even in emulsions, they constitute redox agents in a certain equilibrium. Therefore, the oxidized form and the 15-element form exist even in the emulsion. Therefore, the same effect can be expected even if an oxidized form of the compound represented by general 2) is added.

The compound represented by general 2) used in the present invention is preferably added to the emulsion at the time of chemical ripening or after the completion of chemical ripening.

The amount to be added varies depending on the properties of the silver halide and the degree of selenium sensitization imparted to it, but a range of 10-7 mol to 1O-1 mol per mol of silver is effective, and io A range of -' mole to 10-2 mole is particularly effective.

Margin 22~' Below, typical compounds represented by the general formula [4] used in the present invention are shown, but the invention is not limited thereto.

Cl-1]' Cl-2) Cl-331:I
-O[I=5] ,, lll-6:][:l-
7) Cl-8) l:I-9:)[
I-10: ] CI-11) C
I -12JCI -13) ' -CI
-143 The emulsion used in the present invention includes one culm of its production,
For the purpose of preventing the occurrence of fog during storage or development processing, or for stabilizing photographic performance, various compounds may be added to the composition for the termination of chemical ripening.

For example, azo-7vs, such as benzothiazolium salts, nitroingzoles, nitrobenzimidazoles, RI:11j benzimidazoles, promobenzimitazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles. , benztriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc., also mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, and also benzenethiosulfinic acid. ,
11 inhibitors such as benzene sulfinic acid, benzene sulfonic acid amide, etc. are known as 1f stabilizers.
It is possible to identify many of the compounds found in this study. It is preferable to use these chemicals during chemical ripening (or before coating).

As the emulsion emulsion according to the present invention, various hydrophilic colloids including gelatin can be used.

Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Things, etc. are included. Examples of acid anhydrides used in the reaction with gelatin include maleic anhydride, fucuric anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of isocyanate compounds include: For example phenyl isocyanate, p-
7-romophenyl isocyanate, p-chlorophenylisocyanate, p=)lylisocyanate), p-nitrophenyl isocyanate, naphthylisocyanate>-:, etc. can be mentioned.

Further, examples of compounds having an active hydrogen atom include benzene: 11 chloride, p-methoxybenzenesulfonyl chloride, p-7 enoxybenzenesulfonyl chloride, and p-brff% benzene. Sulfonyl chloride, p-)luenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-carboxyl- Included are 4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, butaryl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethylchlorocarbonate, furoyl chloride, and the like. .

In order to prepare the entire emulsion, hydrophilic colloids such as the above derivative gelatin and ordinary photographic gelatin + 7.
) (j ha, must j, Rini J7:", j dicoidal albumin, sinner, '7' dibiago, dextocin, alginic acid, e.g. acedel-containing 19"-26 force II water splitting Cellulose acetate, such as cellulose cyanoacetate-1, copoly-?-, 4I urethanecarphonic acid RA or cyanohydryl-containing vinyl alcohol ζ remer, bolivinino 2, γ alcohol-L, vinyl pyrrolidone , hydrolyzed polyvinyl acedate, a polymer obtained by polymerizing a protein or a saturated acylated protein with a vinyl group-containing monomer, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine 2.
1' is also possible.

Various known interfaces are used for various purposes such as the emulsion according to the present invention, coating aid, antistatic, slippery improvement, emulsification dispersion, adhesive prevention, and photographic property improvement (for example, development acceleration, high contrast, and sensitization). It may also contain an activator.

That is, U.S. Patent No. 2,240,472;
No. 831,766, No. 3,158,484, No. 3
, No. 210,191, No. 3,294,540, lI
'il No. 3.507,660@, British Patent No. 1.01
No. 2,495, No. 1,022,878, No. 1.1
No. 79,290, U.S. Patent No. 1.198,450, U.S. Patent No. 2,739,891, U.S. Patent No. 2.823.123,
Same No. L179,290, Same No. 1.198,450,
No. 2,739,891, li'-1 No. 2,823,
No. 123, No. 3.058,101, No. 3,415
, No. 649, No. 3,666,478, No. 3.75
6,828, British Patent No. 1,397,218, British Patent No. 3,113,816, British Patent No. 3,411,413, British Patent No. 3,473,174, British Patent No. 3,345,974 ,
No. 3,726,683, No. 3,343,368, Belgian Pestle No. 731,126, British Patent No. 1.1
No. 38,514, same No. 1. ．． No. 159,825, same No. 1
, 374,780 @, U.S. Patent No. 2,271.623
No. 2,288,226, No. 2.944,90
No. 0, No. 3,235,919, No. 3,671,2
No. 47, No. 3,772,021, No. 3,589,
No. 906, No. 3,666.478, No. 3.75.
No. 4,924, West German patent application OL81,961,683
No. 50-1117414, 50.
-59025, Special Publication No. 40-378, No. 40-37
No. 9 and No. 43-13822.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, 7-comylated tylene glycol/polyprohylene glycol condensate,
Polyethylene glycol alkyl 1ef alkylaryl ether polyethylene glycols, polyethylene glycol nobisorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene peroxide adducts of silicone), glycidol derivatives (e.g. alkenyl succinic rβ polyglycerides, alkylphenol polyglycerides) glycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid saponins, alkylcarboxylic acid groups, alkylbenzenesulfuric acid, phosphoric acid group, alkylnaphthalene sulfonic acid group, alkyl sulfate ester, alkyl phosphate ester, N-y/l/-N-alkyl tauric acid, sulfosuccinate ester, sulfoalkyl polyoxyethylene alkylphenyl ether, polyoxy Anionic surfactants containing acidic groups such as carboxyl groups such as ethylene alkyl phosphates, sulfo groups, phosphox, sulfate ester groups, Nisder phosphate groups, amino acids, aminoalkyl sulfonic acids, amines, noalkyl sulfates, etc. Also, amphoteric surfactants such as phosphoric acid esters, alkyl betaines, amine imides, amine oxides, alkyl amines, J aliphatic acids or aromatic quaternary ammonium IIAs, pyridium, imidazolium, etc. It is possible to use a cationic surfactant such as a sulfonium or sulfonium jJ group containing an aliphatic or heterocyclic ring.
C-kill.

In the emulsion according to the present invention, in addition to the above-mentioned surfactant, as an image promoter, OLS patent application No. 2.002, 8
No. 71, No. 2,445,611, No. 2,360,
878%, imidazoles and thioethers described in various specifications of British Patent No. 1,352,196, etc.
It may also contain selenoethers and the like.

In addition, in order to apply the emulsion according to the present invention to a color light-sensitive material, the emulsion according to the present invention may contain a combination of yellow, magenta, yellow and cyanide pullers, respectively, which are used in the color light-sensitive material. Depending on the method and materials, it is desirable that the coupler be non-diffusible and have a hydrophobic group called a ballast group in the molecule. Colored couplers have the effect of color correction.
Alternatively, it may contain a coupler (so-called DIR coupler) that releases a development inhibitor during development. Additionally, the coupler may be one in which the product of the coupling reaction is colorless.

For the yellow coupler and 17, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used are U.S. Pat.
No. 06, No. 3,408,194, No. 3,551,15
No. 5, No. 3,582.322, No. 3,725,072
No. 3,891,445, West German Patent No. 1.547,
No. 868, West German Patent Application (OLS) 2.213,461
No. 2,219,917, No. 2,261,361, No. 2,414,006, No. 12,263,875, etc.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

Specific examples of magenta couplers that can be used are disclosed in U.S. Pat.
No. 600,788, No. 2.9 s, No. 3.60 s, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,419,391, 1 Tsukasa No. 3,519,429, No. 3,558,319, No. 3
．． No. 582,322, Mi + No. 3,615,506, No. 3,834,908, No. 3,891,445, Four German Patent No. 1.81Q, No. 464, West German Patent Application (OLS)
No. 2,408,665, No. 2,417,945, No. 2,418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, etc. (2.c.

As the dian coupler, phenol compounds, naphthol compounds, etc. can be used.

Specific examples thereof include U.S. Patent No. 2,369,929 and U.S. Pat.
．． No. 434,272, No. 2,474,293, No. 2,521,908, No. 2,895,826
No. 3,034,892, No. 3,311.47
No. 6, No. 3,458,315, No. 3,476,5
No. 63, No. 3.583.971, No. 3,519,
No. 383, No. 3,767.411, West German patent application (
OLS) No. 2,414,830, OLS No. 2,454,3
No. 29 and JP-A-48-59838.

As a colored coupler, for example, U.S. Patent No. 3.47
No. 6.560, No. 2,521,908, No. 3.0
No. 34,892, Special Publication No. 44-2016, No. 38-2
No. 2335, No. 42-11304, No. 44-3246
No. 1, Specification of Japanese Patent Application No. 49-98469, No. 50-11
Specification No. 8029, West German Patent Application (OLS) No. 2.4
18,959 can be used.

As a DIR coupler, for example, U.S. Pat.
, No. 554, No. 3,617,291, No. 3,70
No. 1,783, No. 3,790,384, No. 3,6
No. 32,345, West German Patent Application (OLS) No. 2,414
, No. 006, No. 2,454,301, No. 2.45
No. 4,329, British Patent No. 953,454, Patent Application No. 1973
Those described in No. 0-146570 can be used.

In addition to DIR couplers, compounds that release development inhibitors during development may also be included in the light-sensitive material, for example, U.S. Pat. Nos. 3,297,445 and 3,379,5
No. 29, West German Patent Application (OLS) No. 2,417,914
Items listed in the number can be used. Others, JP-A-55-8
No. 5549, No. 57-94752, No. 56-6513
No. 4, No. 56-135841, No. 54-130716
No. 56-1133734, No. 56-135841
No., U.S. Patent No.

4.310,618, British Patent No. 2,083,640
No., Research Disclosure 18360 (197
9), 414850 (1980), rot19033
(1980), genus 19146 (1980 χ rot 205
25 (1981), 421728 (1982) may also be used.

Two or more of the above couplers may be included in the same layer. Further, the same compound may be contained in two or more different layers.

To introduce the coupler' into the emulsion layer, known methods such as those described in U.S. Pat. No. 2,322,027 can be used. For example, 7-tar acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (cyphenylphonophthalate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), or boiling point (9)°C to 1
Organic solvent at 50°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, propionic ethyl Yabu, etc.
It is dissolved in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and a hydrophilic colloid VC is dispersed therein. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

When the coupler has an acid group such as carboxylic acid or sulfone, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

These couplers are generally present in an amount of 2 per mole of coupler in the emulsion layer.
X10"" moles to 5.times.JO"" moles are added, preferably 1X10"" moles to 5X10" moles.

As antistatic agents, diacetylcellulose, styrene perfluoroalkylridium maleate copolymer, alkali salts of reaction products of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethacrylic acid megyl, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. Further, a copolymer with a monomer having a membrane physical property group can be mentioned.

Examples of the gelatin/plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer, alkyvinyl ether-maleic acid copolymer, and the like.

Supports for photosensitive materials made using the emulsion prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypyrene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, Supports include polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the purpose of use of each photosensitive material.

These supports are subjected to undercoat processing if necessary.

After exposure, the light-sensitive material prepared using the emulsion of the present invention can be developed by a commonly used or known method.

The black-and-white developer can include a developing agent such as hydroxybenzenes, aminephenols, aminebenzenes, and the like. Further, when the light-sensitive material is in color, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black negative developer, then exposed to white light or treated with a bath containing a fogging agent, and then color developed with an alkaline developer containing a color developing agent.

There are no particular restrictions on the processing method, and any processing method can be applied; for example, a typical method is to carry out bleach-fixing treatment after color development, and if necessary, wash with water.
It is possible to apply a method in which a stabilizing treatment is performed, or a method in which bleaching and fixing are performed separately after color development.

The above-mentioned emulsion has extremely high sensitivity and low capri, so it is preferably applied to many light-sensitive materials. For example, the photosensitive material related to the EJJK of the present invention can be used for various purposes such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, and diffusion transfer method use.

(Example) The present invention will be specifically explained below with reference to Examples.

Example-1 Average grain size of silver iodobromide containing 7 mol% of silver iodide
The following four types of cubic emulsions A, B, and C of 0μ.

and D were prepared. Here, emulsion A is a core/shell type silver iodobromide emulsion having a silver bromide shell (thickness 0.3 μm). Emulsion B is a core/shell type silver iodobromide emulsion having a silver bromide shell (thickness 0.05 μm). Silver iodobromide emulsion C has silver bromide layers (thickness 0.01 μm).
The core/shell type silver iodobromide emulsions have no silver bromide shells and silver iodide is evenly distributed. , N-dimethylselenourea (designated as unstable selenium sensitizer-X) or sodium selenocyanate (designated as non-labile selenium sensitizer-Y) (each with 0.45 In91 mol Agx
) and ammonium thiocyanate (1501n91 mol kgx) at ω°C, each emulsion was treated with 4-hydroxy-6-methyl-
1,3,3m,7-thitrazaindene was added.

Next, each emulsion was divided, and a portion of the emulsion contained a compound represented by the general formula according to the present invention (250 m91 mol Agx
) was added according to Table 1. Further, samples A1 to A19 were prepared by coating the film to a silver content of 50 m97100 crl on a polyethylene terephthalate film to which appropriate amounts of formalin as a dura mater and saponin as a coating aid were added, and drying. Each of these samples was exposed to 1% O seconds of 3;2 cr ILS using a KS-1fil sensitometer (J-Nishiroku Photo Industry @ Kyoto).
Development was carried out at 40° C. for (9) seconds using an emulsion solution having the following composition, followed by fixing, washing with water, and drying in a conventional manner.

(Developer formulation) Sodium sulfite 70 g Hydroquinone 10 g Boric anhydride
1g sodium carbonate monohydrate
20 gl-phenyl-3-pyrazolidone 0.3
5g Sodium hydroxide 3g 5-methylbenzotriazole 0.05g Potassium bromide
5g Glutaraldehyde bisulfite 15 9 Acetic acid 5g Add water to make 1e.

The results are shown in Table 1. The sensitivity was expressed as a relative sensitivity with the sensitivity of sample A4 as 100. Further, gamma (r) is expressed as an average slope between a point where the photographic density excluding fog is 0.1 and 0.5.

As is clear from the results discussed below, sample AI according to the present invention
, 2 , 3 and 9 , 10 , 12 , 12 , 13
It can be seen that samples 1 and 14 have higher sensitivity and higher r than other samples. Furthermore, the results in Table 1 suggest that the characteristics vary depending on the shell thickness and that there is an optimum shell thickness.

Example-2 Silver iodobromide containing 4 mol% of silver iodide had an average grain size of 1.
The following four 6μ octahedral emulsions E, F, G and H were prepared.

Here, emulsion E is a core/shell type silver iodobromide emulsion with a silver bromide shell (thickness 0.3 μm) and core/shell type silver iodobromide emulsion F is a core/shell type silver iodobromide emulsion with a silver bromide shell (thickness 0.05 μm). Silver emulsion G has a silver bromide shell (thickness: 0.01 μnl). Core/shell type silver iodobromide emulsion H has no silver bromide shell and silver iodide is evenly distributed. Silver Bromide Next, the above emulsions E and F were prepared in the same manner as in Example-1.

G and HKN, N-dimethylselenourea (3) or sodium selenocyanate (7) (0,15■/-
After selenium sensitization at (a) °C using (en=Ag 1-phenyl-5-mercaptotetrazole was added.

Next, each emulsion is divided into parts, and a part thereof contains the compound (250In91) represented by the general formula (I) according to the present invention.
molar Agx) was added according to Table 2.

Further protection dispersed yellow coupler α-C47
(1-benzyl-2-phenyl-3,5-dioquine-1
,2,4-doriazolidinyl)]-]α-pivalyl 2
-Chloro~5-γ-(2゜4-di-t-aj/I/phenoxy)butertemide]acetanilide dispersion (0,
21 mol 1 mol Agx) and 1,
3.5-) Acryloylhexahydro-8-1 riazine and 1,2-bis(vinylsulfonyl)ethane, a coating aid and saponin were added, respectively.

The emulsions thus prepared were each coated on a cellulose triacetate film base.

A white wedge exposure (1
t-6° (processing process) Processing process (38 t; y Processing time color development)
3 minutes 15 seconds bleach, 6 minutes 30 seconds water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds Stabilize for 3 minutes and 15 seconds
The composition of the treatment liquid used in each treatment step was as follows.

(Color developer composition) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfur fl! Salt 4.89 Anhydrous sodium sulfite 0.14g Hydroxylamine % sulfur salt 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10.9 Potassium bromide 1. 155J chloride length triu,
t, 0.14. Add p-nitrilotrivine vinegar 3-sodium monohydrate 1.205' potassium hydroxide 1.4sg water and IC
shall be.

(Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt 100.
0 g Ethylenediaminetetroacetic acid diammonium 10.0
．． '7 Add ammonium bromide 150.0 g glacial acetic acid 10.0 ml water'
Let it be c1e.

Adjust the pH to 6.0.

(Fixer composition) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water was added to make 1e.

Adjust to pH 6, O.

It can be seen that samples 2], 21, n, 4, 30, 31, 32 and 0 have higher sensitivity and higher γ than other samples.

Example 3 Emulsion B and Emulsion F prepared in Example 1 and Example 2 were treated with N,N-
Selenium sensitization was performed using dimethylselenourea ■. The same stabilizers, coupler dispersions, hardeners and coating aids as in Example 2 were then added to each emulsion, and the emulsions were coated on a triacetate film base support and dried. Sensitometry was performed on each of these samples in the same manner as in Example 2.

The results are shown in Table 3.

As is clear from the above table, the sensitizing effect of the samples in which the silver halide grains of the present invention were chemically sensitized in the presence of ammonium thiocyanate as a silver halide solvent was found to be significantly improved.

(Effects of the Invention) At the same time as achieving the objects of the present invention, the utility value of the selenium sensitization method was increased and the sensitivity of silver halide emulsions was improved.

Agent Yoshimi Kuwahara

Claims (3)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion of the emulsion layer substantially contains core/shell type silver halide grains. A silver halide photographic photosensitive material having a silver iodide-containing form in which the shell contains a smaller amount of silver iodide than the core, and the emulsion is chemically ripened in the presence of an unstable selenium compound. material. (2) The silver halide photographic material according to claim 1, wherein the emulsion of the emulsion layer is chemically ripened in the coexistence of a silver halide solvent. (3) The silver halide photograph according to claim 1 or 2, wherein the emulsion of the emulsion layer contains at least one kind of phenol represented by the following general formula (1). Photosensitive material. General formula (Jj block [wherein, bird r Rt r Rs + R4 and R3 are...
Each hydrogen [child, halogen atom, hydroxyl group, alkoxy group, amine group, acylamino group, acyloxy group,
Represents a carboxyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group, a 7+) -l group, a sulfo group, a cyano group, an alkyl group, a carbamoyl group or a sulfamoyl group, any two of which are linked to form a ring. Good too. ]