JPS59188639A - Silver halide emulsion - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to improve graininess sharpness by incorporating a core/shell type silver halide obtained by reacting a water-soluble silver salt soln. with a water-soluble halide soln. in the presence of a silver halide solvent and growing the obtained seed crystals to a specified range of grain diameter. CONSTITUTION:A water-soluble silver salt soln. is reacted with a water-soluble halide soln. in the presence of a silver halide (AgX) solvent and the obtained AgX seed crystals are grown, and the obtained core/shell type AgX having <=0.5m average grain diameter is incorporated in an emulsion. The core/shell type emulsion obtained by growing the AgX seed crystals in an AgX solvent is extremely high in sensitizing effect. As the grain diameter ratio of emulsion grains to seed crystals, a ratio of >= about 1.1:1 is found to be effective, and the upper limit of the growth ratio is about 10:1. Such an emulsion is good in graininess and sharpness, and yet, restrains occurrence of fog, and enhances sensitivity extremely.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a silver halide emulsion with high sensitivity and excellent image quality. Concerning silver emulsions.

There has been a demand for the development of photosensitive materials with high sensitivity and excellent image quality using silver halide photographs (hereinafter referred to as photosensitive materials). Opportunities for taking photos under less adverse conditions have increased,
In addition, with the development of small-for-man H light-sensitive materials, there is a strong demand for the development of light-sensitive materials with high sensitivity, high sharpness, and excellent graininess. However, it has been difficult to achieve both higher sensitivity and improved image quality.

The present invention is an attempt to solve the problems of such incompatible photosensitive materials.

[Prior art]

It is known that in light-sensitive materials, the average size of -.a silver genide grains is an important factor that governs the relationship between sensitivity and graininess. Generally, the finer the particles, the greater the number of pixels and the better the graininess, but the lower the photographic sensitivity becomes. Therefore, the most traditional method for achieving high sensitivity and excellent graininess is to improve the quantum efficiency of silver halogenide grains, in other words, to improve the sensitivity/-tj-is relationship. For this purpose, knowledge of solid state physics is being actively incorporated.

Research that theoretically calculated this quantum efficiency and considered the influence of particle size distribution was published, for example, in the Proceedings of the 1980 Tokyo Symposium on Advances in Photography A, Interactions Between Light and Materials for Photography. It is described in Graphics 9 Applications, page 91.

This research predicts that narrowing the particle size distribution and creating a monodisperse emulsion will be effective in improving the penetration of the Doji effect. In addition, in order to achieve sensitization of silver norogenide emulsions, in one process called chemical sensitization, which will be described in detail later, in order to efficiently achieve high sensitivity while maintaining low fog. , it seems reasonable to infer that a monodisperse emulsion would be advantageous.

On the other hand, in order to provide a light-sensitive material with high sensitivity and excellent sharpness, studies have been conducted on combinations of silver halogenide grain sizes that minimize light scattering. And the average particle size is 0.5μ
In the following cases, it is known that the finer the particles, the less light scattering and the better the sharpness. A specific example of such technology is The Theory of th
e Photographic Process-ss
4th Ed, James, p. 584, and US Pat. No. 3.402.046. Furthermore, it is known that the best method for obtaining the above-mentioned cloth is to combine a silver halide emulsion consisting of monodispersed silver halide grains. Therefore, in order to minimize the light scattering in the emulsion, a silver halide emulsion with monodisperse or fine grains of 0.5 μm or less and an improved sensitivity/size relationship is required.

Monodisperse halogen ratio silver particles control pAg and pH.
It can be obtained by adding a solution of a water-soluble silver salt and a solution of a water-soluble silver halide to a double agent method.

An emulsion consisting of large monodispersed silver halide grains can be obtained in a short time by carrying out the above method in the presence of an AgX solvent. On the other hand, if an emulsion consisting of fine-grained silver halide with an average grain size of less than 0.5 μm is precipitated in the presence of a silver halide solvent, an emulsion with good monodispersity cannot be obtained, and it is difficult to produce such a monodisperse emulsion. As a matter of law, no research had been done on era names.

Conventionally, it has been considered preferable to manufacture such emulsions by a method in which no silver halide solvent other than an excess of halide is present, that is, a method known as a normal neutral method or an acidic method. Ta.

However, monodisperse emulsions obtained by neutral or acidic methods have extremely low sensitivity after chemical sensitization. I couldn't get it.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide emulsion with high sensitivity and improved graininess and sharpness.

Other objects of the invention will become apparent from the following description of the specification.

[Structure of the invention]

The present inventors continued research to improve monodisperse emulsions that have favorable photographic properties but have the defect of low sensitivity after chemical sensitization. A core/shell type halide having an average grain size of 0.5μ or less is formed by reacting a solution of a water-soluble silver salt with a solution of a water-soluble halide to grow seed crystals consisting essentially of silver halide. It has been found that the above-mentioned object of the present invention can be achieved by a silver halide emulsion characterized by containing silver gayide grains.

The silver halide grains of the present invention have an average grain size of 0.
It is 5μ or less. Fio is preferably 3μ or less. The grain size and distribution when silver halogenide emulsions with such a grain size range are produced by conventional methods that do not use seed grains are determined by the presence or absence of a silver halogenide solvent (hereinafter referred to as AgX solvent). It was impossible to obtain a fine-grain monodisperse emulsion on an industrial scale in the presence of an AgX solvent.

The silver rognide emulsion of the present invention is characterized in that seed grains are grown in the presence of an AgX solvent.

Here, it is preferable to use a highly monodisperse emulsion for the seed particles, which is formed by a method that does not contain any AgX solvent other than an excess of noride, ie, by a conventional acidic method or a neutral method. The average size of the seed particles used in the present invention is 0.05μ to 0.3μ
The thickness is preferably 0.1 μ to 0.2 μ.

In the present invention, if the grain size ratio of the seed grains used in the present invention and the emulsion of the present invention is greater than or equal to [It is 0 times.

The X-speed sensitivity of the silver halide emulsion of the present invention is at least four times higher than that of emulsions of the same size that do not contain any AgX solvent other than an excess of -ride, ie, conventional acid or neutral emulsions.

The -.a silver emulsion of the present invention has a core/shell type structure. The silver halide composition of the core in the above-mentioned core/shell type silver halide grains is Al silver iodide containing 0.5 to 15 mol% silver iodide, and the silver halide composition of the shell is preferably a silver halide having a silver iodide content of less than 0.5 mol.

Preferably, the core is silver iodobromide and the shell is pure silver bromide. In addition, in the core/shell type silver halide of the present invention, the core and shell may contain L mol % or less of silver chloride.

The thickness of the shell in the core/shell type silver halide emulsion of the present invention is preferably L to 10 times larger than the diameter of the silver halide grains, and if the thickness is greater than this, the graininess and sensitivity will be poor. , if the value is F or higher, the sensitivity is inferior.

In the core/shell type emulsion of the present invention, the boundary between the core and the shell does not necessarily have to be clear, and the composition of silver halide in the core may be uniform or unevenly distributed. .

The photographic speed of the emulsions of the present invention is at least approximately 1.5 times higher than that of conventional AgX
The sensitizing effect is extremely large compared to the difference in photographic sensitivity (approximately 1.2 times) caused by the presence or absence of a shell in an acidic method or a neutral method that does not contain a solvent. This sensitizing effect far exceeded the expectations of researchers in the photographic industry and was completely surprising.

Width of grain size distribution of silver halide contained in the monodisperse silver halide emulsion according to the present invention L1 Coefficient of variation C expressed by the relational expression (standard deviation/average grain size) x LOO = cV
When expressed as (2), it should have monodispersity with a Cv of 20 mm or less, and preferably a Cv of 15 mm or less.

Note that the grain size is the diameter of a circumscribed circle in an electron micrograph of a silver halide grain.

The monodisperse silver halide grains of the present invention can be obtained by adding a water-soluble silver salt solution and a water-soluble halide solution by a double jet method while controlling pAg and pH. Further, for highly monodisperse silver halide emulsions, the method described in JP-A-54-48521 can be applied. A preferred embodiment of the method is a method in which an aqueous potassium-gelatin solution and an aqueous ammoniacal silver nitrate solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. Manufacture. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc.

The vehicle used in the emulsion of the present invention is preferably gelatin (including ossein gelatin, etc.), but other hydrophilic comids include gelatin derivatives, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as 7-a-z sulfates, sugar derivatives such as alginate, starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, It includes a wide variety of synthetic hydrophilic polymeric materials such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Silver halide solvents used in the present invention include (a) U.S. Pat. Nos. 3,271,157 and 3,531,28;
No. 9, JG3.574.62 S No. 1a*, 0
Organic thioethers described in 8.1019/1982 and 158917/1983, (b) JP-A-53/1983
-82408, 55-77737 and 55-2
Thiourea derivatives described in No. 9829 publications, etc., (C
) Agx solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, (d) t￥f JP-A-54-1007
Imidazoles described in Japanese Patent Publication No. 17, (e) sulfates, (f) thiocyanates, (g) ammonia, (hydroxyalkyl-substituted ethylene diamines described in Japanese Patent Application Laid-Open No. 196228/1983), ( i) Unexamined Japanese Patent Publication No. 5
Examples include substituted mercaptotetrazoles described in JP 7-202531.

Next, specific examples of these silver halide solvents (a) to (i) will be given.

HO(CH2)2S (CH2)2S (CH2)
20HCH2-NHCO-CH2CH2CH3 CH2-8-CH2CH2SC2H5 CH2-NHCO-CH2CH2CH3CH2-8-C
H2CH2SCH2CH2COOH5 CH2CH2SO3K CH5CH
3 (e) K 2 S O3 (f) NHヰSCN, KSCN<
g) NHuOH OHOH H3 When the silver halide of the present invention is arsenic, in the production of silver iodobromide, the addition of iodide salt is carried out by adding an aqueous solution of a mixture of bromide salt and iodide salt. . Alternatively, the odorous salt and the iodine salt may be added simultaneously as separate aqueous solutions. Further, the iodide salt may be added as a suspension of silver iodide microcrystals.

A typical example of a water-soluble silver salt solution used in the present invention, for example, a silver salt aqueous solution is a silver nitrate aqueous solution. Typical examples of water-soluble halide solutions used in the present invention, such as aqueous salt solutions, include potassium bromide, sodium bromide, hypotassium iodide, sodium iodide, and ammonium bromide.

The silver halide grains in the emulsion of the present invention are cubic, 8
It may be of any crystal habit such as hedron, tetrahedron or twin, but particularly preferred are cubic, octahedral,
It is a normal crystal such as a tetradecahedron.

The average grain size of the silver halide grains in the silver halide emulsion according to the present invention is preferably O0L to 4μ, more preferably
//i0.2-2μ.

The photosensitive silver locnide emulsion of the present invention may be doped with various metal salts or metal complex salts during the formation of the silver dunide precipitate, during grain growth, or after the completion of grain growth. For example, gold, platinum, radium, iridium,
Lonrum, Bismuth, Cad.

Metal salts or complex salts such as aluminum, copper, etc. and combinations thereof can be applied.

Incidentally, reduction sensitization in the present invention can be carried out at any time until the end of grain growth and solvent treatment.

When producing the emulsion of the present invention, a noodle washing method, a dialysis method, or a coagulation precipitation method, which are commonly used in general emulsions, can be used as appropriate for desalting.

When producing the emulsion of the present invention, various chemical sensitization methods that are applied to general emulsions can be applied. Namely, activated gelatin, water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt , noble metal sensitizers such as water-soluble rhodium salts and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; Chemical sensitization can be carried out either alone or in combination. Particularly preferred chemical sensitization methods include using a sulfur sensitizer or a selenium sensitizer, and a combination of a sulfur sensitizer and/or a selenium sensitizer with a gold salt. Examples include combinations of

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range. There are particular limitations on the optical sensitization method for the emulsions of the present invention. For example, optical sensitization can be carried out using an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, or a trimethine dye, or an optical sensitizer such as a merocyanine dye (for example, supercolor sensitization). .

These techniques are described in U.S. Patent No. 2,688,545.
No. 2.91.2,329, No. 3,397.0
No. 60, No. 3,615,635, No. 3,628,
954, British Patent No. 1,195,302, British Patent No. 1,
242.588, OLS No. 1,293,862, West German Patent (OLS) No. 2,030,326, OLS No. 2.121.7
No. 80, Special Publication No. 43-4936, No. 44-14030
No., b Z HiF, M. Hamer, “The Fist of Cyanine Die and Relate Compounder (T
heCyanine Dye and Re1ated
Compounds and C, T, H6 James, “The Theory of the Photographic Process Force Etation”
ry of the PhotographicPro
cess Forth Edition) L 94
It is also described on pages 1 to 234. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the light-sensitive material to which the emulsion of the present invention is applied.

The monodisperse silver halide emulsion of the present invention can be used as is with its grain size distribution, or it can be used by blending two or more monodisperse emulsions with different average grain sizes at any time after grain formation. It may be used by blending to obtain a gradation of . However, it also includes those containing silver halide grains other than those of the present invention as long as they do not impede the effects of the present invention.

The emulsion of the present invention can contain various commonly used additives depending on the purpose. Examples of these additives include stabilizers such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds, and antifouling agents: aldehyde-based, aziridine-based, inoxazole-based, vinyl sulfone series,
Hardening agents such as acryloyl, carbonimide, maleimide, methanesulfonic acid ester, and triazine:
Development accelerators such as benzyl alcohol and polyoxyethylene-based compounds; Chroman-based, Claman-based, Bisun-e/-
lubricants such as waxes, glycerides of higher fatty acids, higher alcohol esters of higher fatty acids, and the like. In addition, anionic, cationic, and nonionic surfactants are used as coating aids, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used. As antistatic agents, acetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, styrene-
An alkali salt of a reaction product of maleic anhydride copolymer and p-aminobenzenesulfonic acid is effective. Cloaking agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers with other ethylene group-containing monomers such as acrylic esters and vinyl esters. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-maleic acid copolymer, alkyl vinyl ether-maleic acid copolymer, and the like.

The support for the photosensitive material prepared using the emulsion of the present invention prepared as described above may be any known support, such as baryta paper, polyethylene-coated paper, polyethylene
Pyrene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acecool, polypropylene, polyester films such as lt [polyethylene terephthalate, polystyrene, etc.] are used, and these supports may be used as appropriate depending on the purpose of use of each photosensitive material. selected. These supports may be subjected to undercoat processing if necessary.

The emulsion of the present invention can be effectively applied to photosensitive materials for various uses such as general black and white, X-ray, color, infrared, micro, silver dye bleaching, reversal, and diffusion transfer. I can do it. Among these, it is particularly effective for color applications to which color development is applied.

At this time, it may be applied to any of the red-sensitive, green-sensitive, and blue-sensitive emulsion layers, and each emulsion layer may be applied to high-sensitivity, low-sensitivity,
Alternatively, when the coating is applied separately to layers having two or more sensitivity differences such as high, medium, and low sensitivities, it may be applied to any layer.

In addition, in order to apply the emulsion of the present invention to a color photosensitive material, the emulsion of the present invention adjusted to have red sensitivity, green sensitivity, and blue sensitivity may be combined with cyan, magenta, and yellow couplers. The method and material used for the light-sensitive material may be used for exposing the photosensitive material to the light, and a known open-chain ketomethylene coupler can be used as the yellow coupler.

Among these, benzoylacetanilide-based and hibaloylacetanilide-based compounds are useful.

As magenta couplers, pyrazolone compounds, indacylon compounds, and cyanoacetyl compounds can be used, and as cyan couplers, phenol compounds, naphthol compounds, etc. can be used.

So-called DIR compounds can be used in the emulsion of the present invention. Examples of the DiR compound include compounds that couple with oxidized color developing agents to form dyes, such as those described in U.S. Pat. Nos. 3,148,062 and 3,227,554. Compounds that release development inhibitors (D IR couplers), or U.S. Pat.
Compounds (DIR substances) that release development inhibitors and do not form dyes upon coupling with oxidized forms of color developing agents, such as those described in No. 32,345, are known.

This DIR coupler and DIRIR substance are collectively referred to as a DIR compound.

A feature of these DIR compounds is that they react with the oxidized form of the color developing agent to release the development inhibitor directly from the coupling site.

In addition, JP-A-54-145135 discloses a DIR compound that reacts with the acid 16 form of a color developing agent to release all of the development inhibitor through an intramolecular nucleophilic substitution reaction. 1
Publication No. 14946 describes a DIRfL compound that indirectly releases an inhibitor by electron transfer along a conjugated chain, and any of them can be used in the present invention.

Next, specific examples of DIR couplers that can be used in the present invention will be given.

Below margin N=N CH2CHOH (n-43 2H5 2H5 (D-1,1,3 OR CD-1,2] CD-14] OOH [D-17] CD-18) [D -19] N=N books A light-sensitive material made using the emulsion of the invention may have any conventionally known layer structure.After exposure, this light-sensitive material can be developed by a commonly used known method. .

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, aminobenzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides, iodides, and the like.

Further, when the light-sensitive material is for color use, 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 and white negative developer and then exposed to white light, or
It is treated in a bath containing a fogging agent, and then color developed in 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, typical methods include: after color development;
A method in which a bleach-fixing process is carried out, followed by further washing and stabilization treatment if necessary, or a method in which bleaching and fixing are carried out separately after color development, and further washing and stabilization treatment are carried out if necessary [Effects of the Invention] The present invention According to the method, it is possible to improve graininess and sharpness with high sensitivity, and to suppress the occurrence of scabbing, while eliminating the presence or absence of shells in conventional acidic or neutral methods that do not contain AgX solvents. This brings about a remarkable increase in sensitivity compared to the difference in photographic sensitivity that results.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example-1 A I, B 1-(11, f2) and (
3) Five types of solutions of C1 were prepared. Using these, in the following operation, grains having a core with a silver iodide content of 7 mol and a shell of pure silver bromide with an average diameter of 0. A core/shell type monodisperse cubic emulsion of the present invention was prepared using LSI and an average shell thickness of 0.0075 μm.

[Solution Al] rOssein gelatin 17g Table-L [Solution C1] Solution B 1-(1) and solution C1 were added to solution A1 stirred at 40°C by double jet method for 10 minutes until solution 331 disappeared. Then, add solution B1-(3) and solution C1 using the double jet method! ,
The shell was grown by adding for 110 minutes. The pH during growth was continuously varied from 8.5 to 8.0 using acetic acid, and the pAg was adjusted to 9.65 using potassium bromide solution.
It was changed continuously from [0,4]. After the particles were formed, they were desalinated and washed with water in a conventional manner.

This emulsion is called fE m-tl). When the silver halogenide grains in Em-tlJ were examined by electron microscopy, the grain size distribution was found to be a 13% cubic emulsion.

Next, the same operation as Em-[1) is performed, but solution B1-
A non-core/shell type comparative emulsion E m -(2)k was prepared instead of (3) for use in Solution 1B1-42+. When the silver halide grains in this emulsion were examined using an electron microscope, it was found to be a cubic emulsion with a grain size distribution of 13%''''C.

Next, A2, B2-dll shown below, (2),
Seven types of solutions (3) and (4), C2-fil, and (2) were prepared, and using these, the core with a silver iodide content of 7 mol and pure silver bromide were prepared using the following operations. Average grain size 0.15μ, average shell thickness 0.0075
Comparative core/shell type emulsion Em grown by acidic method of μ
-I made (3).

[Solution A2] Margin table below -2 Table-3 Solution A20 pH stirred at 45℃ was diluted with nitric acid to 2.0
Solution B 2-+13 and solution C2-+1) were added in 10 minutes until all of the solution B 2-flJ was used up, and then solution B 2-(2) and solution C2- (2) Solution B2 obtained by 'e double jet method
Add solution B 2-(4) and solution C2-(2) to solution B 2-(4) in 10 minutes using the double entrant method until 2-(2) is used up. did.

During the addition, the pH was maintained at 2.00 with nitric acid, and the pAg was maintained at 8.2 with potassium bromide solution. After the particles were formed, they were desalinated and washed with water in a conventional manner.

When the silver halide grains in E m 7 (31) produced in this way were examined with an electron microscope, the grain size distribution was 1.
12 cubic emulsions.

Next, E m -(same operation as in 31, but solution B2
-(2) and B 2-(41) solution B 2-(3
Comparative emulsion E using non-core/shell type acidic method using Emulsion E
I made m-(4). The size distribution and shape of the silver halide grains in Em-(41) were the same as El-(3).

Next, Em-
(A comparison emulsion of monodisperse core/shell bottles Em-(51) was prepared using the neutral method using the same procedure as in Example 31. Em-(51)
Silver halide grains in 1 - When examined with an electron microscope, the average grain size was 0.15μ, and the grain size distribution was ttg.
It was a cubic emulsion.

Next, except for keeping the pH at 5.80 during particle formation, E
A non-core/shell type monodisperse comparative emulsion B m-(61k was prepared using the neutral method using the same procedure as m-f4). Em
- Silver halide grains in (6) were examined with an electron microscope and found to have an average grain size of 0.15μ and a grain size distribution of 11
It was coated with a cubic emulsion.

Next, Em-(1) to E adjusted to pAg8.2 at 40℃
Ammonium thiocyanate aqueous solution, chloroauric acid tetrahydrate aqueous solution, and sodium thiosulfate dihydrate aqueous solution were added to m-(61, and chemically aged at 55°C by a conventional method. After completion of aging, these six types Methanol solutions of two types of sensitizing dyes (11 and (2)) were added to the emulsion so that the amount of dye per mole of AgXL was 15 to wi, and 46
Stirring was continued for LO minutes at °C. After this, after the end 4-
and droxy-6-methyl-L, 3.3aj7-thitraazaindene and phenylmercaptotetrazole.

As a cyan coupler, [- and doxy-N-(4-(
2,4-9-t-amylphenoxy)butyl]-2-naphthamide 1 O, 6 g, and ethyl acetate 30 tn1. This mixture was dissolved in 15 m/ml of this alcoholanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and mixed with 200 m/ml of a 10% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 m/ml of a 5% aqueous gelatin solution, and emulsified and dispersed in a colloid mill. After that, this dispersion liquid k E m −(υ〜(6)
0400 g was added to the triacetate base having an antihalation layer so that the amount of silver was 15 mg/di, and dried to prepare samples L to 6.

Sensitizing dye (1): Anhydro 5.5'-9chloro-3,3'-cisulfopyl-9-ethyl-thiacarbocyanine hydroxide, salt sensitizing dye (2): Anhydro 9-ethyl- 3,31-di(3-sulfob avir) 4. ．． 5,4',5'-y-benzothiacarbocyanine hydroxide triethylamine salt 6 above
Samples of various types were exposed to wedge light, and color development was performed at 38° C. for 2 minutes using a color developer having the composition shown below, followed by bleaching and fixing, followed by washing with water.

Exposure was carried out using a light source with a color temperature of 5400 DEG through the entire Toshiba glass filter Y-48.

(Color developing solution composition) The photographic properties of the obtained color images were measured and the obtained results are shown in Table 4. Note that the sensitivity is expressed as a relative sensitivity with the sensitivity of sample NILL as LOO.

Table 4 As can be seen from Table 4, the silver oxide emulsion according to the present invention has higher image quality than emulsions of the same size made by the conventional acidic method or neutral method that do not contain AgX solvent. It was shown that the sensitivity was significantly high by suppressing the occurrence of fog, and the sensitization efficiency was also high when a core/shell structure was used.

Patent Applicant: Konishiroku Photo Industry Co., Ltd. Procedural Amendment (own ship May 1980 IS) Commissioner of the Patent Office Kazuo Wakasugi 1 Description of the case 1980 Patent Application No. 62126 2 Name of the invention Silver halide emulsion 3 Relationship with the case of the person making the amendment Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent 105 5 Date of notice of reasons for refusal (voluntary) 6 Contents of the number of inventions increased by amendment (patent application) (Sho 58-+12126) The specification is amended as follows.

1. In the first line of page 85, the phrase "other than halides" is corrected to "contains relatively few halides."

2. On page 15, lines 18 to 20, it says, “According to the present invention...
・It is. ” will be deleted.

3 Correct the structural formula (D-17) on page 29 as follows.

N=N 4 In structural formula CD-18) on page 30, 5 Structural formula (D-18) on page 30 is corrected as follows.

Record u that's all

Claims (1)

[Claims] A solution of a water-soluble silver salt and a solution of a water-soluble halide are allowed to react in the presence of a silver halide solvent to grow seed crystals consisting essentially of silver halide.
A halogen fullS silver emulsion characterized by containing core/shell type silver halide grains of 5 μm or less.