JPH0687121B2 - Method for producing photographic silver halide emulsion - Google Patents

Description

The present invention relates to a method for producing a photographic silver halide emulsion. In particular, a tetrahedron with (111) faces, an octahedron,
It also relates to a method for producing a photographic silver halide emulsion comprising tabular silver chloride or silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a high silver chloride content.

(Prior Art) In the photographic industry in recent years, shortening access time has been eagerly awaited, and development of a silver halide photographic light-sensitive material suitable for rapid processing has been urgently required.

Increasing the silver chloride content results in increased water solubility, faster development and fixing, and a silver halide suitable for rapid processing.

Silver halide grains having a high silver chloride content (hereinafter referred to as "high silver chloride grains") tend to be cubic grains generally composed of (100) faces, and grains other than cubic grains, specifically (11
1) It is necessary to devise a great deal of effort to obtain regular crystal grains and tabular grains such as octahedrons and tetrahedra with faces.

In order to increase the sensitivity of photographic silver halide emulsions, and to improve the sharpness, graininess, color sensitization efficiency of sensitizing dyes, and covering power, so-called tabular grains having a grain size considerably larger than the grain thickness are used. It is well known to those skilled in the art that, for tabular grains with high silver chloride having a silver chloride content of 50 mol% or more, bromide and iodide are not contained therein, and pAg is 6.5 to. In the range of 10 and
The method of US Pat. No. 4,399,215 in which pH is maintained in the range of 8 to 10 to form particles using ammonia, and US Pat. No. 4400463 in which particles are formed in the presence of aminoazaidene and a peptizer having a thioether bond. And the method disclosed in JP-A-62-218959, which uses a thiourea compound.

The method using ammonia, however, further increases the solubility of high-solubility high-silver chloride grains, and is often used as a photosensitive material for rapid processing, and it is difficult to form an emulsion having a relatively small grain volume of 1 μm ³ or less. And during particle formation
Since the pH inevitably becomes high, the fog of a high silver chloride emulsion which is sensitive to fog is often increased, and the conditions for forming grains are significantly restricted.

In the method using a peptizer having a thioether bond, it is difficult to obtain a reproducible copolymer because the peptizer is a synthetic polymer, or the polymerization initiator contains photographically harmful impurities, and desalting is also performed. There was a drawback that the process became complicated. In addition, there are many drawbacks from an industrial point of view, such as cost increase in order to eliminate these adverse effects.

From the above, in the acidic to neutral range, low cost low molecular weight compounds that are easy to synthesize and easy to purify are simply used in combination with gelatin, which is a general-purpose peptizer, with good reproducibility and flat plate shape. The development of a method for obtaining high silver chloride grains has been strongly desired.

The tabular grains described above are grains having twin planes within the grains and having an outer surface of (111) plane, but they do not have twin planes and are normal crystals and have (111) planes on the outer surface. The preparation of octahedral to tetrahedral high silver chloride grains with faces is only known in a few documents.

Specifically, Claeo et al .; The Journal of Photographic Sc
ience 21:39 (1973) and Wyrsch; International Con
Known for the progress of Photographic Science III-13, 122 (1978).

The former uses compounds such as adenine, dimethylthiourea and thiourea, but no report has been made on the photographic properties of the prepared octahedral grains. However, considering the structural aspects of the compounds, compounds such as adenine are compounds that have a fairly strong adsorption to silver halide.
It is presumed that the compound has an unstable sulfur molecule and easily causes fog.

The latter obtains octahedral silver chloride grains using ammonia and a large amount of cadmium nitrate, and obtains photographic performance similar to that of a cube, but cadmium is not suitable for practical use in terms of pollution. Further, it is not preferable to use ammonia because grains of high silver chloride are apt to cause fog, and it has been desired to prepare octagonal grains of high silver chloride without the problem of pollution without using ammonia.

As described above, in the high silver chloride emulsion, tabular grains having a normal (111) plane on the outer surface and stable tetrahedral or octahedral grains and twin grains within the grain are newly generated. It was desired to develop a new preparation method for

(Object of the invention) The first object of the present invention is to provide a method for producing a silver halide emulsion having (111) having a high silver chloride content on the outer surface, which is suitable for rapid development and has an extremely rapid development. The second object is to provide a method for producing a tabular silver halide emulsion having a high silver emulsion content by using a compound which is easy to synthesize and low in cost, and the third object is to provide: It is an object of the present invention to provide a method for producing a high-silver chloride emulsion having many (11) -faced tetrahedral and octahedral normal crystal grains in the acidic region, which is free from pollution problems and is easy to suppress fogging.

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that at least 50 mol% of particles is formed by forming particles in the presence of at least one compound represented by the following general formula (I) or general formula (II). Even in high silver chloride grains where the above is chloride, (11
1) By adjusting the chloride concentration at the initial stage of grain formation (so-called nucleation) and controlling the addition timing of normal crystal grains and tabular grains with octahedron to tetrahedron having faces. It was found that they can be easily made separately and the above-mentioned object can be achieved.

General formula (I) General formula (II) (A1, A2, A3 and A4 represent a group of non-metal atoms for completing the nitrogen-containing heterocycle, which may be the same or different. B represents a divalent linking group, m represents 0 or 1) R1 and R2 each represent an alkyl group, X represents an anion, n represents 0 or 1, and n is 0 in the case of an inner salt.) The following general formulas (I) and (II) Will be described in more detail.

A1, A2, A3 and A4 represent a group of non-metal atoms for completing the nitrogen-containing heterocycle, which may contain oxygen atom, nitrogen atom and sulfur atom, and the benzene ring may be condensed. The heterocycle composed of A1, A2, A3 and A4 may have a substituent, and each may be the same or different.
Substituents include alkyl groups, aryl groups, aralkyl groups, alkenyl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, sulfo groups, carboxy groups, hydroxy groups, alkoxy groups, aryloxy groups, amide groups. , A sulfamoyl group, a carbamoyl group, a ureido group, an amino group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group and an arylthio group. Preferred examples are A1, A2, A3 and
A4 can be a 5- or 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiozole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, etc.), and a more preferred example is a pyridine ring.

B represents a divalent linking group. The divalent linking group include an alkylene, arylene, alkenylene, -SO ₂ -, - SO
-, -O-, -S-, (R ₃ represents an alkyl group, an aryl group or a hydrogen atom.)
Represents a single or a combination of. Preferred examples of B include alkylene and alkenylene.

R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms.
R ₁ and R ₂ may be the same or different.

The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents listed as the substituents of A1, A2, A3 and A4.

As a preferred example, R ₁ and R ₂ each represent an alkyl group having 4 to 10 carbon atoms. Furthermore, as a preferable example, a substituted or unsubstituted aryl-substituted alkyl group is represented.

X represents an anion. Examples thereof include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate. n represents 0 or 1, and in the case of an inner salt, n is 0.

Specific examples of the compounds represented by formula (I) or formula (II) are listed below, but the present invention is not limited to these compounds.

(Compound example) (Synthesis method of compound) Synthesis of compound (6) To 800 ml of methanol, 100 g of 4,4'-dipyridyl and 190 ml of benzyl bromide were added and heated under reflux for 3 hours. After filtering the reaction solution, 800 ml of isopropyl alcohol was added, and the obtained crystals were collected by filtration to obtain the compound (6).

Yield 386g (90%) Synthesis of compound (12) 1,3-di-4-pyridylpropane 20 in 400ml ethanol
g and 30 ml of benzyl bromide were added, and the mixture was heated and supervised for 2 hours. After filtering the reaction solution, 400 ml of ethyl acetate was added and the obtained crystals were collected by filtration to obtain the compound (12).

Yield 41 g (76%) The addition amount of the compound represented by formula (I) or (II) of the present invention is 2 × 10 ^-5 mol to 1 mol of silver halide.
It can be used in the range of 3 × 10 ^-1 mol, and 2 × 10 ^-4 mol to 1 × 10 ^-1 mol is particularly preferable.

The compound of the present invention may be added so that it is present at any time during grain formation from the nucleus formation of silver halide grains to the end of physical ripening in the production process of silver halide emulsion. In the case of producing tabular grains, it is preferable that at least a part of them is present from the initial stage of grain formation.

In order to separately prepare normal crystal (octahedral to tetradecahedral) grains and tabular grains using the compound of the present invention, the chloride concentration at the initial stage of grain formation (so-called nucleation) is adjusted, and / or the present invention It is possible by selecting the time of addition of the compound.
Specifically, there are some differences depending on the type of compound and the amount added, but it is roughly as follows. That is, (1) In the preparation of tabular grains, the concentration of chloride when the compound of the present invention is present during nucleation is 0.05 mol / l or more, preferably 0.75 mol / l or more, more preferably 0.15 mol / l or more. Is.

The concentration of chloride when the compound of the present invention is present during grain growth is 5 mol / l or less, preferably 0.1 to 2 mol / l.

(2) For the preparation of normal crystal particles, the concentration of chloride when the compound of the present invention is present during nucleation is 0.5 mol / l or less, preferably 0.2 mol / l or less, more preferably 0.1 mol / l or less. Is.

The concentration of chloride when the compound of the present invention is present during grain growth is 5 mol / l or less, preferably 0.07 to 2.0 mol / l.

The temperature during grain formation in the present invention can be used in the range of 10 ° C to 95 ° C, preferably 40 ° C to 90 ° C.

The pH may be any, but a neutral to acidic range is preferable.

The high silver chloride grains of the present invention have a silver chloride content of at least 50.
It means more than mol%. It is preferably 70 mol%, more preferably 90 mol% or more.

The balance consists of silver bromide and / or silver iodide, and the content of silver iodide is preferably 20 mol% or less, more preferably 10 mol% or less. It is particularly desirable that a layer mainly composed of silver bromide or silver iodide is localized near the surface of the grain.

In the case where so-called core / shell type grains may be used, it is preferable that the silver chloride content of the core portion is higher than that of the shell portion. For example, it may be a grain composed of a core portion made of silver chloride and a shell portion made of silver bromide.

The silver halide grain of the present invention has a surface composed of (111) faces and has a surface area of at least 30% or more, preferably 40% or more.
% Or more, and more preferably 60% or more is composed of the (111) plane. The (111) plane can be quantified from the electron micrograph of the formed silver halide grains.

When the silver halide grains of the present invention are normal crystals, the average grain size is not particularly limited, but it is 0.1 µ-5 µ, preferably 0.2 µ.
μ to 3 μ.

When the silver halide grains of the present invention are tabular, the diameter / thickness ratio thereof is preferably 2 or more, more preferably 2 or more and 50 or less, particularly preferably 2 or more and 20 or less, and 3 or more. Most preferred is 10 or less.

Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the tabular silver halide grains have a diameter of 0.3 to 5.0 μm, preferably 0.5 to 3.0 μm.
is μ.

The thickness is 0.4 μm or less, preferably 0.3 μm or less, more preferably 0.2 μm or less. The average volumetric load of the particles is preferably 2 μm ³ or less. Further, it is preferably 1.0 μm ³ or less.

In general, tabular silver halide grains are tabular having two parallel planes, and therefore "thickness" in the present invention means a distance between two parallel planes constituting the tabular silver halide grain. Represented.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse, but monodisperse is more preferable.

The silver halide emulsion of the present invention may be an internal latent image type emulsion or a surface latent image type emulsion.

A silver halide solvent may be used during the production of the silver halide grains of the present invention.

Frequently used silver halide solvents include, for example, thiocyanates (see, for example, US Pat.
Nos. 2,448,534 and 3,320,069), thioether compounds (for example, US Pat. Nos. 3,271,157, and 3,5).
74,628, 3,704,130, 4,297,439, 4,
276,347), thione compounds and thiourea compounds (for example, JP-A-53-144319, JP-A-53-82408, and JP-A-55-7773).
No. 7, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like, and these can be used. Ammonia can also be used as long as it does not have any adverse effect.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist. Particularly, an iridium salt or a rhodium salt is preferable.

Addition speed, addition amount, and addition concentration of a silver salt solution (for example, AgNO ₃ aqueous solution) and a halide solution (for example, NaCl aqueous solution), which is added in order to accelerate grain growth during the production of the silver halide grains of the present invention, The method of increasing the temperature is preferably used.

For these methods see, for example, British Patent No. 1,335,925.
U.S. Pat.Nos. 3,672,900, 3,650,757, and 4,
242,445, JP-A-55-142329, 55-158124, 58-
113927, 58-113928, 58-111934, 58-11193
You can refer to the description of No. 6 etc.

The tabular silver halide grain of the present invention may remain unchemically sensitized but can be chemically sensitized if necessary.

As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, U.S. Pat.Nos. 2,448,060 and 3,320,069) or a sensitization method using a metal such as iridium, platinum, rhodium, and palladium (for example, U.S. Pat. 2,566,245
No. 2,566,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), a selenium sensitizing method using a selenium compound, or a reduction sensitizing method using tin salts, thiourea dioxide, polyamine, etc. US Patent No.
2,487,850, 2,518,698, 2,521,825), or a combination of two or more of these.

In particular, the silver halide grain of the present invention is preferably gold-sensitized or sulfur-sensitized, or a combination thereof.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to the silver halide grains of the present invention.

In the photographic emulsion of the present invention containing high silver chloride grains according to the present invention, the high silver chloride grains have a projected area of 50% or more, preferably 70% or more, particularly preferably 70% or more of the total silver halide grains in the emulsion. Is preferably 90% or more.

When the photographic emulsion of the present invention and other photographic emulsions are mixed and used, the high silver chloride grains according to the present invention are contained in the emulsion after mixing.
It is preferable to use a mixture so that 50% or more of them are present.

When the photographic emulsion of the present invention is mixed with another photographic emulsion, the emulsion to be mixed is preferably a high silver chloride emulsion containing 50 mol% or more of silver chloride.

The emulsions of this invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a dye belonging to the complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these After the aromatic hydrocarbon ring is fused to the nucleus of, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus,
Benzoxadol nucleus, nfutoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

For example, the compounds described in RESERCH DISCLOSURE Item. 17643, page 23, item IV (December 1978) or the compounds described in the cited documents can be used.

The dye may be added to the emulsion at any stage known to be useful in the preparation of the emulsion.
Usually, it is usually carried out after the completion of chemical sensitization and before coating, but U.S. Pat.Nos. 3,628,969 and 4,22.
It is also possible to add spectral sensitization at the same time as chemical sensitizers as described in JP-A-5,666 and to perform chemical sensitization simultaneously with chemical sensitization, as described in JP-A-58-113,928. It can be carried out in advance, or it can be added before the completion of the silver halide grain precipitation to start the spectral sensitization.
Furthermore, it is possible to add these said compounds separately, as taught in U.S. Pat.No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the balance after chemical sensitization. Can be added at any time during the formation of the silver halide grains, including the method taught in US Pat. No. 4,183,756.

The addition amount is 4 × 10 ^-6 to 8 × 10 per mol of silver halide.
^-3 mol can be used, but in the case of a more preferred silver halide grain size of 0.2 to 3 μm, it is about 5 × 10 ⁻⁵ to 2 ×.
^-3 mol is more effective.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials.

Examples of the color photographic light-sensitive material include color paper, color photographic film, color reversal film, and black-and-white photographic light-sensitive material, X-ray film, general photographic film, printing light-sensitive material film, and the like. It can be preferably used for color paper.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure, Volume 176, Item 17
643 (RD17643) and the same volume 187 Item 18716 (RD18716)
Can be referred to.

The description points of various additives in RD17643 and RD18716 are listed below.

Among the additives, antifoggants and stabilizers are azoles (for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles). , Aminotriazoles, etc .; mercapto compounds {eg mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a , 7) Tetrazaindenes), pentaazaindenes, etc.}; Benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule or a polymerized type. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion, and includes a colored coupler having a color-correcting effect, or a coupler (so-called DIR coupler) which releases a development inhibitor upon development. But it's okay. The product of the coupling reaction may be colorless and may also contain a colorless DIR coupling compound which releases a development inhibitor.

For example, as a mazetan coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, a pyrazolotetrazole coupler,
There are cyanoacetylchroman couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), etc.,
Examples of cyan couplers include naphthol couplers and phenol couplers. As cyan couplers, U.S. Pat.Nos. 3772002, 2772162, 3758308, 412
6396, 4334011, 4327173, 3446622, 4
No. 333999, No. 4451559, No. 4427767 and the like phenolic coupler having an ethyl group at the meta position of the phenol nucleus, 2,5-diacylamino-substituted phenolic coupler,
Phenol-based couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, couplers having naphthol substituted with a sulfonamide or an amide at the 5-position, and the like are preferable because of excellent image fastness.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

As the anti-fading agent, hyldoquinones, 6-hydroxychromans, 5-hydroxyclamans, spirochroman, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives,
Typical examples are methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Also, (bissalicylaldoximato) nickel complex and (bis-
A metal complex represented by N, N-dialkyldithiocarbamato) nickel complex can also be used.

Any known method can be used for the photographic processing of the light-sensitive material using the present invention, and a known processing solution can be used. Also, the processing temperature is usually from 18 ℃
It is chosen to be between 50 ° C but may be below 18 ° C or above 50 ° C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied.

The black-and-white developing solution contains known developing agents such as dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol) and the like. They can be used alone or in combination.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, for example, phenylenediamine (for example, 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Menansulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, LFA Messon's "Photograph Processing Processor Chemistry", published by Focal Press (1966)
226 to 229, U.S. Patents 2,193,015 and 2,592,364,
Those described in JP-A-42-64933 may be used.

The developer may also contain a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, a development inhibitor such as bromide, iodide, and an organic antifoggant, or an antifoggant. Can be included. Also, if necessary,
Water softener, preservative such as hydroxylamine, organic solvent such as benzyl alcohol, diethylene glycol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, antifoggants such as sodium boron hydride,
An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, a polycarboxylic acid type chelating agent described in U.S. Pat. No. 4,083,723, and an antioxidant described in West German Publication (OLS) 2,622,950 may be contained.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), copper (II), peracids, quinones, nitroso compounds and the like are used. For example, ferriciyanide, dichromate, organic complex salts of iron (III) or cobalt (III), such as ethylenediamine tetracomplex salt, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanol quaternary acetic acid, or A complex salt of an organic acid such as citric acid, tartaric acid or malic acid; a persulfate salt, a permanganate salt; notrosophenol or the like can be used. Of these, potassium ferricyanide, ethylenediaminetetracomplex iron (III) sodium salt and ethylenediaminetetracomplex iron (III) ammonium salt are particularly useful. The ethylenediaminetetracomplex salt iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives can be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506, JP-B-45-8836, and the thiol compounds described in JP-A-53-65732.
Further, after bleaching or bleaching / fixing treatment, washing treatment may be carried out or only stabilizing bath treatment may be carried out.

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

Example 1 (Preparation of AgCl emulsion) A silver halide emulsion was prepared as follows.

While vigorously stirring the solution (1) kept at 50 ° C,
As shown in the table, each of the compounds of the present invention was added, and then the solution (2) and the solution (3) were simultaneously added over 3 minutes.

Further, the solution (4) and the solution (5) were simultaneously added for 20 minutes to obtain a silver chloride emulsion.

The comparative emulsion (emulsion (A)) prepared without adding the compound included in the present invention was cubic, but the emulsions (emulsion (B) to (H)) added with the compound included in the present invention were cubic. First
As shown in the table, when the amount of NaCl in (a) is small, it is relatively 8
When the tetrahedron or tetradecahedral grains had a large amount of NaCl in (a), tabular grains were obtained.

Example-2 Preparation of emulsion (A) of Example 1 except that the compound included in the present invention was added after the addition of solution (2) and solution (3) in the preparation of emulsion (A) of Example 1. A silver chloride emulsion was obtained in the same manner.

While the emulsion (A) prepared without adding the compound included in the present invention was cubic, the emulsion (I, J) added with the compound included in the present invention had octahedral or 14-sided grains. Was obtained.

Example 3 A cubic emulsion (Emulsion K) was obtained in the same manner as in the preparation of the emulsion A of Example 1 except that the temperature of the solution 1 was kept at 75 ° C. When the average volume of the volume load was determined by the Coulter counter method, Emulsion B (average grain size / grain thickness ratio was about 5.2
Was 0.24 μm ³ and Emulsion K was 0.25 μm ³ . After washing with water by a usual flocculation method, desalting, gelatin was added, and then pH was adjusted to 6.4 and pAg was adjusted to 7.5 at 40 ° C. Both emulsions were optimally chemically sensitized with diphenylthiourea to prepare Samples 1 and 2 below.

The emulsion and protective layer were coated by adding the additives as shown in Table 1 to a triacetyl cellulose film support provided with an undercoat layer.

Table 1 (1) Emulsion layer Emulsion ... Emulsion shown in Table 3 Coupler Stabilizer: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Coating aid: Sodium dodecylbenzenesulfonate tricresylphosphate gelatin (2) Protective layer 2,4-dichloro-6 -Hydroxy-1,3,5-triazine sodium salt gelatin These samples were exposed through a light wedge and then subjected to the following treatments.

Fuji Photo Film Co., Ltd. designated CN-16 treatment 〃 CP-20 treatment Toastman Kodak Co., Ltd. designated D-76 treatment Measure the density of the treated sample (in case of color development, insert green filter) (Measurement) Table 3 shows the obtained photographic performance.

As shown in Table 3, the development of the tabular silver chloride emulsion (Emulsion B) of the present invention is much faster than that of the cubic emulsion (Emulsion K), and the fog is preferable. Therefore, it is apparent that it is preferable as an emulsion for rapid processing.

However, the relative sensitivity shown in Table 3 is expressed as the relative value of the reciprocal of the exposure required to obtain an optical density of fog value +0.2. In CN-16 processing, that of 3'15 "of sample 1 is For CP-20 treatment, that for sample 3'30 "was set to 100, and for D-76 treatment, that of sample 1 7'was set to 100.

Example 4 Emulsion A (cube) of Example 1 has an average grain size of about 0.5 μm.
The average grain size of emulsion C (octahedral grains and tabular grains) was about 0.6 μm.

Washing and desalting in the same manner as in Example 1 and adding gelatin to adjust pH and pA
After adjusting g to 6.4 and 7.5, optimal chemical sensitization was performed with diphenylthiourea and chloroauric acid.

Thereafter, the same additives as in Example 3 were added, and 1-phenyl-5-mercaptotetrazole was further added as an antifoggant, which was coated on a support to obtain Samples 3 and 4.

After exposing these samples through an optical wedge, CN-16 treatment specified by Fuji Photo Film Co., Ltd. (color processing temperature 38 ° C)
The results shown in Table 4 were obtained.

However, the relative sensitivity in Table 4 is expressed as the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value +1.0.
It was set to 100 at 3'15 "development.

As is clear from Table 4, the emulsion of the present invention is preferred as an emulsion for rapid processing as compared with the cubic emulsion (emulsion A).

Example 5 After tabular silver chloride grains were formed in the same manner as in the emulsion (B) of Example 1, 10 ^-2 mol of potassium bromide was added per mol of silver chloride to give an odor in the vicinity of the grain surface. After locally forming a layer of silver chloride, an emulsion (emulsion (L)) which was optimally chemically sensitized in the same manner as in Example 3 was obtained.

The following compounds were added to emulsions (B), (K) and (L), respectively.

Blue-sensitive sensitizing dye (a) Yellow coupler (b) Color image stabilizer (c) Further stabilizers: 4-hydroxy-6-methyl-1,3-, 3a, 7-tetrazaindene antifoggant; 1-phenyl-5-mercaptotetrazole hardener; 2,4-dichloro-6-hydroxy- s-Triazine sodium Coating aid: Sodium dodecylbenzene sulfonate was sequentially added and coated with a gelatin protective layer on a paper support laminated on both sides with polyethylene to prepare a sample (5),
(6) and (7) were obtained.

The sample was exposed under a light wedge and developed according to the following steps to obtain the results shown in Table 5.

However, the relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to give a density of the fog value + 0.5, and that of 3'30 "of sample 7 was set to 100.

As is clear from Table 5, Emulsion (B) and Emulsion (L) prepared using the compound of the present invention have a higher sensitivity than Comparative Emulsion (K), and the development progress is extremely fast, which is suitable for rapid processing. It will be clear that it is a suitable emulsion.

Color developer 33 ℃ Development water 800cc Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N, N-diethylhydroxylamine 4.2g Potassium bromide 0.01g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate 30g N-Ethyl-N- ( β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 4.5g 4,4'-Diaminostilbene type fluorescent whitening agent (White x 4 from Sumitomo Chemical Co., Ltd.) 2.0g Add water and add 1000cc KOH to pH10.25 (bleach Fixer formulation) 35 ℃ 45 seconds Ammonium thiosulfate (54wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (III) (EDTA)] 55g EDTA ・ 2Na 4g glacial acetic acid 8.61g Add water to a total volume of 1000ml (pH 5. 4) (Rinse solution formulation) 35 ℃ 90 seconds EDTA ・ 2Na ・ 2H ₂ O 0.4g Add water to make 1000ml (pH7.0) Example 6 Emulsion B prepared in Example-1 was chemically sensitized as in Example 3 to obtain emulsions, and the emulsions of Sample-1 of Example-1 described in JP-A-62-215272 were used. Was used instead of.

When the obtained sample was processed by the method described in Example 1 of the same publication, the result that the development progress was good was obtained.

Example 7 Emulsion B prepared in Example-1 was optimally chemically sensitized with hypo and chloroauric acid salt, and then the sample (101) in the example described in JP-A-62-954 was used. The sample used in place of each emulsion was prepared.

When processed in the same manner as in the example, a good development progress was shown.

A preferred embodiment of the present invention is as follows.

1. The method for producing a photographic silver halide emulsion according to the claims, characterized in that at least 70 mol% of the total silver halide is chloride.

2. The method for producing a photographic silver halide emulsion according to the claims, characterized in that at least 90 mol% of the total silver halide is chloride.

3. The method for producing a photographic silver halide emulsion according to claim 1, wherein 40% or more of the total surface area of the silver halide grains is the (111) plane.

4. 60% or more of the total surface area of the silver halide grains is the (111) plane, and the method for producing a photographic silver halide emulsion according to the claims.

5. The method for producing a photographic silver halide emulsion according to claim 1, wherein the silver halide grains having (111) faces are tabular grains having a diameter / thickness ratio of 2 or more.

6. The method for producing a photographic silver halide emulsion according to claim 1, wherein the silver halide grains having a (111) plane are octahedral or tetradecahedral grains.

7. The method for producing a photographic silver halide emulsion according to claim 1, wherein the silver halide grains having a (111) plane are composed of a mixture of tabular grains and normal crystal grains.

8. The method according to claim 1, wherein a bromine- or iodine-containing layer is provided in the vicinity of the surface of the (111) plane particles.

9. The method according to claim 1, wherein the grains having the (111) plane are spectrally sensitized with a methine sensitizing dye.

10. The method according to claim 1, wherein the grain composed of the (111) plane is chemically sensitized with a sulfur sensitizer and / or a gold sensitizer.

[Brief description of drawings]

1 and 2 are the emulsion D of Example 1 and Example 2, respectively.
2 is an electron micrograph showing the structure of a silver halide crystal grain contained in Emulsion I of Example 1. The photographing magnification is 12,500 times each.

Claims (1)

[Claims] 1. A method for producing a photographic silver halide emulsion containing silver halide grains comprising at least 50 mol% of silver chloride and 30% or more of its surface area consisting of (111) faces. A method for producing a photographic silver halide emulsion, characterized in that the silver grains are formed in the presence of at least one compound represented by the following general formula (I) or general formula (II). (Claim) General formula (I) General formula (II) (A1, A2, A3 and A4 represent a group of non-metal atoms for completing the nitrogen-containing heterocycle, which may be the same or different. B represents a divalent linking group. M represents 0 or 1) R1 and R2 each represent an alkyl group, X represents an anion, n represents 0 or 1, and n is 0 in the case of an inner salt.)