JPH0769585B2 - 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, and silver chloroiodobromide having a high variable silver content.

(Prior Art) In the photographic industry in recent years, there has been a strong demand for shortening access time, 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 sharpness, graininess, color sensitization efficiency with sensitizing dyes, and covering power, so-called tabular grains whose grain size is 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 or less. The method of US Pat. No. 4,399,215, in which the particles are formed with ammonia while maintaining the pH in the range of 10 to 10 and the pH in the range of 8 to 10, and the particles are prepared in the presence of aminoazaindene and a peptizer having a thioether bond. Only the method of US Pat. No. 4,400,463 for forming is known.

The method using ammonia, however, further increases the solubility of high-solubility high-silver chloride grains, so that it is often used as a sensitive material for rapid processing, and it is difficult to form an emulsion having a relatively small grain size 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 copolymer having good reproducibility because the peptizer is a synthetic polymer, and the polymerization initiator contains photographically harmful impurities, and is also removed. There was a drawback that the salt 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.

Further, the tabular grain is a grain having a twin plane in the grain and an outer surface being a (111) plane, but does not have a twin plane and is a normal crystal and has a (111) plane on the outer surface. The preparation of octahedral to tetrahedral high silver chloride grains with faces is only known in a few documents.

Specifically, Claes et al .; The Journal of Photographic Sc
ience 21, 39 (1973), and Wyrsch; International Cong
Ress 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 compound, compounds such as adenine are compounds that adsorb strongly 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, the tabular grains having the (111) plane newly generated stably on the outer surface and having the tetrahedral or octahedral regular grains or twin grains within the grain It was desired to develop a new preparation method for

(Problems to be Solved by the Invention) The first object of the present invention is to prepare 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. A second object of the present invention is to provide a method for producing a tabular silver halide emulsion having a high silver chloride content by using a compound having a low molecular weight and a low cost which is easy to synthesize. The third object of the present invention is to provide a method for producing a high-silver chloride emulsion having a large number of normal crystal grains of tetrahedron to octahedron composed of (111) faces in the acidic region which is free from pollution problems and is easy to suppress fogging. That is.

(Means for Solving the Problems) As a result of earnest studies, the present inventors have conducted particle formation in the presence of at least one thione compound represented by the following general formula (I) to obtain at least 50 High-silver chloride grains having a chloride content of not less than mol%, and octahedral to decahedron having (111) faces on the outer surface and normal crystal grains or tabular grains are used at the initial stage of grain formation (so-called (At the time of nucleation)
It was found that the above objects can be achieved by easily adjusting the chloride concentration of the above.

X represents a sulfur atom or an oxygen atom, and preferably a sulfur atom.

Q represents an atomic group necessary for completing a 5- or 6-membered heterocycle, for example, a thiazolidine-2-thione ring,
4-thiazoline-2-thione ring, 1,3,4-thiadiazoline-2-thione ring, benzthiazoline-2-thione ring,
Examples thereof include a benzoxazoline-2-thione ring.

R ₀ is an alkyl group (eg, methyl, ethyl, propyl, butyl, octyl), an alkenyl group (eg, allyl), an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl), or a heterocyclic residue. Represents a group (eg, pyridyl).

The heterocycle formed by Q and R ₀ may be unsubstituted or further substituted.

As the substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl group,
Sulfonamide group, amide group, acyl group, sulfamoyl group, carbamoyl group, ureido group, alkoxycarbonylamino group, allyloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonylthio group, alkylcarbonylthio group, aryl It can be appropriately selected from carbonylthio group, cyano group, hydroxy group, mercapto group, carboxy group, sulfo group, nitro group, amino group, alkylthio group, arylthio group, heterocyclic residue and the like.

Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

The emulsion production method in which the compound represented by formula (I) is used as a silver halide solvent at the time of grain formation is described in JP-B-60-11.
No. 341, which relates to a method for producing a silver bromide or silver iodobromide emulsion, but does not refer to a method for producing a silver halide emulsion having a high silver chloride content.

Furthermore, there is no description of any technique for controlling the crystal habit of high silver chloride grains using these compounds.

The method for producing the compound of the present invention can be synthesized from the literatures exemplified or cited in JP-B-60-11341.

The compound of formula (I) of the present invention is disclosed in Japanese Patent Application No. 61-146599.
No. 61-186481 describes that it can be used as a silver halide solvent in the production of a high silver chloride emulsion such as the present invention. It does not suggest that it can be prepared.

Further, the compound of the general formula (I) may be included in the compound disclosed in Japanese Patent Application No. 61-146599 in terms of text, but in the present invention, a thione group is essential, while Japanese Patent Application No. 61-146599. The issue does not disclose it at all.

The addition amount of the compound represented by the general formula (I) of the present invention is
It can be used in the range of 2 × 10 ^-5 mol to 3 × 10 ^-1 mol per mol of silver halide, and 2 × 10 ^-4 mol to 3 × 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. It is preferable that at least a part of them is present from the initial stage of particle formation.

The normal crystal (octahedral to tetradecahedral) grains and the tabular grains can be separately produced by using the compound of the present invention by adjusting the chloride concentration at the initial stage of grain formation (so-called nucleation). Specifically, although there are some differences depending on the type of compound and the amount added, the chloride concentration during nucleation is generally 0.5 mol / l or less, preferably 0.2 mol / l or less when normal crystal grains are obtained.
Mol / l or less, more preferably 0.15 mol / l or less, when obtaining tabular grains, 0.05 mol / l or more, preferably
It is 0.1 mol / l or more, more preferably 0.15 mol / l or more.

In any case, the chloride concentration during grain growth is preferably 5 molar concentration or less, and particularly preferably 0.07 to 3 molar concentration.

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 that it is more than mol%. Preferably 70 mol%,
More preferably, it is 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. Quantification of the (111) plane can be carried out from an electron micrograph of silver halide grains formed.

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 volume 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 the distance between two parallel planes constituting tabular silver halide grains. It is represented by.

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.

As the silver halide solvent often used, thiocyanates, thioethers, thioureas and the like can be mentioned, and ammonia can also be used in combination so long as it does not have a bad effect.

For example, thiocyanate (U.S. Pat.
2,448,534, 3,320,069, etc.), thioether compounds (eg, US Pat. Nos. 3,271,157, 3,574,628)
No. 3, No. 3,704, 130, No. 4,297, 439, No. 4,276, 34
No. 7, etc.), thioureas (JP-B-58-51252, JP-A-55)
-77737, U.S. Pat. No. 4,221,863 and the like) amine compounds (for example, JP-A-54-100717) and the like can be used.

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.

During the production of the silver halide grains of the present invention, the addition rate, the amount and the concentration of addition of the silver salt solution (for example, AgNO ₃ aqueous solution) and the halide solution (for example, NaCl aqueous solution), which are added to accelerate the grain growth, are increased. The method 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, JP-A-55-158124, JP-A-5
8-113927, 58-113928, 58-111934, 58
-111936 etc. can be referred to.

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, 2,521,925), 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 projected area of all silver halide grains in the emulsion. It 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.

The emulsions of this invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
Any of the nuclei 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 Nuclei of aromatic hydrocarbon ring fused to nuclei of, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus,
Benzoxazole nucleus, naphthoxazole 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 pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
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 RESEARCH 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.
Normally, it is performed after the completion of chemical sensitization and before the application, but U.S. Pat.Nos. 3,628,969 and 4,2
As described in JP-A No. 58-113,928, it is also possible to add spectral sensitization at the same time as the chemical sensitizer as described in JP-A No. 58-113,928. It can be carried out in advance, or it can be added before the completion of silver halide grain precipitation to start 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 mol to 8 mol per mol of silver halide.
While × can be used in 10 ^-3 molar in the case of more preferable silver halide grain size 0.2~1.2μm about 5 × 10 ^-5 mol to 2 × 10 ^-3 mol and 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 1764
3 (RD17643) and 187 items 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), mercapuipyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3, 3a, 7) Tetraazaindenes), 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 ions. Further, a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. It may also contain a colorless DIR coupling compound which is colorless in the product of the coupling reaction and which releases a development inhibitor.

For example, as a magenta coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, a pyrazolotetrazole coupler,
There are cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (eg, 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 couplers and the like can be used in combination of 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 to two or more different layers.

Examples of anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Representative examples thereof include ethers, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Also,
A metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-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. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxydiethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 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)
226-229, U.S. Patent Nos. 2,193,015 and 2,592,364.
Nos. 48-64933, and the like.

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 solution 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 (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, an organic complex salt of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or a quenching agent. Complex salts of organic acids such as acids, tartaric acid and malic acid; persulfates, permanganates, nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a 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.

(Example) Hereinafter, the present invention will be further described 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.

Emulsions A to G were prepared as follows.

The solution (1) kept at 60 ° C. with pH adjusted to 4.5 with 1 NH ₂ SO ₄ was added to the compound of the present invention as shown in Table 1 with vigorous stirring, and then the solutions (2) and (3) were added. Simultaneously added over 7 minutes.

After a further 10 minutes, the solution (4) and the solution (5) were simultaneously added over 50 minutes to obtain silver chloride emulsions A to G.

Emulsions H to J were added as follows.

The solution (6), which was adjusted to pH 4.5 with 1 NH ₂ SO ₄ and kept at 60 ° C., was added with vigorous stirring as shown in Table 1 and then the solution (2) was added over 7 minutes. .

After a further 10 minutes, solution (4) and solution (5) were simultaneously added over 50 minutes to obtain silver chloride emulsions HJ.

The comparative emulsion (A) prepared without adding the compound of the present invention was cubic, while the emulsions (emulsions B to J) containing the compound included in the present invention were as shown in Table 1 (a). ) To Na
When the amount of Cl is small, tetradecahedral and octahedral particles are
Tabular grains were obtained when the amount of NaCl was high.

Emulsion K is a compound described in Claes et al. And is a sample outside the present invention.

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 (K, L) containing the compound included in the present invention had octahedral or 14-sided grains. Was obtained.

Example 3 With respect to the cubic emulsion A and the tabular emulsion H, the average volume of the volume load was determined by the Coulter counter method. As a result, the emulsion A was 0.27 μm ³ , and the emulsion H (average grain size / grain thickness ratio was about 6.2). Was 0.26 μm ³ . Similarly, the average volumetric load of octahedral emulsions E and K was found to be 0.28 μm ³ . After sedimentation and desalting by a conventional flocculation method, gelatin was added, and then the pH was adjusted to 6.4 at 40 ° C.
Ag was adjusted to 7.5. Both emulsions were optimally chemically sensitized with diphenylthiourea to prepare samples 1 to 3 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 Eastman Kodak Co., Ltd. designated D-76 treatment Measure the density of the treated sample (in the case of color development, insert a green filter) (Measurement) Table 3 shows the obtained photographic performance.

In Comparative Emulsion K, fogging occurred over the entire surface in any of the treatments.

Further, as shown in Table 3, the development of the tabular silver chloride emulsion (Emulsion H) and the octahedral emulsion (Emulsion E) of the present invention is much faster than that of the cubic emulsion (Emulsion A), and it is preferable that the fog is low. The characteristics are shown. Therefore, it is clear that it is preferable as an emulsion for rapid processing.

However, the relative sensitivity 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 In CP-20 processing, it is 3'30 "of sample 1 and in D-76 processing, it is sample 1
7's of each of them are set to 100.

Example 4 After tabular silver chloride grains were formed in the same manner as in the emulsion (H) 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 made of silver chloride, an emulsion (emulsion (N)) optimally chemically sensitized in the same manner as in Example 3 was obtained.

The following compounds were added to emulsions (A), (H) and (N), respectively.

Blue-sensitive sensitizing dye (a) Yellow coupler (b) Color image stabilizer (c) Stabilizer: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene antifoggant: 1-phenyl-5-mercaptotetrazole Hardener: 2,4-dichloro-6-hydroxy-s Sodium triazine coating aid: Sodium dodecylbenzene sulfonate was added in sequence and coated with a gelatin protective layer on a paper support laminated on both sides with polyethylene to give sample (4),
(5) and (6) were obtained.

The sample was exposed under a light wedge and developed according to the following steps to obtain the results shown in Table 4.

However, the relative sensitivity is represented by the relative value of the reciprocal of the exposure amount required to give the density of the fog value + 0.5, and the sample (6)
The 3'30 "is set to 100.

As is clear from Table 5, Emulsion (H) and Emulsion (M) prepared by using the compound of the present invention have a higher sensitivity than Comparative Emulsion (A), 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 ° C Developing 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 (Whitex4 from Sumitomo Chemical Co., Ltd.) 2.0g Add water and 1000cc KOH to pH 10.25 (bleach-fix) Liquid 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 ℃ for 90 seconds EDTA ・ 2Na ・ 2H ₂ O 0.4g Add water to a total volume of 1000 ml (pH 7.0) Example 5 In the same manner as in Example 3, cubic emulsion A, octahedral emulsion E,
Optimal chemically sensitized emulsions were prepared using tabular emulsion H, diphenylthiourea and chloroauric acid, and coating samples 7 to 9 were prepared. The same effect as in Example 3 was confirmed with the emulsion system sensitized with gold and sulfur.

Example 6 An emulsion obtained by chemically sensitizing the emulsion H prepared in Example-1 as in Example 3 was used as each emulsion of Sample-1 of Example-1 described in JP-A-62-215272. 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 The emulsion H 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. 40% or more of the total projected area of silver halide grains is (111)
The method for producing a photographic silver halide emulsion according to the claims.

4. 60% or more of the total projected area of silver halide grains is (111)
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]

FIG. 1 shows the emulsion H of Example 1, FIG. 2 shows the emulsion I of Example 1, FIG. 3 shows the emulsion J of Example 1, and FIG. 4 shows the silver halide crystals contained in emulsion K of Example 2. It is an electron micrograph which shows the structure of a particle. The magnification is 10,000 times in Figs. 1-3, and 5 in Fig. 4.
It is 000 times.

Claims (1)

[Claims] 1. A process for producing a photographic silver halide emulsion containing silver halide grains in which at least 50 mol% is silver chloride and 30% or more of the surface area thereof is a (111) surface. The silver halide grains have the following general formula (I)
A method for producing a photographic silver halide emulsion, wherein grains are formed in the presence of at least one crystal habit controlling agent of the thione compound represented by In the formula, X represents a sulfur atom or an oxygen atom. Q is 5
Represents a group of atoms necessary to complete a 6-membered or 6-membered heterocycle. R ₀ represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic residue.