JPH0232A - Production of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To make possible to produce a silver halide emulsion which has a high silver chloride content and is suitable for a rapid development processing and contins octahedral-tetradecahedral normal crystal particle and tabular particle having the outer surface of crystal face (111) by forming an emulsion particle in the presence of a specified compd. CONSTITUTION:The emulsion particle is formed in the presence of at least one kind of the compd. shown by formula I or II. In the formula, A1-A4 are each a nonmetal atomic group capable of being completed a nitrogen contg. heterocyclic ring, B is a divalent binding group, (m) is 0 or 1, R1 and R2 are each alkyl group, X is an anion, (n) is 0 or 1, when the compd. is an inner complex salt, (n) is 0. Thus, the emulsion which has the high silver chloride content and contains a many normal crystal particle and tabular particle composed of the octahedral-tetradecahedral particles having >=30% of the outer surface of the crystal face (111), is easily formed, even in the case that the emulsion is composed of a particle contg. >=50mol% of the high silver chloride. Accordingly, the silver halide emulsion which is suitable for the rapid development processing and has a very rapid developing speed, is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a photographic silver halide emulsion. In particular, photographic silver halide emulsions consisting of 1411-plane, octahedral, or tabular silver chloride with (111) planes, or silver chlorobromide, silver chloroiodide, or silver chloroiodobromide with a high silver chloride content. The present invention relates to a manufacturing method.

(Prior Art) In recent years, the photographic industry has been eager to shorten access time, and there is an urgent need to develop silver halide photographic materials suitable for rapid processing.

Increasing the silver chloride content increases water solubility, allowing development and fixing to be achieved in a shorter time, resulting in a silver halide suitable for rapid processing.

Halogenated with high silver chloride content! I grains (hereinafter referred to as "high silver chloride grains")) generally tend to be cubic grains consisting of (100) planes, and non-cubic grains, specifically (
111) Considerable efforts are required to obtain normal crystal grains and tabular grains such as octahedrons and tetradecahedrons having faces.

In order to increase the sensitivity of photographic silver halide emulsions, as well as sharpness, graininess, color sensitization efficiency using sensitizing dyes, and covering power, so-called tabular grains, whose grain size is considerably larger than grain thickness, are used. Preferably, it is well known among those skilled in the art that the silver chloride content is 50 mol%.
The above tabular grains with high silver chloride do not contain bromide or ioside, have PAg in the range of 6.5 to 10, and maintain the pH in the range of 8 to 10 using ammonia. The method of US Pat. No. 4,399,215 for forming particles, the method of US Pat. No. 4,400,463 for forming particles in the coexistence of an aminoazaindene and a peptizer having a thioether bond, and the method of JP-A-62-1999 using a thiourea compound. Only No. 218959 is known.

' However, the method using ammonia further increases the solubility of highly soluble silver chloride grains, making it difficult to produce relatively small emulsions with a grain volume of less than lpm, which is often used in rapid-processing sensitizers. In addition, the pH during grain formation inevitably increases, which often increases fog in high-silver chloride emulsions that are sensitive to fog (grain formation conditions are severely restricted). .

In the method using a peptizer having a thioether bond, since the peptizer is a synthetic polymer, it is difficult to obtain a copolymer with good reproducibility, the polymerization initiator contains impurities that are harmful to photography, and the desalting process is difficult. The disadvantage was that it became complicated. In addition, there are many disadvantages from an industrial perspective, such as eliminating these disadvantages (in order to do so, the cost becomes high).

Based on the above, in the acidic to neutral range, simply using a low-cost, low-molecular-weight compound that is easy to synthesize and purify in combination with gelatin, which is a general-purpose peptizer, has good reproducibility (such as There was a strong desire to develop a method for obtaining high silver chloride grains.

The tabular grains mentioned above have twin planes within the grain and the outer surface is (111) plane, but they do not have twin planes and are normal crystals, with (111) planes on the outer surface. A method for preparing octahedral or tetradecahedral high silver chloride grains with ° faces is also described in 2.
It is only known from the literature No. 3.

Specifically, Claeo et al.; The Journal
ofPhotographic Science
21, 39 (1973) and Wyrsch; Ia
ternaLional Coagress of Ph
otographic Science-13,1
22 (1978).

The former uses compounds such as adenine, dimethylthiourea, and thiourea, but the photographic properties of the prepared octahedral particles have not been reported, but considering the structure of the compound, compounds such as adenine is a compound that has a fairly strong adsorption to silver halide, and
It is presumed to be a compound that has unstable sulfur molecules and is likely to cause fogging.

The latter uses ammonia and a large amount of cadmium nitrate to obtain octahedral silver chloride grains, and obtains photographic performance similar to that of cubic grains, but cadmium is completely unsuitable for practical use in terms of pollution, and is highly chlorinated. Since silver particles tend to fog, it is not preferable to use ammonia, and there is no problem with pollution even without the use of asimonia (it was desired to be able to produce ml of high silver chloride octahedral particles).

As described above, in high silver chloride emulsions, (111) planes are newly stably generated on the outer surface, and tabular grains with normal crystal grains such as tetradecahedrons or octahedrons or twin planes within the grains are created. What! [The development of the W method was desired.

(Objects of the Invention) The first object of the present invention is to provide a method for producing a silver halide emulsion having a high silver chloride content (111) on the outer surface, which progresses extremely quickly and is suitable for rapid development processing. The second objective is to provide a method for producing a tabular silver halide emulsion with a high emulsified tin content using a compound that is easy to synthesize and at low cost. It is an object of the present invention to provide a method for producing a high silver chloride emulsion containing many normal crystal grains of tetradecahedron or octahedron consisting of (111) planes in an acidic region that does not cause pollution problems (and easily suppresses fogging).

(Disclosure of the Invention) As a result of extensive studies, the present inventors have found that by forming particles in the presence of at least one type of compound represented by the following general formula (1) or general formula (rl),
Even in high-chloride grains in which more than mol% of chloride is chloride, normal crystal grains and tabular grains such as octahedral to tetradecahedral grains with (111) planes on the outer surface are formed during the initial stage of grain formation (so-called nucleation), as described below. It has been found that the above object can be achieved by easily making different products by adjusting the chloride concentration of ) and the timing of addition.

General formula ([)%Formula% (A1.A2.A3 and A4 represent a group of nonmetallic atoms to complete the nitrogen-containing heterocycle, and each may be the same or different, B is a divalent linking group , m is O
or l, R1゜R2 each represents an alkyl group, X represents an anion, n represents 0 or 1, and n is 0 in the case of an inner salt.) Hereinafter, general formula (1) and (II) will be explained in more detail.

AI, ^2. A3t? and A4 represent a group of nonmetallic atoms for completing a nitrogen-containing heterocycle, and may contain a w1 elementary atom, a nitrogen atom, and a sulfur atom, and a benzene ring may be fused. A2. The heterocycle composed of A3 and A4 may have a substituent (which may be the same or different; examples of the substituent include an alkyl group and an aryl group.

ara/″alkyl group, alkenyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, 7mido group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonyl group,
Examples include a cyano group and a nido-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.

8 represents a divalent linking group; divalent ambiguous groups include alkylene, arylene, alkenylene, -Soffi-,
Preferred examples representing those composed of -SO-, -〇-, -S-, -C-, and -N- (R3 represents an alkyl group, an aryl group, or a hydrogen R3 atom) alone or in combination. , B can be alkylene or alkenylene.

R and R8 represent an alkyl group having 1 to 20 carbon atoms, and R and R2 may be the same or different.

This is the same as the substituents listed above.

As a preferable example, R and R2 each have 4 to 4 carbon atoms.
A more preferred example of 10 alkyl groups is a substituted or unsubstituted aryl R-substituted furkyl group.

X represents an anion, for example, chloride ion, bromide ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, nl! 0
& represents l, and in the case of an inner salt, n is 0.

Specific examples of compounds represented by general formula (1) or general formula (II) are listed below, but the present invention is not limited only to these compounds.

(Compound example) 2 CHs ('';1 SOs・2CHs { )-SOx● 28,・2B- B-28, “2ct” B-2 (4@r″′1 B-2C1・B-28, @2Cj・2(j@Convex-CHRrN ”-S~S~N'NCHtStoneB- 庺-Convex1...2C1 3-CH1-N S 2(4"(》(">20...Ama O △ CHs -N (CHJz N
N CHs ω WCHz OhaN N-CH, -N N 2C1@U? -8m. Hzo□N N-CH*N, ) 2 (4.
g and 190 mj of benzyl bromide were added, and the mixture was heated under reflux for 3 hours. After filtering the reaction solution, add 80% isopropyl alcohol.
0 mj was added, and the obtained crystals were collected by filtration to obtain compound (6).

Yield: 286 g (9G%) Synthesis of Compound (Incorporated) 20 g of 1,3-di-4-pyridylpropane and 30 mj of benzyl bromide were added to 400 ml of etasol, and heated under reflux for 2 hours. After filtering the reaction solution, ethyl acetate was added. 400m
The crystals obtained by adding A were collected by filtration to obtain compound (2).

Yield: 41 g () 6%》 The amount of the compound represented by the general formula <1) or (II) of the present invention can be used in the range of 2XIO-mol to 3XIG-mol per mol of halogenated at, and 2C1
Particular preference is given to 0-mol 1z to IXIO-mol.

The compound of the present invention can be added at any time during grain formation from the time of nucleation of silver halide grains to the end of annular ripening in the production process of silver halide emulsions. However, when tabular grains are produced in an il process, it is preferable that at least a portion of them be present from the beginning of grain formation.

Using the compound of the present invention, normal crystal (octahedral to tetradecahedral)
In order to distinguish between grains and tabular grains, the initial stage of grain formation (
This is possible by adjusting the chloride concentration at the time of nucleation (so-called nucleation) and/or by selecting the timing of addition of the compound (of the present invention).Specifically, there are slight differences depending on the compound Ill and the amount added. (1) When preparing tabular grains, when the compound of the present invention is present during nucleation, the concentration of chloride is O,OS mol/1 or more, preferably 0.07. It is mol/1 or more, more preferably 0.15 mol/1 or more.

Further, when the compound of the present invention is present during grain growth, the concentration of chloride is 5 mol/l or less, preferably 0.1 to 2 mol/11.

{4 For the preparation of normal crystal grains, when the compound of the present invention is present during nucleation, the concentration of chloride is 0.5 mol/l or less, preferably 0.2 mol/l or less, more preferably 0.2 mol/l or less. It is 0.1 mol/l or less.

Further, when the compound of the present invention is present during grain growth, the concentration of chloride is 5 mol/l or less, preferably 0.07 to 2.0 mol/1.

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

9H may be any type, but is preferably in the neutral to acidic range.

The high silver chloride grains of the present invention have a silver chloride content of at least 5
It means 0 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.

The remainder consists of silver bromide and/or silver iodide, and the content of silver iodide is preferably 20 mol% or less, preferably 1G mol% or less. It is particularly desirable that the layer of silver is localized.

In addition, even in the case of so-called core/shell type particles, it is preferable that the silver chloride content in the core part is higher than that in the shell part (for example, if the core part is made of silver chloride and the silver bromide content is The particles may be composed of a shell portion.

The silver halide grains of the present invention have surfaces consisting of (111) planes, and a small amount (at least 30%, preferably at least 40%, more preferably at least 60% of the total surface area) is (l l
1) The (111) plane, which consists of planes, can be quantified from an electron micrograph of the formed halogenated lI particle.

When the silver halide grains of the present invention are normal crystals, the average grain size is not particularly limited, but may be 0. 1x to 5p, preferably 0.2μ to 3μ.

When the silver halide grains of the present invention are tabular, the diameter/thickness ratio 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 preferably it is 1O or less.

The diameter of a silver halide grain herein refers to the diameter of a circle with an area equal to the projected area of the grain. In the present invention, the diameter of a tabular silver halide grain is 0.3 to 5°0μ, preferably (
L is 5 to 3.0μ.

Further, the thickness is o,<am or less, preferably 0.3 pm or less, more preferably 0.2 μm or less.

The average volume of the particle volume load is preferably 2 μm or less,
Furthermore, it is preferably less than 1 Gum.

- At t1, the tabular silver halide grains are tabular with two parallel surfaces, and therefore the "thickness" in the present invention
is expressed as the distance between two parallel planes constituting a tabular silver halide grain.

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 when producing the silver halide grains of the present invention.

Frequently used silver halide solvents include, for example, thiocyanates (e.g., U.S. Pat. No. 2,222,264).
U.S. Patent No. 2,448.534, U.S. Pat. 3.704.130, 4.297.43
No. 9, No. 4,276.347, etc.), thione compounds and thiourea compounds 113 (e.g., JP-A No. 1443-1983), thione compounds and thiourea compounds
No. 19, No. 53-82408, No. 55-77737, etc.), amine compounds (e.g., JP-A-54-10071)
No. 7), etc., and these can be used. Ammonia can also be used as long as it does not cause any adverse effects.

In the process of halide II particle formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may coexist, especially , iridium salts or rhodium salts are preferred.

Silver salt solution (e.g. AgNO, aqueous solution) added to accelerate grain growth during production of silver halide grains of the present invention
Preferably, a method is used in which the addition rate, amount, and concentration of a halide solution (for example, an aqueous N a Cj solution) are increased according to the addition time.

These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3.672.900, U.S. Patent No. 3.
650,757, 4.242.445, JP 55-142329, 55-158124, 5
B-113927, No. 58-113928, No. 5B
The descriptions in No.-111934, No. 5g-111936, etc. can be referred to.

The tabular silver halide grains of the present invention may be left unchemically sensitized, but can be chemically sensitized if necessary.

Chemical sensitization methods include -gold sensitization using so-called gold compound proboscis (for example, U.S. Pat. No. 2.448.060, U.S. Patent No. 3.
320,069) or iridium, platinum, rhodium,
Sensitization method using metals such as palladium (for example, U.S. Patent No. 2
．． No. 448.060, No. 2.566.245, No. 2,
566.263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222.264), a selenium sensitization method using a selenium compound, or reduction sensitization using tin salts, thiourea dioxide, polyamines, etc. (e.g., U.S. Pat. No. 2,487,850, U.S. Pat. No. 2,518.698,
2,521,925), or a combination of two or more of these can be used.

In particular, the silver halide grains of the present invention are preferably gold-sensitized, 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 octaride grains of the present invention.

In the photographic emulsion of the present invention containing high chloride particles according to the present invention, the high silver chloride grains account for at least 50%, preferably 70%, of the projected area of all silver halide grains in the emulsion.
Above, it is particularly preferable that the content is 90% or more.

Even when the photographic emulsion of the present invention and other photographic emulsions are mixed and used, it is preferable to mix them so that 50% or more of the high silver chloride grains according to the present invention are present in the mixed emulsion.

Further, when the photographic emulsion of the present invention and other photographic emulsions are mixed and used, it is more preferable that the emulsion to be mixed is also a high-silver chloride emulsion in which silver chloride accounts for 50 mol % or more.

The emulsion of the present invention may be spectrally sensitized with methine dyes and others. 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 commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxapurine nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, tetrazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these After the aromatic hydrocarbon ring is fused to the nucleus of Imidazole core, quinoline extraction, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes have ketomethylene structures such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic ring nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thioparbyl M nucleus can be used.

For example, RESERCII OISCLOSIIRE
I tea, 17643, page 23, section ■ (1978
(December 2013) or the compounds described in the cited literature can be used.

The dye may be added to the emulsion at any stage of preparation of the emulsion heretofore known to be useful, although it is usually done after the completion of chemical sensitization and before coating. However, as described in U.S. Pat. , as described in JP-A-58-113.928, it can be carried out prior to chemical sensitization, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. . Furthermore, U.S. Pat.
．． It is also possible to add these said compounds separately as taught in No. 225.666, i.e. some of these compounds are added prior to chemical sensitization and the rest after chemical sensitization. Possible and described in U.S. Pat. No. 4.183.
No. 756, or at any time during silver halide grain formation.

The amount added is 4XIO- to 8X per mole of silver halide.
1 G-" moles can be used, but for a more preferred silver halide grain size of 0.2 to 3 um, about 5X1
0-2x-2 mol is more effective for growth.

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

Examples of color photographic materials include color paper, color photographic film, and color reversal film, and black and white photographic materials include X-ray film, -a photographic film, printing sensitive film, etc. It can be particularly preferably used for color paper.

Regarding other additives for the photographic material to which the emulsion of the present invention is applied, there are no particular additives, such as research additives.
Disclosure magazine (Research Discl.
osure) 176t! Item 17643 (RD
17643) and volume 187 item 18716 (R
D18716) can be referred to.

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

1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral enhancer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right Column 4 Brightener Page 24 5 Antifogging Agent Page 24-25 Page 649 Right Column and Stabilizer 6 Light Absorber, 7 Pages 25-26 Page 649 Right Column - Ilter Dyes 650 Left Column Ultraviolet Absorber 7 Anti-staining agent Page 25 right a 650 page left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 651 left column 10 Binder page 26 Same as above 11
Plasticizer, lubricant Page 27 650 Right column 12
Coating aids, pages 26-27 Same as above Surfactant 13 Static prevention page 27 Same as above As antifoggants and stabilizers among the above additives, 7zoles (e.g. benzothiazolium salts, nitroimidazoles, nitro Benzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, pencitotazoles, aminotriazoles, etc.); Mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles) , mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.): thioketo compounds such as oxadorinthione niazaindene II
I (e.g. triazaindenes, tetraazaindene [
(In particular, 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.): Benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be preferably used.

The color coupler is preferably a non-diffusible one that has a hydrophobic group called a ballast group in its molecule, or a polymerized one.The coupler can be either 4-equivalent or 2-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called D-IR coupler). , a colorless DIR coupling compound that releases the development fqIw4 agent.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers,
Cyanoacetyl coumaron coupler, +aF4! J
, etc., and examples of cyan couplers include naphthol couplers and phenol couplers. As cyan couplers, U.S. Patent No. 3772002 and U.S. Patent No. 277216
No. 2, No. 3 Fu No. 58308, No. 4126396,
No. 4334011, No. 4327173, No. 3446
No. 622, No. 4333999, No. 4451559,
No. 4427767, etc. A phenol coupler having an ethyl group at the meta position before the phenol, a 2,5-diacyl amino substituted phenol coupler, a phenylureido group at the 2-position and an acyl 7-mino group at the 5-position. Phenolic Kabra, sulfonamide at the 5th position of naphthol,
Couplers substituted with amide or the like are preferred because they provide excellent image fastness.

In order to satisfy the characteristics required of a photosensitive material, two or more types of the above couplers can be used together in the same layer, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

Antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols such as bisphenols, gN-form of gallic acid, and methylenedioxybenzene. , aminophenonyls,
Typical examples include hindered amines and ethers or esters Wi1 obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also,(
Metal complexes typified by (bissalicylaldoximad)nickel complex and (bis-N,N-dialkyldithiocarbamad)nickel complex can also be used.

For photographic processing of light-sensitive materials using the present invention, any known method can be used, and known processing solutions can be used. Further, the processing temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C. Depending on the purpose, development processing to form a silver image (black and white photographic processing) , or a color photographic process consisting of a development process to form a dye image.

The black and white developer contains known developing agents such as dihydroxybenzene II (e.g. hydroquinone), 3-pyrazolidone (e.g. l-phenyl-3-pyrazolidone), and aminophenols (e.g. k-methyl-p-aminophenol). They can be used alone or in combination.

The color developer consists of an alkaline aqueous solution containing -a and a color developing agent. Color developing agent: Known primary aromatic amine developers, such as phenylene diamine 11 (e.g. 4
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N, N-diethyl J-reaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N-ethyl -N-β-methoxyethylaniline, etc.) can be used.

In addition, I F. A. Meson, “Photographics - Brothecine Chemistry”, published by Focal Press (1
966), pp. 226-229, U.S. Pat. No. 2,193.
No. 015, No. 2,592゜364, Japanese Unexamined Patent Publication No. 48-64
Those described in No. 933 may also be used.

The developer may also contain pH 11 agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants;
Antifoggants and the like can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, 4wL ammonium salts, and amines, dye-forming blurs, and competitors may be added. Fogging agents such as fogler, sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid group chelating agents described in U.S. Pat. No. 4,083°723, West German Publication (OLS)2
, 622.950, etc., may also be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. ft white processing may be performed simultaneously with fixing processing or separately. Examples of bleaching agents include iron (II), cobalt (■), chromium (Vl), w4 (II), etc. Compounds of polyvalent metals, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, complex salts of iron or cobalt, 7-minopolycarbonates such as ethylenediamine tetracomplex, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc. Acids or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitronephenol, etc. can be used. Among these, potassium ferricyanide, sodium ethylenediamine tetracomplex iron(1), and ammonium iron(■) ethylenediamine tetracomplex are useful for 11. Ethylenediamine tetracomplex iron(I) complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions.

Bleach or bleach-fix solutions are described in U.S. Patent 3. o42.52
No. 0, No. 3,241.966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added. Further, after the bleaching or bleaching/fixing treatment, a water washing treatment or a stabilizing bath treatment may be sufficient.

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

Example 1 (Preparation of AgCj emulsion) Silver halide emulsions were prepared as follows.

Solution (1) Inert gelatin 30gN
a CJ (a) g(H2
Add O and make 200cc solution (cloudy NaCj
l (b) Add gH, O
200cc solution (4) A g N Os
Add 9 G gHxO
600cc solution (5) NaC&
Add 42gH and O to 600cc5
While vigorously stirring the solution (1) kept at 0°C,
Each of the compounds of the present invention was added as shown in the table, and then solution (2) and solution (31) were added simultaneously over a period of 3 minutes.

Furthermore, solution (4) and solution (l) were added simultaneously over 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 emulsion (emulsion (B) to (H)) prepared with the compound included in the present invention was cubic. 1st
As shown in the table, when the amount of NaCl in (a) is small, relatively octahedral and tetradecahedral particles are (≧) NaCjii
When the amount was large, tabular grains were obtained.

Table 1 A Ilg 45g □ Cube 8
fig 4-5g Nl-110.5g Planar grain C5g3.0g ” ” 811
One particle h￥Ttm;x+D Iig 4.5g
k-50, 3g Tabular grain 10 excitation E 5g
3.0g ” ” Octahedral particle and right F l1g 4.5g tk-7-jl, 3
g 8-stroke tug of war rF and Ft&am+G l1g
4.5g tk-80, 3g 8-sided elongation) T and flat W
afi+Hfig 4-5g llk-120-3
g 平葡I埒子ト8i111fa+Example-2 Example 1 except that the compound included in the present invention was added after the addition of the solution (Lito solution (3)) in the emulsion (A) of Example 1. A silver chloride emulsion was obtained in the same manner as in the preparation of Emulsion (A) in No. 1.

Emulsion (A), which is included in the present invention and is illumination without adding the φ compound, has cubic shapes, whereas emulsion (1, J) in which the compound included in the present invention is added has octahedral or tetradecahedral grains. was gotten.

Table 2 A □ Cubic particles I Nm-110,5g Octahedral particles (Figure 2) J
tk-240, 58-hedral grains and 14-hedral grains Example 3 A cubic emulsion (emulsion layer) was obtained in the same manner as in Example 1 except that the temperature of Solution 1 was kept at 75°C.

When the average volume of the volume load was determined by the Coulter counter method, it was found that the emulsion layer (average grain size/grain thickness ratio is approximately 5
．． 2) was 0.24 am''-, and the emulsion layer was O
It was -25pm3. After washing with water and desalting using the usual flocculagecon method, gelatin was added, and the pH was adjusted to 6.4 and pAg to 7.5 at 40°C. Both emulsions were optimally chemically sensitized using diphenylthiourea to prepare the following samples 1 and 2.

Additives as shown in Table 1 were added to the triacetylcellulose film support on which the subbing layer was provided, and the emulsion and protective layer were coated.

Table 1 (1) Emulsion layer 0 Emulsion... - Emulsion 0 shown in Table 3 Coupler zHs Convex L +Cs OCHCON HβCs H++
eONIIrλ\N to C〒”-cCj 0 Stabilizer: 4-hydroxy-6-methyl-1゜3.3
a, 7-tetrazaindene aim fabric aid sodium nidodecylbenzenesulfonate 0 tricresyl phosphate 0 gelatin (2) protective layer 02.4-dichloro-6-hydroxy-1゜3.5-}
Lyazine Sodium Salt 0 Gelatin These samples were pre-exposed to light and then subjected to the following treatments.

0 Fuji photo film machine specified CN-16 processing■
Table 3 shows the photographic performance obtained by measuring the density of the sample treated with CF-20 (Toastman Kodak) and D-76 (in the case of color development, a green filter was used).

Table 3 138℃ l 315 l 100 (0,20)11
05 (0,25)1133℃ l 3301000
(0,11) 1100 (0,12) ID-76 development
330" 100 6020℃?
l OO((LO6) 86 (0,06) 3rd
As shown in the table, the development progress of the tabular silver chloride emulsion (emulsion B) of the present invention is much faster than that of the cubic emulsion (emulsion K), and it also exhibits favorable characteristics such as low fog, and is therefore preferred as an emulsion for rapid processing. That is clear.

However, the relative sensitivity in Table 3 is expressed as the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2.
For the 20 treatment, that of sample 1, 330, and for the D-76 treatment, that of sample 1, 7', were each 10.0.

Example 4 Emulsion A (cubic) average grain size of Example 1 is approximately 0.5
The average grain size of Emulsion C (octahedral grains and tabular grains) was about 0.6μ.

Precipitate in water and desalinate in the same manner as in Example 1, add gelatin, and adjust the pH to %.
After adjusting p and Ag to 6.4 and 7.5, optimal chemical sensitization was performed using diphenylthiourea and chloroauric acid.

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

After exposing these samples to light through a preemptive method, they were subjected to Fuji Photo Film-specified CN-16 processing (color processing temperature 38°C).
) and obtained the results shown in Table 4.

However, the relative sensitivity in Table 4 is expressed as a relative value of the reciprocal of the exposure amount necessary to obtain an optical density of fog value + l 0, and in each case, the value at the time of 3'15 development was set as 100.

Table 4 11 Relative sensitivity I11
Sample 3 (invention) I Sample 4 (comparative example) 1 Development time 30 4.1 30115"
74 58As is clear from Table 4,
It is clear that the emulsion of the present invention is preferred as an emulsion for rapid processing compared to the cubic emulsion (emulsion A).

Example 5 In the same manner as emulsion (B) of Example 1, a tabular mr chloride
After i-element formation, 10-w mol of potassium bromide per 1 ml of chloride was added to locally form a layer of silver bromochloride near the surface of the particles, and then chemical amplification was carried out in the same manner as in Example 3. An emulsion (emulsion (L)) with optimal texture 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) (2) Blue-sensitive sensitizing dye (b) Yellow Kabra °3)! CCOC°°′Sakae□. Just in case.

0 COCHHu(t)Cj\hI tHs f13 Furthermore, stabilizer: 4-hydroxy-6-methyl-1,3°3a,
7-tetrazaindene capri test inhibitor; l-phenyl-5-mercap + tetrazole hardener: 2,4-dichloro-6-hydroxy-S-tri7dine sodium coating auxiliary oil nidodecylbenzene sodium sulfonate sequentially In addition, sample 6》, (
6), Cη was obtained.

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

However, the relative sensitivity is expressed as the relative value of the reciprocal of the exposure amount necessary to give a density of Capri value 10 and the value b, and that of Sample 7 of 3'36'' was jtoo-a.

As is clear from Table 5, the emulsions (B) and (L) prepared using the compounds of the present invention have higher sensitivity than the comparative emulsion (K), and furthermore, the development progresses much faster. Early (
It will be clear that there are emulsions suitable for rapid processing.

Color developer 33℃ developing water 800
cc Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N,N-diethylhydroxylamine 4.2g Potassium bromide 0.01g Sodium chloride 1.5g Triethanolamine 110g Potassium carbonate
30gN-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-7minoaniline sulfate 4.5g4.4'-
Diaminostilbene-based fluorescent whitening agent (Sumitomo Chemical ill Whitex 4) 2
．． Add 0g water and make 1000c
At cKOH -, pH 10,25 (Bleach-fix solution formulation): 35°C 45 seconds Ammonium thiosulfate (54vrt%) 150mff1
N3g SOs --15g NHa (Fe (I) (EDTA)3 55gE
DTA2Ng -4g Glacial acetic acid Add 8.61g water and make a total amount of 1000 mJ (pH 5,4) <<Rinse liquid prescription>> 35℃ 90 seconds E07A -2Na ・2 Hz O0.4g Add water and make a total amount of 1000 mA (pH 0) Table 5 151 Emulsion 81 45 ltosl 120 1 This invention 1 fruit unpulled fruit ", Mimi, -2 = 1;
The desire for chemical aggravation; to humiliate it: temple opening edict 52
Public No. 2152-2 ÷ 4. :Recorded 0 practice guide-12 exam L-
In place of each of the two milks and the three, there was one.

The obtained test C was treated with a shosai C method to obtain a plant with good behavior.

In the example, it is true, -: De I split - T emulsion 3, Hasbo and salt, Otsu-synthetic acid; No. Publication (above);

I processed it with Mr. Nikoji Shimizu, and the development was good.
The preferred fruit of 2' and ``JJ -〇raikai) is as follows;

：、Photographic version of a patent poem characterized by the fact that all eight = a small amount of silver and τC mol% are salt and proboscis =
Gen.'Hi-Chicken Breast 2 manufacturing method.

2. A method for producing silver halide in which at least 3: mol % of all silver halides are salt and amber.

30 Claim C characterized in that 42% or more of the total projection = product of one or two halogen particles is C-i:G plane
Photo-1 Method of using silver hacodenate emulsion.

4. Total projection of halogen °hi11≠ child = product 35: %
I remember that the above is [nininini=' + I want to carry 2 photos of stomach C: silver genide T-agent S; how to spend.

D1. S L L; surface; + cutting halogen/arsenic particles are particles with a diameter/I ratio of 2 or more; Method for producing limited emulsion.

Bow, C: Halogen consisting of 2r>X: -:,
Waiting for the limit to be normal crystal grains with 8 sides and 2224 = rest.

(Photograph 1 of the patent claim characterized by the fact that the halogen I3S consisting of ni'J=power is combined with the 1S-like particles and the normal crystal grains CJ1)・Production method of silver arsenal emulsion.

3. Nini LA: TZ・filtered particle C table= and beside] com also ;; Co γ-containing fu The manufacturing method of claim O 3C characterized by this.

C
How to send, cloud.

′, :, :￥ni Ni: = Ni ra naru! Tatsuko is sulfur 243 agent and also. A method for manufacturing a paper towel as claimed in Patent 81, which is characterized in that it is chemically enlarged in 45 steps.

,,2. . ]-No1shi,! -, Mimo Z: 20th and 2nd
Σ2=Respectively Real': Finish S:0 This is an electronic v-mograph showing the structure of silver halide crystal grains 2 contained in Emulsion 2 and Milk t;: of Emulsion 2.

:Kokage double:=Each;2. . , 5.4-no.

Procurement; Person Tomi: Photo Funorum Co., Ltd.---1-, Procedural amendment

Claims (1)

[Scope of Claims] A method 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 consists of (111) planes, A method for producing a photographic silver halide emulsion, characterized in that silver halide grains are formed in the presence of at least one compound of the following general formula (I) or general formula (II). (Claim) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A1, A2, A3 and A4 are to complete the nitrogen-containing heterocycle represents a group of nonmetallic atoms, each of which may be the same or different.B represents a divalent linking group.m is 0
Or represents 1. R1 and R2 each represent an alkyl group. X represents an anion. n represents 0 or 1, and in the case of an inner salt, n is 0. )