JPH046546A - Production of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain an emulsion having photographic performance high in gradation by narrowing distributions of the volume and projection area of each silver halide grain. CONSTITUTION:The silver halide grains are formed in the presence of at least one of the compounds represented by formulae I and II in which each of A1 - A4 is a nonmetallic atomic group necessary to complete an N-containing hereto ring; B is a divalent bonding group; (m) is 0 or 1; each of R1 and R2 alkyl; X is an anion; and (n) is 0 or 1. The obtained silver halide grains are rich in the silver chloride content as high as >= 80 mol%, they contain flat grains having a thickness of <= 0.5 mum and a diameter of >= 0.5 mum and an aspect ratio of >= 2 in a projection area of >= 50% of that of the total silver halide grains, and in an early stage of forming the grains, the concentration of the chlorine ions is controlled to 3X10<-2> - 1X10<-1> mol/l and that in the later half stage is controlled to 5X10<-3> - 5X10<-2> mol/l, thus permitting the obtained individual grains to be flat grains high in the silver chloride content and yet narrow in the volume distribution and high in gradation.

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, the present invention relates to a tabular silver chlorobromide, silver chloroiodobromide or silver chloroiodide emulsion having a high silver chloride content and excellent rapid processability and high sensitivity.

(Prior Art) Currently, in the development processing of X-ray photosensitive materials, there is a demand for shortening the processing time and reducing the amount of waste liquid accompanying the processing. Generally, silver iodobromide emulsions are used in X-ray sensitive materials, but to meet the above requirements, it is advantageous to use silver chlorobromide emulsions with a high amount of dissolved carbon. On the other hand, in order to reduce waste liquid, it is desirable to increase image density with a small amount of silver.
It is well known among those skilled in the art that tabular grains are suitable in terms of graininess, sharpness, color sensitization efficiency, and the like.

Silver halide grains with a high silver chloride content (hereinafter referred to as "high silver chloride grains") generally tend to form cubic grains, and some measures are required to form them into tabular grains.

The method for producing silver chlorobromide tabular grains is already known, for example, as described in Japanese Patent Publication No. 8324/1983,
A method in which chloride and silver salt solutions are simultaneously introduced into a dispersion medium in the presence of ammonia by a double jet method, ■ In the presence of a pebutizer containing aminoazaindene and thioether condensation, as described in Japanese Patent Publication No. 8326/1983. A method of reacting a silver salt aqueous solution with a chloride-containing halide salt aqueous solution, as described in Japanese Patent Publication No. 5B-111936, the molar ratio of chloride ions to promide ions in the reaction vessel is set at 1.6:1 to 1.6:1. 258:1 and the total concentration of halogen ions is 0.10~
Method of simultaneously introducing silver, chloride and bromide salts while maintaining the range of 0.90 normal, ■ JP-A-62-163
046, a method of introducing silver ions into a dispersion medium containing a gelatin peptizer made from at least 0.5 molar concentration of chloride ions and less than 30 μmol of methionine per gram, Kaisho 63-28114
As described in No. 9, a method of bringing a chloride-containing halide salt into contact with an aqueous silver salt in the presence of a dispersion medium in the presence of aminoazapyridine and a crystal habit-changing amount of its salt, JP-A No. 62-218959, JP-A No. 63-2
13836, a method in which a halide and a silver salt solution are mixed in the presence of thiourea or a thiourea derivative, and a method using a gold compound; As described in JP-A No. 6341845, a method of forming particles in the presence of a compound containing a sulfur atom in the heterocycle, and a method of forming particles in the presence of a compound containing a sulfur atom in the molecule, A method of forming particles in the presence of such a substance is known.

Among these, the silver chloride content in the tabular grains is limited to 40 mol%, making it unsuitable for producing high-silver chloride grains. It is difficult to make and the pH during particle formation
This inevitably increases the capri of high silver chloride emulsions which are sensitive to capri, and the grain formation conditions are severely restricted. Thiourea derivatives such as (2) have the disadvantage of being prone to capri formation during ripening. In ■, a synthetic polymer is used, and in ■, gelatin with a reduced methionine content is used as a pebtizer, but in ■, it is difficult to obtain a copolymer with good reproducibility, and the polymerization initiator contains impurities that are harmful to photography. In some cases, the desalting process becomes complicated, and the cost to remove these problems increases, which has many drawbacks from an industrial perspective. There are problems with the associated cost increase and reproducibility.

Synthetic crystal phase control agents such as ■, ■, and ■, even after particle formation,
It remains adsorbed on silver chloride grains and is difficult to remove by a simple method, which poses a problem for subsequent chemical sensitization and spectral sensitization.

From the above, it is possible to obtain tabular high-silver chloride grains with good reproducibility by simply using a low-cost, low-molecular-weight compound that is easy to synthesize and purify in the acidic to neutral region with gelatin, which is a general-purpose veptizer. Furthermore, after grain formation, the crystal phase control agent adsorbed on silver chloride grains can be relatively easily removed by a normal desalting process, etc. in the production using bispyridinium salts, etc. as shown in JP-A-2-32. It was a method.

However, high silver chloride tabular grains have a wide volume distribution of individual grains, making it difficult to obtain emulsions with sharp gradation.

As described above, it has been desired to develop a method for preparing an emulsion that is capable of producing high-silver chloride tabular grains, but with a narrow volume distribution of individual grains and a high contrast gradation.

(Objective of the Invention) The object of the present invention is to provide stable and highly sensitive processing even in rapid processing;
A tabular silver halide emulsion with a high silver chloride content that has low fog and fast development and fixing speeds.It has high gradation photographic properties by narrowing the distribution of the volume and projected area of each silver halide grain. The object of the present invention is to provide a method for obtaining an emulsion having the following properties.

(Disclosure of the Invention) As a result of intensive studies, the present inventors have found that at least High silver chloride grains in which 80 mol% or more is chloride, and tabular grains with a thickness of less than 0.5 μm, a diameter of 0.5 μm or more, and an aspect ratio of 2 or more account for 50% or more of the projected area of all silver halide grains. In a silver halide emulsion that accounts for 10% of the total chloride ion concentration during grain formation, the chloride ion concentration at the initial stage of grain formation should be set to 3×10−′ mol/1 or more I×10−′ mol/1.
1, and the chloride ion concentration in the latter half of particle formation is 5.
It has been found that the above object can be achieved by setting the amount to be at least X10-"mol/1 and less than 5X10-"mol/1.

General formula (I) General formula (II) (At , Ax , As and A represent nonmetallic atomic groups for completing the nitrogen-containing heterocycle, and each may be the same or different. B is a divalent m represents a linking group of
Hail 0 or 1. RR2 each represents an alkyl group. X represents an anion. n represents O or 1, and n is O in the case of an inner salt. ) The tabular grains of the present invention have a diameter/thickness ratio (aspect ratio) of 2=1 or more, preferably 2:1 to 20:1, more preferably 3:1 to 15:1. l
It is.

The diameter of a tabular grain herein refers to the diameter of a circle having an area equal to the projected area of the grain.

Here, the meanings of the words "early stage of particle formation" and "later half of particle formation" will be explained.

Generally, the formation of tabular grains can be considered in two stages. First, silver ions in an amount of 0.5% to 20% of the total amount of added silver are added into a grain forming container to form small tabular core grains. Second, non-tab grains are eliminated by physical ripening, and then remaining silver ions are added to grow small tabular core grains.

Here, "chloride ion concentration at the initial stage of grain formation" refers to the chloride ion concentration at the stage of forming tabular core grains. Specifically, the chloride ion concentration in the particle forming container immediately before adding the first silver ion was set to 3×10−” mol/1.
The above is to set I x 10-' mol/1 or more.

0.5% to 20% of the total amount of added silver necessary to form a tabular nucleus by adding silver and halogen by the double jet method.
The chloride ion concentration in the medium grain forming vessel may be kept constant during the addition of silver ions, or the chloride ion concentration may be varied during plate nucleation by changing the ratio of silver and halogen added. At this time, the chloride ion concentration before the first silver ion addition is 3X10-' mol/1 or less IX10-'
As long as it is less than 1 mol/l, the chloride ion concentration may be 3×10 4 mol/l or less during plate nucleation.

Next, the chloride ion concentration in the latter half of grain formation refers to the concentration in the grain formation container at the stage of growing small tabular grain nuclei. Specifically, the chloride ion concentration during the addition of the latter 50% of the total amount of silver added required for grain formation was adjusted to 5×1.
0-'mol/7! The amount should be 5×10 4 mol/l or more.

Below, -11ffi formulas (I) and (It) will be explained in more detail.

A3, At, As, and A4 represent a group of nonmetallic atoms for completing the nitrogen-containing heterocycle, and may contain an oxygen atom, a nitrogen atom, and a sulfur atom, and a benzene ring may be fused. A, , At.

The heterocycle composed of A and A4 may have a substituent, and each may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, an anlu group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonyl group,
Examples include a cyano group and a nido-membered ring (eg, 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 organic group. The divalent organic group is alkylene, arylene, alkenylene, SCh
So -0-S--C--N- (R represents an alkyl group, an aryl group, a hydrogen R coatom) alone or in combination; as a preferred example, B is an alkylene , alkenylene can be given.

R1 and R2 represent an alkyl group having 1 to 20 carbon atoms. eRI and R1 may be the same or different.

(Compound example) This is the same as the substituents listed above.

As a preferable example, R1 and R2 each have 4 to 4 carbon atoms.
A more preferred example of 10 alkyl groups is a substituted or unsubstituted aryl-substituted alkyl group.

X represents an anion 0 For example, chlorine ion, bromide ion, iodide ion, nitrate ion, g-acid ion, p-toluenesulfonate, oxalate, n represents O zero or 1, in the case of an inner salt , n is zero.

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

2B. Synthesis of (6) 100 g of 4,4'-dipyridyl and 190 Jd of benzyl bromide were added to methanol 80 (lI11), heated under reflux for 3 hours. After filtering the reaction solution, 800 ml of isopropyl alcohol was added to obtain crystals. was collected by filtration, and the compound (
6) was obtained.

Yield: 286 g (90%) Synthesis of Compound Q21 20 g of 1,3-di-4-pyridylpropane and 30 m of benzyl bromide were added to 400 d of ethanol, and the mixture was heated under reflux for 2 hours. After filtering the reaction solution, 400 d of ethyl acetate was added and the resulting crystals were collected by filtration to obtain Compound 021.

Yield: 41g (76%) The amount of the compound represented by formula (I) or (II) added is 2X10-' mol to 3 mol per mol of silver halide.
It can be used in the range of
For the preparation of 'mole-lXl0-' tabular grains, it is preferred that at least a portion of these compounds be present from the beginning of grain formation.

Furthermore, in order to prepare high-silver chloride tabular grains having a narrow volume and projected area of the silver halide grains of the present invention, it is important to have these compounds present during nucleation and to control the chloride ion concentration. The preferred chloride ion concentration will be explained in more detail below.

First, the initial chloride ion concentration when mixing silver and halogen is 3×1O4 mol/j2 to form tabular grains.
It is important to do the above. If it is less than this, a sufficient number of high-silver chloride tabular grain nuclei cannot be formed, and the proportion of octahedral grains increases. However, if the chloride ion concentration after the formation of tabular grain nuclei is too high, the volume and projected area distribution of the sides of the silver halide grains will expand due to physical ripening. Therefore, it is important that the subsequent growth of tabular grains be carried out at a chloride ion concentration of 5X10-'' mol/l or less.
If it is 0-'' mol/l or less, the generation of new tabular grain nuclei can be suppressed, which is more preferable.

As described above, it is preferable that the chloride ion concentration be relatively high during the initial stage of grain formation, and that the subsequent growth be performed at a relatively low chloride ion concentration.

However, if the chloride ion concentration at the initial stage of grain formation is too high, it will take time to add silver to achieve the low chloride ion concentration necessary for growth, and physical ripening will reduce the volume and projection of the sides of the silver halide grains. The area distribution becomes wider. However, if the rate of addition of silver is increased, new tabular grain nuclei will be generated, and the volume and projected area distribution will become wider.

Therefore, the chloride ion concentration at the initial stage of particle formation is 3×1O−
2 moles/! It is important that the amount is above and less than 1×1 O mol/1.

In addition, it is preferable that the chloride ion concentration in the latter half of grain formation be relatively low in order to narrow the volume and projected area distribution of silver halide grains, but if it is too low, the thickness of the tabular grains will become too thick, which is not practical. This is not preferable because the advantages of tabular grains cannot be utilized. Therefore, the chloride ion concentration in the latter half of particle formation is less than 5X10-"mol/I! and 5X10-"mol/I!
It is important that the value is 1 or more.

The temperature at which these particles are formed can range from 10°C to 95°C, preferably from 30°C to 90°C. In particular, the temperature in the first half of grain formation is preferable because the lower the temperature, the more tabular nuclei will occur.
Particularly preferred is a range of 0°C to 40°C.

Conversely, in the latter half of grain formation, it is necessary to reduce the generation of new tabular grain nuclei in order to narrow the volume and projected area distribution of silver halide grains, so the temperature in the latter half of grain formation is 50°C.
It is particularly preferable to keep the temperature above °C.

Any pH may be used, but a neutral to acidic range is preferred.

The high silver chloride grains of the present invention produced in this manner refer to grains having a silver chloride content of at least 80 mol % or more. Preferably it is 90 mol%, more preferably 95 mol% or more.

The remainder consists of silver bromide and/or silver iodide, and the content of silver iodide is preferably 5 mol% or less, preferably 1 mol% or less. It is particularly desirable that a layer consisting mainly of silver bromide or silver iodide be localized near the surface of the grains.

As a method for localizing the layer made of silver bromide or silver iodide, a method such as that described in Japanese Patent Application No. 1-276527 can be used.

Furthermore, in the case of so-called core/shell type particles, it is preferable that the silver chloride content in the core portion is higher than that in the shell portion. For example, particles may be composed of a core portion made of silver chloride and a shell portion made of silver bromide.

The silver halide grains of the present invention have surfaces consisting of (I11) planes, and at least 30% or more, preferably 40% or more, more preferably 60% or more of the total surface area is (I11).
Consists of a surface. The (I11) plane can be quantified from an electron micrograph of the formed silver halide grains.

The silver halide grains of the present invention have a diameter/thickness ratio of 2.
It is more preferably 2 or more and 50 or less, particularly preferably 2 or more and 20 or less, and most preferably 3 or more and 10 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°0 μ, preferably 0.
．． It is 5 to 3.0μ.

Further, the thickness is less than 0.5 μm, preferably 0.3 μm or less, and more preferably 0.2 μm or less.

The average volume of the volume load of the particles is preferably 2μ or less. Further, it is preferably 1.0 μm or less.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore "thickness" in the present invention refers to the distance between the two parallel surfaces constituting the tabular silver halide grains. expressed.

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
No. 2.448,534, No. 3,320,06
No. 9), thioether compounds (such as U.S. Pat. No. 3), thioether compounds (such as U.S. Pat.
, 271,157, 3,574,628, 3,704,130, 4,297,439, 4.276.347, etc.), thione compounds and thiourea compounds (For example, JP-A-53-144319, JP-A No. 53-144319,
No. 3-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.), and these can be used.

Ammonia can also be used within a range that does not cause sensitizing effects.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present, and an iridium salt or a rhodium salt is particularly preferred.

During the production of silver halide grains of the present invention, the addition rate, amount, and concentration of silver salt solution (e.g., A g N O3 aqueous solution) and halide solution (e.g., NaC1 aqueous solution), which are added to accelerate grain growth, are determined. A method of increasing the addition time according to the addition time is preferably used.

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, 5B-113928, 58
-111934, No. 58-111936, 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 so-called gold sensitization methods using gold compounds (for example, U.S. Pat. Nos. 2,448,060 and 3,32).
No. 0,069) or sensitization methods using metals such as iridium, platinum, rhodium, palladium (for example, U.S. Pat.
No. 48.060, No. 2.566.245, No. 2,56
6.263) 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 a reduction aggravation method using tin salts, thiourea dioxide, polyamines, etc. (For example, U.S. Pat. No. 2,487,850, U.S. Pat. No. 2,518.698, U.S. Pat.
, 521, 925), or a combination of two or more thereof.

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 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 account for at least 50%, preferably at least 70%, of the projected area of all silver halide grains in the emulsion.
Particularly preferably, it is present in an amount of 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.

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

The emulsion of the present invention may be spectrally enhanced 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. For these dyes, any of the basic submerged ring nuclei commonly used for cyanine dyes can be used. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; 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 Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

For example, RESERCB DISCLO5URE I
tea, 17643, page 23, section ■ (I978 1
(February) or the compounds described in the cited literature can be used.

The dye may be added to the emulsion at any stage of emulsion preparation that has been known to be useful.
Although it is usually carried out after the completion of chemical sensitization and before application, chemical aggravating agents and as described in U.S. Pat. Spectral enhancement can be carried out at the same time as chemical sensitization by adding it at the same time, or it can be carried out prior to chemical sensitization as described in JP-A-58-113,928.
It is also possible to start spectral sensitization by adding it before the completion of silver halide grain precipitation. Furthermore, U.S. Pat.
225,666 by adding these said compounds separately, i.e., some of these compounds are added prior to chemical sensitization and the rest are added after chemical sensitization. is also possible, as described in U.S. Patent No. 4. 183.
No. 756, or at any time during silver halide grain formation.

The amount added is 4X10-' to 8 per mole of silver halide.
It can be used in an amount of X10-3 mol, but in the case of a more preferred silver halide grain size of 0.2 to 3 μm, approximately
10-' to 2x-3 moles are more effective.

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; examples of black and white photographic materials include X-ray film, general photographic film, and printing material film.
It can be particularly preferably used for color paper.

There are no particular restrictions on other additives for photographic window optical materials to which the emulsion of the present invention is applied;
e) Volume 176 Item 17643 (RD17643)
and Volume 187 Item 18716 (RD18716
) can be referred to.

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

9 Hardener page 26 651 Left column io Binder page 26 Same as above 11
Plasticizer, lubricant Page 27 650 Right column 12
Coating aid, pages 26-27 Same as above Surfactant 13 Static prevention page 27 Same as above 1
Chemical enhancers 2 Sensitivity increasing side 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Antifoggants and stabilizers 6 Light absorbers, fu pages 25-26 Irk dye UV absorbers 7 Anti-stain agents page 25 Right column 8 Dye image stabilizer Page 25 Page 24 Page 23 Page 23-24 Pages 24-25 Page 648 Right column Same as above Page 648 Right column ~ Page 649 Right column Page 649 Right column Page 649 Right column ~ 650 Left column Page 650 Left ~Among the additives in the right column, antifoggants and stabilizers include azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promohensimidazoles, nitroindazoles, penztriazoles, aminotriazoles) mercapto compounds (e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,
mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.); thioketo compounds such as oxadorinthione; azaindenes (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (I, 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 DIR coupler), or the product of the coupling reaction is colorless and has a development inhibitory effect. It may also include a colorless DIR coupling compound that releases the agent.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilide cyan couplers include naphthol couplers and phenol couplers. As cyan couplers, U.S. Patent Nos. 3,772,002, 2,772,162, and 37
No. 58308, No. 4126396, No. 4334011
No. 4327173, No. 3446622, No. 43
No. 33999, No. 4451559, No. 4427767
Phenolic couplers having an ethyl group at the meta-position of the phenol nucleus, 2,5-diacylamino monovalent phenolic couplers, and phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. ,
Couplers in which the 5th position of naphthol is substituted with sulfonamide, amide, etc. are preferred because they provide excellent image fastness.

In order to satisfy the characteristics required for the photonic material, two or more types of couplers etc. can be used together in the same layer, or the same compound can be added to different 2N or more.
Of course it doesn't matter.

Antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic a derivatives,
Typical examples include methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)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. ) 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 dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminephenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

The color developing solution is composed of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as a phenylene diamine (e.g.
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N
-ethyl-Nβ-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (I
966), pages 226-229, U.S. Patent 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 buffering agents such as alkali metal gnites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. etc. can be included. Also, if necessary,
water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1
- Auxiliary developers such as phenyl-3-virapritone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in US Pat.
It may also contain antioxidants such as those described in No. 950.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment or separately. Examples of bleaching agents include iron (III), cobalt (■), chromium (■), copper (II), etc. Polyvalent metal compounds, peracids,
Quinones, nitroso compounds, etc. are used.1 For example, ferricyanide, dichromate, organic complex salts of iron (I(I) or cobal) (I[I), such as ethylenediamine tetracomplex, nitrilotriacetic acid, 1.3 -diamino-2-
Complex salts of aminopolycarboxylic acids such as propatooltetraacetic acid or f-organic acids such as citric acid, tartaric acid, and malic acid;
Persulfates, permanganates; nitrosophenols, etc. can be used. Among these, potassium ferricyanide, sodium ferric(III) ethylenediamine tetracomplex, and ammonium iron(I[I) ethylenediamine tetracomplex are particularly useful. Ethylenediamine tetracomplex iron (III) 1
8 salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3,042.52
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) Silver chloride emulsions A-E were prepared as follows.

Solution (]) 'H! 0 Solution (2) Solution (3) Solution (4) Solution (5) Solution (6) Solution (7) Add tH and o to 400cc at 35℃
While vigorously stirring the solution (I) kept at
2) and solution (3) were added simultaneously over 1 minute and 30 seconds.

After further raising the temperature to 75℃, solution (4) and solution (5)
were added simultaneously over 25 minutes.

Thereafter, solution (6) and solution (7) were added simultaneously over 40 minutes.

After washing and desalting this emulsion with water using the usual flocculation method and adding gelatin, the emulsion was heated to 40°C with a PTT of 6.4 and a PTT of 6.4.
Ag was adjusted to 7.5 to obtain silver chloride emulsions A to E. A-
The chloride ion concentration during H grain formation and the shape of the obtained silver halide are shown in Table 1.

The volume variation coefficients in the table were determined by measurement using a Coulter Counter Model TAII manufactured by Coulter Electronics, Inc., USA.

700cc Aspect ratio 2 made up of parallel (I11) planes like this
In order to create an emulsion containing 80% or more (projected area) of tabular grains, the chloride ion concentration at the time of grain formation must be 3X.
Must be greater than or equal to 10-'' mole/1.

Moreover, as the chloride ion concentration decreases from 0.1 mol/l to 0.05 mol/1 → 0.03 mol/1 in the range of 3×10-' mol/1 or more, the particle size distribution of tabular grains becomes narrower. This is preferable because a more monodisperse emulsion can be obtained.

Samples 101 to 105 were prepared by applying the emulsions of A-H to a polyethylene terephthalate film support and adding the additives shown in Table 2 to coat the emulsions and protective layers.

Each sample was exposed to mercury light at 4000 lux for 1150 seconds through an optical wedge, using an FPM manufactured by Fuji Photo Film ■.
The film was developed using an RD-1 [1 developer specified by Fuji Photo Film Co., Ltd.] using a -4000 automatic processor under processing conditions of 35°C and 190 seconds.

Table 2 (emulsion layer) Emulsion Each of the above emulsions Coated silver amount 2.0 g/rrf gelatin 1. 3g/rrr Stabilizer: 4-hydroxy-6-methyl-1,3°3a,7-chitrazaindene Adder: Potassium poly-p-styrenesulfonate 1'1lilFI: 1,2-bis(vinylsulfonylacetamidoethane) ( Surface protective layer) Gelatin 1.0g/rrf coating aid' P-CsHtt-CJa-(OCHzCHg
) 5sOsNa preservative: 3-benzisothiazolidone Matting agent: Polymethyl methacrylate fine particles The evaluation results are shown in Table 3.

The sensitivity in the table is 0 from the fog value for each sample.
．． 5 and 1.0 The sensitivity of sample 101 is 0.5 as the relative value of the logarithm of the reciprocal of the exposure required to give a higher optical density.
0 gradation shown in relative sensitivity with 1.00 is sensitivity 0.5
, using a sensitivity of 1.0.

Table 3 Samples 103 and 104, which are plate-like emulsions with a narrower volume distribution, have high sensitivity and hard gradation and are useful, but they are still insufficient for applications that require hard gradation such as for X-ray film. It is a level.

(Example 2) In order to obtain a high-silver chloride tabular emulsion with a narrower grain size distribution, emulsion F-K was prepared using the following solutions (8) to (8) in place of solutions (I) to (7).

Similarly to Example 1, solution (9) and solution 0ω were heated for 1 minute and 30 minutes while vigorously stirring solution (8) kept at 35°C.
They were added simultaneously over a period of seconds.

After further increasing the temperature to 75℃, the solution θ0 and the solution (+2
1 was added simultaneously over 25 minutes. By changing the ratio of the amounts of silver ions and chloride ions added in this solution 00 and solution QZ, the chloride ion concentration in the reaction vessel is changed.

Thereafter, particles were grown by simultaneously adding solution a9 and solution (goods), which were adjusted so as not to change the chloride ion concentration in the reaction vessel, over a period of 40 minutes.

After washing and desalting this emulsion with water using the usual flochieracin method, gelatin was added, and the pH was adjusted to 7.4 pAg at 40°C.
65 to obtain silver chloride emulsions F to J. The chloride ion concentration during grain formation of F-J and the shape of the obtained silver halide are shown in Table 4.

As shown in Table 4, after forming a silver chloride plate with a chloride ion concentration sufficient to form plate nuclei, silver and halogen were gradually added while gradually shifting the chloride ion concentration to a lower level. It can be seen that by growing, monodispersity is achieved. However, if the chloride ion concentration in the latter half of grain formation is too low as in F, the thickness becomes too thick, the characteristics of the tabular grains are not utilized, and the original purpose cannot be achieved.

Furthermore, if particles are formed from the beginning at a chloride ion concentration such as F-H, where monodispersity has been achieved, a high tabularization rate cannot be obtained as shown in Example 1. Therefore, it is important to change the chloride concentration during particle formation.

The average projected area of emulsion H shown in Table 4 is 1.6μ,
Its projected area dispersion was 0.17.

The average aspect ratio is 6.2.

Samples 106 to 111 were prepared by applying the emulsion of F- to a polyethylene terephthalate film support in the same manner as in Example 1, adding the additives shown in Table 2, and applying the emulsion and protective layer. Thereafter, each sample was passed through an optical wedge in the same way.
Exposure to mercury light of 000 lux for 1150 seconds, and process at 35°C using an FPM-4000 automatic processor manufactured by Fuji Photo Film ■.
Under processing conditions of 90 seconds, Fuji Photo Film ■ Specified RD
-1 [[Developed with developer.

These evaluation results are shown in Table 5. The sensitivity and gradation are the same as in Example 1.

Table 5 As is clear from Table 5, by adjusting the chloride ion concentration during grain formation, a photosensitive material in which 80% or more of the projected area is tabular grains, monodisperse, and high in gradation can be obtained. be able to.

(Example 3) Samples 106 to 111 obtained in Example 2 were treated with the following treatment liquid.

Adjustment of pH to 10.5 by adding IKOH Fixer: Fuji-F fixer manufactured by Fuji Photo Film Company.

Table 6 shows the results of 30'' development at 35° C., fixation at 20° C. for 2 minutes, washing with water and drying using the above-mentioned developers (1) and (2).

As described above, the characteristics of the high-contrast sample of the present invention become clearer when processed with a developer that contains less SS and does not contain Br. Furthermore, treatment with such a treatment liquid is preferable because the sensitivity can be increased.

(Example 4) The following method can also be used to increase the chloride ion concentration in the early stage of nucleation and to lower the chloride ion concentration in the latter half.

Table 7 First, while solution 051 was kept at 35° C. and vigorously stirred, solution 05) was simultaneously added alone over 1 minute and 30 seconds.

After further raising the temperature to 75° C., solution 07) and the solution side were added simultaneously over 25 minutes.

Thereafter, Solution 09 and Solution (To) were added simultaneously over 40 minutes.

This emulsion was washed with water and dispersed in the same manner as in Example 1 to obtain an emulsion. This product was coated on a polyethylene terephthalate film support in the same manner as in Example 2 to obtain Sample 112.

Sample 112 was exposed to haze light in the same manner as in Example 1, and then developed using RD-3 under the conditions shown in Example 1. The grain shape of this emulsion L- and the development results of sample 112 are shown in Table 7.8.

Table 8 As is clear from this table, it is possible to obtain monodisperse and high-contrast silver chloride tabular grains even with this method. By doing so, the chloride ion concentration during plate nucleation may be changed.

The present invention involves doping metal ions as shown below,
A halogen convergence run using Br or the like was performed. Chemical sensitization and color sensitization can also be applied.

(Example 5) Here, an example of doping with metal ions is shown.

After raising the temperature to 75°C, the solutions (24) and (25) were
After simultaneous addition over 5 minutes, solutions (26) and (2)
7) was added simultaneously over 40 minutes. This emulsion was desalted, dispersed and adjusted in the same manner as in Example 1 to obtain emulsions M and N.

(Table 9) These M and N were coated on a polyethylene terephthalate film support in the same manner as in Example 1 to obtain samples 113 and 114.

Samples 113 and 114 were exposed and developed in the same manner as in Example 1, and the results obtained are shown in Table 10.

While vigorously stirring the solution (21) kept at 35°C in the same way as in Example 1, the solution (22) and solution (23) were mixed in 1 part.
They were added simultaneously over a period of 30 minutes.

Table 10 As is clear from Table 9.10, even when high sensitivity is achieved by doping with metal, a hard gradation can be obtained, which is preferable.

(Example 6) After forming high silver chloride tabular grains in the same manner as Emulsion H of Example 2, ultrafine silver bromide grain emulsion ( particle size 0.05μm)
was added and aged at 60°C for 10 minutes. After that, diphenylthiourea and chloroauric acid were added to optimally chemically sensitize the
Emulsion O was obtained by adding 1-phenyl-5-mercaptotetrazole as an anti-capri agent.

This was coated on a polyethylene terephthalate film support in the same manner as in Example 1 to obtain Sample 115. Sample 115 was exposed and developed in the same manner as in Example 1, and the results obtained are shown in Table 11.

As is clear from this table, the emulsion of this example can be suitably chemically sensitized to increase sensitivity and harden the gradation, which is preferable.

Claims (1)

[Scope of Claims] At least 80 mol% of silver chloride is formed by forming particles in the presence of at least one compound of the following general formula (I) or (II), and the thickness is less than 0.5 μm, Diameter 0
．． In a method for producing a silver halide emulsion in which tabular grains with a diameter of 5 μm or more and an aspect ratio of 2 or more account for 50% or more of the projected area of all silver halide grains, the chloride ion concentration in the reaction vessel at the initial stage of grain formation is increased by 3×. 10^-^2 mol/
l or more and less than 1 x 10^-^1 mol/l, and the chloride ion concentration in the latter half of particle formation is 5 x 10^-^3 mol/l.
A method for producing a silver halide emulsion, characterized in that the concentration is 1 or more and less than 5x10^-^2 mol/l. General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. Represents an atomic group, each of which may be the same or different. B represents a divalent linking group. m represents 0 or 1. R_1 and R_2 each represent an alkyl group. X represents an anion. n represents It represents 0 or 1, and n is 0 when it is an inner salt.)