JPH04283742A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide emulsion which is suitable for rapid development processing, is fast in progression of development and has a high silver chloride content by forming particles in the presence of the compds. expressed by specific formula. CONSTITUTION:At least >=50mol% of the particles of the silver halide emulsion of an emulsion layer having one layer on a base consists of the silver chloride. At least 50% of the total projection area of the silver halide particles consists of the particles having a (111) face and the silver halide particles are formed in the presence of at least one kind of the compds. expressed by the formula I. In the formula I, R<1> and R<2> denote a hydrogen atom, aryl group or aralkyl group; R<3> denotes an amino group or carboxyl group; n denotes 1 to 5 integer.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to silver halide photographic materials. In particular, silver halide photography using a silver halide emulsion consisting of 14-hedral, octahedral, or tabular silver chloride, or silver chlorobromide, silver chloroiodide, or silver chloroiodobromide with a high silver chloride content. It's about materials.

0002

[Prior Art] In recent years, there has been a desire in the photographic industry for shorter access times, no waste water, no replenishment of processing solutions, etc., and there has been an urgent need to develop silver halide photographic materials suitable for such processing. There is. Increasing the silver chloride content increases water solubility, allowing development and fixing to be accomplished in less time, resulting in a silver halide suitable for rapid processing. Silver halide grains with a high silver chloride content (hereinafter referred to as "high silver chloride grains") generally tend to be cubic grains consisting of (100) faces, and grains other than cubes, specifically octahedral and tetradecahedral grains. Considerable effort is required to obtain normal crystal grains and tabular grains.

[0003] Tabular grains herein refer to grains having two parallel or substantially parallel crystal faces that are substantially larger than other faces of the grain.

[0004] Increasing the sensitivity of photographic silver halide emulsions, and improving sharpness, graininess, color sensitization efficiency using sensitizing dyes,
It is well known among those skilled in the art that so-called tabular grains, in which the grain size is considerably larger than the grain thickness, are preferable in order to increase covering power, etc. For tabular grains with high silver chloride, no internal bromide or iodide and a pAg of 6.
US Pat. No. 43, Particle formation using ammonia with pH in the range of 5 to 10 and maintaining the pH in the range of 8 to 10.
The method of No. 9215, the method of U.S. Pat. No. 4,400,463 in which particles are formed in the coexistence of an aminoazaindene and a peptizer having a thioether bond, and the method of JP-A-62-218959 using a thiourea compound are known. There is.

However, since the method using ammonia further increases the solubility of highly soluble silver chloride grains, the grain volume is often 1 μm, which is often used in sensitive materials for rapid processing.
It is difficult to make emulsions with a relatively small size of 3 or less, and the pH during grain formation is inevitably high, which often increases the fog of high-silver chloride emulsions that are sensitive to fog. 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 There was a drawback that the desalting process became complicated. Furthermore, there were many drawbacks from an industrial standpoint, such as the high cost required to eliminate these disadvantages. From the above, in the acidic to neutral region, low-cost, low-molecular-weight compounds that are easy to synthesize and purify are simply
There has been a strong desire to develop a method for obtaining tabular high-silver chloride grains with good reproducibility by using gelatin, which is a general-purpose peptizer.

[0007] Furthermore, the above-mentioned tabular grains are grains that have twin planes within the grains and whose outer surfaces are (111) planes.
Only a few documents are known about the method for preparing octahedral or tetradecahedral high silver chloride grains which have no twin planes, are normal crystals, and have (111) planes on their outer surfaces. Specifically, Claes et al.; The Journal of
Photographic Science vol. 21, 39 (1973) and Wyrsch; Inter
National Congress of Photos
graphic ScienceIII-13, 12
2 (1978).

The former method uses compounds such as adenine, dimethylthiourea, and thiourea, but there has been no report on the photographic properties of the prepared octahedral particles. As expected from the structure of the compound, compounds such as adenine have a fairly strong adsorption to silver halide, and thioureas have unstable sulfur molecules that cause fogging. These compounds are easy to use, and both can only form octahedral grains, but they cannot be used at all for spectral sensitization, which is essential for producing silver halide photographic materials.

The latter method 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. Further, it is not preferable to use ammonia because high silver chloride grains tend to fog, and it has been desired to be able to prepare high silver chloride octahedral grains without causing pollution problems without using ammonia.

0010

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic material using a silver halide emulsion with a high silver chloride content, which is suitable for rapid development processing and whose development progresses extremely quickly. The second object is to provide a silver halide photographic material using a silver halide emulsion with a high silver chloride content using a compound that can be synthesized easily and at low cost. It is an object of the present invention to provide a silver halide photographic material using a high silver chloride emulsion containing many normal crystal grains of tetradecahedron or octahedron consisting of (111) planes in an acidic region where the occurrence of .

[0011]

[Means for Solving the Problems] As a result of intensive 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 (I), at least 50 mol% or more of Even with high silver chloride grains that are chloride,
Normal crystal grains and tabular grains such as octahedral to tetradecahedral,
As will be described later, we have found that the above object can be achieved by adjusting the chloride concentration at the initial stage of particle formation (so-called nucleation) and by adjusting the timing of addition.

That is, the present invention provides a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least 50 mol% of the grains of the silver halide emulsion in the emulsion layer are composed of silver chloride. , and at least 50% of the total projected area of the silver halide grains is (111)
This was achieved by using a silver halide photographic light-sensitive material consisting of grains having surfaces, the silver halide grains being formed in the presence of at least one compound represented by the following general formula (I). General formula (I)

[0013]

[Case 2]

R1 and R2 represent a hydrogen atom, an aryl group or an aralkyl group, and may be further substituted with a substituent. R1 and R2 may be the same or different. Substituents on the phenyl group of aryl and aralkyl groups include alkyl groups (methyl, ethyl, etc.), hydroxy groups, carboxy groups, halogen atoms (
Cl, Br), etc. R1 and R2
is preferably a hydrogen atom or a phenyl group. R3 represents an amino group or a carboxy group, the amino group may be substituted with alkyl, and the alkyl group represents an alkyl group having 1 to 5 carbon atoms. Preferred are amino groups and methyl-substituted amino groups. n represents an integer of 1 to 5. Preferably it is 2-3.

The compound represented by the general formula (I) used in the present invention can be obtained by reacting a corresponding halide with a thiourea derivative or the like. O. Cli
nton etal,. J. Am. Chem.
Soc. , 70, 950 (1948) and D. G. Do
Herty et al. , J. Am. Chem
．． Soc. , 79, 5670 (1957). Next, the general formula (
Although specific examples of the compound represented by I) are listed to more specifically explain the content of the present invention, the present invention is not limited to these compounds.

[0016]

[Chemical formula 3]

[0017]

[C4]

The compound of the present invention may be added at any time during grain formation from the time of nucleation of silver halide grains to the end of physical ripening in the production process of silver halide emulsions. However, when producing tabular grains, it is preferable that at least a portion of the grains be present from the initial stage of grain formation. In order to separately produce normal crystal (octahedral to tetradecahedral) grains and tabular grains using the compound of the present invention, the chloride concentration at the initial stage of grain formation (so-called nucleation time) can be adjusted and/or the present invention This is possible by selecting the timing of addition of the compound. Specifically, although there are some differences depending on the type of compound and the amount added, it is roughly as follows. That is,

(1) When preparing tabular grains, the chloride concentration when the compound of the present invention is present during nucleation is 0.01.
It is at least mol/liter, preferably at least 0.02 mol/liter, more preferably at least 0.03 mol/liter. Further, when the compound of the present invention is present during particle growth, the concentration of chloride is 5 mol/liter or less,
Preferably it is 0.02 to 1 mol/liter.

(2) For the preparation of normal crystal grains, the concentration of chloride when the compound of the present invention is present during nucleation is 2.
It is 0 mol/liter or less, preferably 1.0 mol/liter or less, more preferably 0.25 mol/liter or less. Further, when the compound of the present invention is present during particle growth, the concentration of chloride is 5 mol/liter or less,
Preferably it is 0.02 to 0.5 mol/liter. The temperature during particle formation in the present invention can be used in the range of 10°C to 95°C, preferably 25°C to 90°C.

[0021] The pH may be any value, but is preferably in the neutral to acidic range. The silver chloride grains of the present invention have a silver chloride content of at least 50 mol%, preferably 70 mol%.
, more preferably 90 mol% or more. The remainder consists of silver bromide and/or silver iodide, with a silver iodide content of 2
It is preferably 0 mol% or less, preferably 10 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.

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 are (11
1) The particles have a surface area consisting of planes, and the projected area of the particles is 50% or more of the total projected area, preferably 60% or more.

The grain surface can be quantified from an electron micrograph of the formed silver halide grains. When the silver halide grains of the present invention are normal crystals, the average grain size is not particularly limited, but is 0.1 to 5μ, preferably 0.
．． It is 2 to 3μ. When the silver halide grains of the present invention are tabular, the diameter/thickness ratio is 2 or more, preferably 2 or more and 50 or less, particularly preferably 2 or more and 20 or less, and 3 or more and 10 or less. Most preferred.

The diameter of a silver halide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular silver halide grains is 0.3 to 5.0μ,
Preferably it is 0.5-3.0μ. Also, the thickness is 0.4
The thickness is not more than μm, preferably not more than 0.3 μm, more preferably not more than 0.2 μm. The average volume of the particle volume load is 2
It is preferably 3 μm or less. Further, it is preferably 1.0 μm3 or less.

Generally, tabular silver halide grains are tabular with two parallel surfaces, and therefore, "thickness" in the present invention refers to the thickness of the two parallel surfaces constituting the tabular silver halide grains. It is expressed as a distance. 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.

In the process of silver halide grain 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 be coexisting. good. Particularly preferred are iridium salts or rhodium salts. During the production of silver halide grains of the present invention, the addition rate, amount, and concentration of silver salt solution (e.g., AgNO3 aqueous solution) and halide solution (e.g., NaCl aqueous solution), which are added to accelerate grain growth, are determined according to the addition time. A method of raising the temperature is preferably used.

These methods are described, for example, in British Patent No. 1,335,925 and British Patent No. 3,672,900.
No. 3,650,757, No. 4,242,44
No. 5, JP-A-55-142329, JP-A No. 55-1581
No. 24, No. 58-113927, No. 58-11392
No. 8, No. 58-111934, No. 58-111936
You can refer to the description of the number etc. 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 compounds (for example, US Pat. sensitization method (for example, U.S. Pat. No. 2,448,060, U.S. Pat. No. 2,566,245, U.S. Pat. No. 2,566,263) or sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222,264). ), selenium sensitization method using selenium compounds or tin salts,
Reduction sensitization using thiourea dioxide, polyamines, etc. (e.g., U.S. Pat. Nos. 2,487,850 and 2,518,6)
No. 98, No. 2,521,925), or two of these
Combinations of more than one 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 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.

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 emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are 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, oxazoline nucleus,
Chinazoline nucleus, pyrrole 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 an aromatic hydrocarbon ring in these nuclei After fusion, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. 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-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus having a ketomethylene structure. 5 such as nuclei, thiobarbituric acid nuclei, etc.
~6-membered heteroartic ring nuclei can be applied. For example, research disclosure (RESERCH DISCLO)
SURE) Item. 17643, page 23, section IV (1)
(December 978) 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 known to be useful heretofore. It is most commonly carried out after the completion of chemical sensitization and before application, but US Patent No. 3,628,9
69 and No. 4,225,666, it is also possible to add the chemical sensitizer at the same time and perform spectral sensitization at the same time as chemical sensitization.
It can be carried out prior to chemical sensitization as described in No. 8, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization.

Furthermore, US Pat. No. 4,225,666
It is also possible to add these said compounds separately as taught in No. or at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756.

The amount added is 4× per mole of silver halide.
Although it can be used at 10-5 to 15 x 10-2 mol, the more preferred silver halide grain size is 0.2 to 3 μm.
In this case, about 5 x 10-4 to 5 x 10-2 mol is 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, and examples of black and white photographic materials include X-ray film, general photographic film, and print-sensitive film. It can be preferably used for color paper.

There are no particular restrictions on other additives for the photographic light-sensitive material to which the emulsion of the present invention is applied;
losure) Volume 176, Item 17643 (RD1
7643) and volume 187, item 18716 (RD
18716) can be referred to. RD1
The locations where various additives are described in 7643 and RD18716 are listed below.

[0039] Additive type
RD17643 RD1871
61 Chemical sensitizer
23 pages 64
Page 8 right column 2 Sensitivity enhancer

Same as above 3 Spectral sensitizer, supersensitizer
pages 23-24 64
Page 8 right column~

Page 649 right column 4 Masu Haku
agent
Page 24 5 Antifoggants and stabilizers
Pages 24-25 Page 649 Right column 6
Light absorber, filter dye 25~
Page 26 Page 649 Right column ~ Ultraviolet absorber
Page 650 left column

[
7 Stain inhibitor
Page 25 right column Page 650 left to right column 8 Dye image stabilizer
Page 25 9 Hardener
Page 26 Page 651 Left column 10 Binder
Page 26 Same as above 11 Plasticizer, lubricant
Page 27 Page 650 Right column 12
Coating aids, surfactants 26
~Page 27 Same as above 13 Static inhibitor
Page 27 Same as above

[0041]
Among the above additives, antifoggants and stabilizers include azoles {for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, and benzotriazoles. , aminotriazoles, etc.}; Mercapto compounds {e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-
mercaptotetrazole), mercaptopyrimidines,
mercaptotriazines, etc.}; thioketo compounds such as oxadolinthion; azaindenes {e.g., triazaindenes, tetraazaindenes (especially 4-
Hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.}; benzenethiosulfones, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in its molecule, or a polymerized one. The coupler may 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). The product of the coupling reaction may also be colorless and include a colorless DIR coupling compound that releases a development inhibitor.

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. benzoylacetanilides, pivaloylacetanilides)
, etc., and examples of cyan couplers include naphthol couplers and phenol couplers.

As a cyan coupler, US Pat. No. 377
No. 2002, No. 2772162, No. 3758308
No. 4126396, No. 4334011, No. 43
No. 27173, No. 3446622, No. 4333999
Phenolic couplers having an ethyl group at the meta position of the phenol nucleus, 2,5-diacylamino substituted phenolic couplers, having a phenylureido group at the 2-position and the 5-position described in Phenolic couplers having an acylamino group, couplers in which the 5th position of naphthol is substituted with sulfonatemide, amide, etc. are preferred because they have excellent image fastness.

[0045] Of course, two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. do not have.

Hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochroman, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylated and alkylated phenolic hydroxyl groups of each of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximato)nickel complexes and (bis-N,N-dialkyldithiocarbamato)nickel complexes can also be used.

Photographic processing of light-sensitive materials using the present invention includes:
Any known method can be used, and any known treatment liquid can be used. Further, the treatment 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, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

[0048] The black-and-white developer includes known compounds such as dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-p-aminophenol). Developing agents can be used alone or in combination.

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

[0050] In addition, L. F. A. Meson, “Photographic Processing Chemistry”, Focal
Those described in Press Publishing (1966), pages 226-229, US Pat. No. 2,193,015, US Pat.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates;
Development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants may be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development inhibitors such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Pat. No. 4,083,723
The polycarboxylic acid chelating agent described in No.
LS) No. 2,622,950, etc. may also be included.

When color photographic processing is performed, the photographic material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (III) and cobalt (
III), compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, iron dichromate, organic complexes of iron(III) or cobalt(III), such as ethylenediamine tetrasa complex, nitrilotriacetic acid,
, 3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols.

Among these, potassium ferricyanide, sodium iron(III) ethylenediamine tetracomplex and ammonium iron(III) ethylenediamine tetracomplex are particularly useful. Ethylenediamine tetracomplex iron(III) complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions.

Bleaching or bleach-fixing solutions include US Pat.
No. 042,520, No. 3,241,966, Special Publication No. 4
In addition to the bleaching accelerators described in Japanese Patent Publication No. 5-8506 and Japanese Patent Publication No. 45-8836, and the thiol compounds described in Japanese Patent Application Laid-open No. 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.

[0055]

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (Preparation of AgCl emulsion) A silver halide emulsion was prepared as follows. Solution (1) Inert gelatin

30g NaC
l
(a)
g H2O

1000cc solution (2)
AgNO3

Add 17g H2O
200cc solution (3)
NaCl

(b) Add g H2O
200cc solution (
4) AgNO3

Add 70g H2O
600cc solution (5) NaCl

36g H2
add O
600cc

[
While vigorously stirring the solution (1) kept at 75° C., each of the compounds of the present invention was added as shown in Table 1, and then the solution (2) and the solution (3) were added simultaneously over a period of 10 minutes. Furthermore, solution (4) and solution (5) are
They were added simultaneously for 0 minutes to obtain a silver chloride emulsion. Comparative emulsion (emulsion (
A)) was cubic, but as shown in Table 1, the emulsions containing the compounds included in the present invention (emulsions (B) to (H)) were cubic when the amount of NaCl in (a) was small. When relatively octahedral or tetradecahedral particles had a large amount of NaCl in (a), tabular particles were obtained. Incidentally, an enlarged photograph of the grain crystal structure of Emulsion B is shown in FIG.

[0057]

[Table 1]

Example 2 The procedure of Example 1 was repeated, except that in the preparation of emulsion (A) of Example 1, the compounds included in the present invention were added as shown in Table 2 after addition of solution (2) and solution (3). A silver chloride emulsion was obtained in the same manner as in the preparation of Emulsion (A) in No. 1. The emulsion (A) prepared without adding the compound included in the present invention was cubic, whereas the emulsion (A) prepared without adding the compound included in the present invention was cubic.
For I) and (J), octahedral and tetradecahedral particles were obtained. Incidentally, an enlarged photograph of the grain crystal structure of Emulsion I is shown in FIG.

[0059]

[Table 2]

Example 3 The volume loads of the grains of emulsion (A) and emulsion (B) of Example 1 and the grains of emulsion (I) of Example 2 were determined by the Coulter counter method, and they were found to be 0.30 μm3 and 0.30 μm3, respectively.
．． They were 34 μm3 and 0.31 μm3. Wash with water and desalinate using the normal flocculation method, add gelatin, and hold at 40°C.
After adjusting the pH to 6.2 and pAg to 7.5, sodium thiosulfate, chloroauric acid and 4-hydroxy-6-methyl-
Chemical sensitization was optimally performed with 1,3,3a,7-tetrazaindene. Next, the following additives were added to the triacetyl cellulose film support provided with the undercoat layer, and an emulsion and a protective layer were coated to obtain Samples 1, 2, and 3. (1) Emulsion layer/emulsion...emulsion shown in Table 3

[0061]

[C5]

・Stabilizer: 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene・Coating aid: Sodium dodecylbenzenesulfonate・
Tricresyl phosphate/gelatin (2) Protective layer/2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt/gelatin

After exposing these samples to light through a light wedge, the following treatments were performed. ■ CN-16 processing specified by Fuji Photo Film Co., Ltd. ■
The optical density of the sample after CP-20 processing and development was measured (with a green filter installed). 2854°
Table 3 shows the development time and the optical density obtained when the film was exposed to K for 4000 lux for 10 seconds.

[0064]

[Table 3]

As shown in Table 3, the development progress of emulsions (B) and (I) of the present invention is faster than that of emulsion (A), and it is clear that they are preferable as emulsions for rapid processing. However, the relative densities in Table 3 are expressed as relative values to the optical density obtained with a development time of 2 minutes.

Example 4 After forming tabular silver chloride grains in the same manner as in emulsion (B) of Example 1, 10 −2 mol of potassium bromide per 1 mol of silver chloride was added to improve the grain surface. After locally forming a layer of silver bromochloride in the vicinity, an emulsion (emulsion (K)) which was optimally chemically sensitized in the same manner as in Example 3 was obtained. Emulsion (B),
Emulsion (A) was also optimally chemically sensitized in the same manner as in Example 3. The following compounds were added to each of emulsions (B), (A), and (K). Blue-sensitive sensitizing dye (a) Yellow coupler (b) Color image stabilizer (c)

[0067]

[C6]

[0068]

[C7]

Furthermore, stabilizer; 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene antifoggant; 1-phenyl-5-mercaptotetrazole hardener; 2,4-dichloro-6-hydroxy-s-s-triazine sodium coating aid; sodium dodecylbenzenesulfonate; sample (4), (
5) and (6) were obtained.

The sample was exposed under a light wedge and developed for 20 seconds, 30 seconds, and 45 seconds according to the following steps to obtain the results shown in Table 4. However, the relative sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to give a density of fog value + 0.5, and that of Sample 6 at 45 seconds was taken as 100. Treatment process temperature
Time color development 30~
45 seconds bleach fixation
Rinse at 30-35℃ for 45 seconds ■
30-35℃ 60 seconds

0
(Color developer)

(tank liquid) water

800ml
Ethylenediamine-N,N,N,N-tetramethylene phosphonic acid

1.5g potassium bromide
0.015g
triethanolamine

8.0g sodium chloride

1.4g potassium carbonate

25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4
-aminoaniline sulfate
5.0g N,N-bis(carboxymethyl)hydrazine
5.5g Fluorescent whitening agent (WHITBX 4
B, manufactured by Sumitomo Chemical)
Add 1.0g water

1000m
l pH (25℃)

10.05

(Bleach-fix solution) Water

400ml ammonium thiosulfate (70%)
100ml
sodium sulfite

17g Iron ethylenediaminetetraacetate (
III) Ammonium
55g Disodium ethylenediaminetetraacetate
5g ammonium bromide

40g
add water

1000ml pH (25℃)

6.0 (Rinse solution (tank solution and refill solution are the same)) Ion exchange water (
Calcium and magnesium are each less than 3 ppm)

00
73]

[Table 4]

As is clear from Table 4, emulsion (B) and emulsion (K) prepared using the compound of the present invention are comparable to comparative emulsion (A).
It is an emulsion that has high sensitivity compared to , and furthermore, development progresses quickly, making it suitable for rapid processing. The same results were obtained for the green-sensitive sensitizing dye and the red-sensitive sensitizing dye as for the blue-sensitive sensitizing dye.

Preferred embodiments of the emulsion of the present invention are as follows. 1. At least 70 mole percent of the total silver halide is chloride. 2. At least 90 mole percent of the total silver halide is chloride. 3. More than 6% of the total projected area of silver halide grains is (11
1) It is a surface.

4. The silver halide grains consist of a mixture of tabular grains and normal crystal grains. 5. The particles have a bromine- or iodine-containing layer near their surface. 6. The particles are spectrally sensitized with a methine sensitizing dye. 7. The particles are chemically sensitized with a sulfur sensitizer and/or a gold sensitizer.

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph showing the structure of silver halide crystal grains contained in emulsion (B) of Example 1. The photographing magnification is 8500x.

FIG. 2 is an electron micrograph showing the structure of silver halide crystal grains contained in emulsion (I) of Example 2. The photographing magnification is 8500x.

Claims (3)

[Claims] Claim 1: A silver halide photographic material having at least one silver halide emulsion layer on a support, comprising:
At least 50 mol% of the grains of the silver halide emulsion in the emulsion layer are composed of silver chloride, at least 50% of the total projected area of the silver halide grains are composed of grains having (111) planes, and the silver halide grains are composed of grains having (111) planes. 1. A silver halide photographic light-sensitive material, characterized in that grains are formed in the presence of at least one type of compound represented by the following general formula (I). General formula (I) [Image Omitted] In the formula, R1 and R2 represent a hydrogen atom, an aryl group or an aralkyl group. R1 and R2 may be the same or different. R3 represents an amino group or a carboxyl group. n represents an integer from 1 to 5. 2. The silver halide photographic material according to claim 1, wherein the silver halide grains are tabular grains having a diameter/thickness ratio of 2 or more. 3. The silver halide photographic material according to claim 1, wherein the silver halide grains are octahedral or tetradecahedral normal crystal grains.