JPH09166835A - Silver halide photographic emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high sensitivity and excellent pressure desensitizing and to improve storage property in a high humidity environment. SOLUTION: This photographic emulsion is prepared in such a manner that >=50% of the projected area of the whole particles consists of particles each having five or more dislocation lines on the host particle. These particles are such planer silver halide particles that the silver iodide content in the outermost layer of the host particle differs by <=5mol% from the silver iodide content in the first coating layer which covers the host particle and that the layer having the lower silver iodide content of the both layers has the silver iodide content between >=5mol% and <15mol%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic emulsion and a light-sensitive material which are excellent in sensitivity, pressure desensitization and storage stability under high humidity.

[0002]

2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more intense. For example, they have extremely high performance such as high sensitivity, excellent graininess, high sharpness, and excellent pressure resistance. It has been demanded.

For example, as a silver halide grain technique for achieving high sharpness, the grain thickness in the light entering direction is set so as to reduce light scattering by the silver halide grains, which is one factor that deteriorates sharpness. It is known to design by shifting from the light scattering length. In this case, in order not to deteriorate the granularity, it is necessary to design the thinner side with respect to the particle thickness that causes light scattering. Therefore, it is known that the grain size of the silver halide grains having a shape such as an octahedron or a hexahedron is reduced, the light receiving efficiency per grain is reduced, and the sensitivity is lowered.

As one method for solving this problem, it is known to use tabular grains. Regarding tabular silver halide grains, U.S. Pat.
No. 6, 4,439, 520, 4,414,310
Nos. 4,433,048 and 4,414,306
No. 4,459,353, JP-A-58-11193.
5, No. 58-111936, No. 58-111937.
No. 58-113927, No. 59-99433 and the like.

As a technique for increasing the quantum efficiency of photosensitization of silver halide grains, a technique of using a core having a high silver iodide content inside the grain is known. A technique for providing a high core is disclosed in JP-A-63-
No. 92942.

In recent years, demands for higher sensitivity and higher image quality have become more and more intense, and the use of silver halide grains provided with such a high iodine core phase is not limited to high-sensitivity light-sensitive materials but also to common color negative light-sensitive materials. Was also mandatory.

On the other hand, grains having such an internal high iodine core have a drawback that pressure desensitization is remarkable, which is a big problem in handling a light-sensitive material using such silver halide grains. There is. Pressure desensitization is improved by decreasing the silver iodide content of the internal high-iodity core phase,
Deteriorates photographic sensitivity and does not stand for practical use. Furthermore,
When tabular grains are used, the pressure resistance tends to be further deteriorated due to the shape factor. Therefore, it has been desired to develop a silver halide emulsion with less light scattering, high sensitivity, and improved pressure desensitization.

By the way, as a technique for improving the pressure fog of silver halide grains, iodide ions are rapidly added to the mixed solution during the formation of silver halide grains to locally increase the silver iodide content inside the grains. JP-A-62-58237
No. These techniques improve pressure resistance characteristics by localizing dislocation lines, silver iodide or high silver iodide-containing phases inside the silver halide grains. The effect is to improve pressure fog. there were.

Further, in JP-A-4-182635, a tabular grain having a phase having a silver iodide content of 8 mol% inside the grain, introducing a dislocation line, and thereafter having a shell phase of silver bromide. However, the effect on pressure desensitization is not mentioned. JP-A-4-350850 discloses a case of tabular grains having a phase having a silver iodide content of 8.9 mol% inside the grain, introducing a dislocation line and thereafter having a shell phase of silver bromide. Although shown, it does not mention pressure desensitization.

On the other hand, with the recent popularization of simple systems such as photographing units (films with lenses), films have come to be used and stored under harsh conditions that have never been expected.

Conventionally, silver halide color photographic light-sensitive materials tend to cause fog due to the presence of nuclei that can be developed even if they are not exposed to light. In many cases, reduction or deterioration of gradation is caused.

It is known to add an antifoggant, a stabilizer, or the like to a silver halide emulsion because it is desirable to minimize such an undesirable phenomenon. For example, US Pat. No. 2,403,927
Nos. 3,804,633, and JP-B-39-2825, and 4-hydroxy-6-methyl-1,3,3.
A, 7-tetrazaindene and the like have been used as antifoggants.

However, these compounds are not always sufficient in the effect of suppressing fogging during storage with time, and there are drawbacks such as lowering of sensitivity and softening of gradation, which are not satisfactory.

[0014]

An object of the present invention is to provide a silver halide photographic emulsion having high sensitivity, excellent pressure desensitization, and improved storage stability under high humidity, and a silver halide color using the same. To provide a photographic light-sensitive material.

[0015]

The above object of the present invention is achieved by the following constitution.

(1) 50% or more of the projected area of all silver halide grains is formed by forming five or more dislocation lines on the host grain, and the silver iodide content of the outermost layer of the host grain is: The difference in the silver iodide content of the first coating layer for coating the host grains is 5 mol% or less, and the silver iodide content of the layer having the smaller silver iodide content is 5 mol%. % Or more 15
A silver halide photographic emulsion comprising tabular silver halide grains of less than mol%.

(2) The silver halide photographic emulsion as described in 1 above, which is selenium-sensitized or tellurium-sensitized.

(3) The silver halide photographic emulsion as described in 1 or 2 above, wherein the coefficient of variation of the circle conversion diameter of the tabular grain projection surface is 20% or less.

(4) A photosensitive silver halide emulsion layer is provided on a support, and at least one of the silver halide emulsion layers contains the silver halide photographic emulsion described in 1, 2, or 3 above. A silver halide color photographic light-sensitive material characterized by:

The present invention will be described in more detail below. The tabular grains in the present invention are two parallel principal planes and have a circle equivalent diameter (diameter of a circle having the same projected area as that of the principal planes) and a distance between the principal planes (that is, of grains). A particle having a thickness ratio, that is, an aspect ratio of 2 or more.

It is preferable that 50% or more of the total projected area of all tabular grains of the present invention is tabular grains having an aspect ratio of 5 or more, and more preferably 8 or more.

The diameter of the tabular grains of the present invention is from 0.3 to 1
It is 0 μm, preferably 0.5 to 5.0 μm, and more preferably 0.5 to 2.0 μm. The particle thickness is preferably from 0.05 to 0.8 μm.

The measurement of the particle diameter and the particle thickness in the present invention can be obtained by the method described in US Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane) by dividing the standard deviation of the diameter distribution by the average diameter. ) Is preferably 30% or less, and 20%
It is more preferred that:

The halogen composition of the silver halide grains is preferably silver iodobromide or silver chloroiodobromide, and the silver iodide content is preferably 1 to 15 mol%.
It is more preferably from 10 to 10 mol%.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is the variation coefficient of the silver iodide content (the standard deviation of the silver iodide content intergrain distribution is the average silver iodide content. It is preferably 30% or less, more preferably 20% or less.

As the method for producing tabular grains, methods known in the art can be appropriately combined. For example, JP-A 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 63-151618, No. 63-16
No. 3451, No. 63-220238, No. 63-311
A known method such as No. 244 can be referred to.
For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is a type of the double jet method, and a soluble silver halide having a different composition, respectively. A triple jet method, which is added independently, can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. For thioethers, reference can be made to U.S. Pat. Nos. 3,271,157, 3,790,387, 3,574,628 and the like.
Further, the mixing method is not particularly limited, and a neutral method without using ammonia, an ammonia method, an acidic method, or the like can be used. However, from the viewpoint of reducing fogging of silver halide grains, it is preferably pH (hydrogen). The logarithm of the reciprocal of the ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention may contain iodide ions. In this case, the method of adding iodide ions in grain growth is not particularly limited, and iodide ions such as potassium iodide may be added. Alternatively, it may be added as fine silver iodide grains.

The silver halide emulsion of the present invention is disclosed in JP-A-1-
183417, 1-183644, 1-183
It is also preferable to grow grains by using fine silver halide grains in the same manner as the grains disclosed in Japanese Patent No. 645. In particular, as in the claims of JP-A-5-5966, the number of silver halide fine grains used for grain growth is two or more, and at least one of them is preferably composed of only one type of halogen element.

As in the claims of JP-A-2-167537, the grains are grown in the presence of silver halide grains having a solubility lower than that of the growing silver halide grains for at least one period of the grain growth process. An emulsion containing the above silver halide grains is desirable, and silver iodide is particularly desirable as the silver halide grains having a small solubility product.

The silver halide grains contained in the silver halide emulsion of the present invention have a projected area of 5 of the total silver halide grains.
0% or more has 5 or more dislocation lines. Further, in the present invention, the projected area of all silver halide grains is 50
% Or more is more preferable to have 10 or more dislocation lines, and it is more preferable to have 20 to 100 dislocation lines.

The dislocation line in the present invention means a linear lattice defect that forms a boundary between a region that has already slipped and a region that has not slipped yet on the slip surface of the crystal.

The dislocations of tabular silver halide grains are described in, for example, J. F. Hamilton, Photo. Sci. En
g. , 11, 57, (1967) and T.W. Shiozaw
a, J. et al. Soc. Photo. Sci. Jap. , 35,
213, (1972), etc., it can be observed by a direct method using a transmission electron microscope at low temperature.

That is, the silver halide grains taken out carefully so as not to apply a pressure such that dislocations were generated from the silver halide emulsion were placed on a mesh for electron microscope observation, and damaged by an electron beam (printout, etc.). In order to prevent), the sample is cooled and observed by the transmission method. At this time, since the electron beam is more difficult to transmit as the thickness of the particles is larger, the use of an electron microscope with a higher accelerating voltage enables more clear observation. From the photograph of the particles obtained by such a method, the position and number of dislocation lines of each particle when viewed from the direction perpendicular to the main plane can be obtained.

In the present invention, 50% or more of the projected area of all silver halide grains means that a transmission electron micrograph of silver halide grains contained in a silver halide emulsion is taken and the presence or absence of dislocation lines is confirmed. Randomly extracting 500 or more tabular silver halide grains that can be formed and integrating the projected areas of grains having 5 or more dislocation lines and grains having less than 5 dislocation lines, the projected area of the grains having dislocation lines is integrated. The value is equal to or more than the integrated value of the projected area of particles less than 5.

The position of the dislocation line of the tabular silver halide grain of the present invention is not particularly required to be at a specific position, but it is preferable that it is present at the fringe portion and inside the grain.

The fringe portion of the tabular silver halide grain as referred to in the present invention means the outer peripheral portion of the tabular silver halide grain, and more specifically, the center of gravity of the projection plane of the tabular silver halide grain as seen from the main plane side. In the perpendicular line drawn from the particle to each side of the particle, it means a region outside 60% (side side) of the length of the perpendicular line, preferably outside 70%, and more preferably outside 80%.

The dislocation line existing inside the grain in the present invention means a dislocation line existing in a region other than the above-mentioned fringe portion.

The method of introducing dislocation lines in the present invention is not particularly limited, but an aqueous potassium iodide solution or an iodine ion releasing agent such as iodide ethanol is added at the position where dislocations are to be introduced to cause halogen conversion on the grain surface. Preferred is a method of adding or adding a potassium iodide aqueous solution and a silver nitrate aqueous solution by a control double jet method,
The method of adding fine silver iodide grains is more preferable. that time,
While taking into account the particle size and aspect ratio of the silver halide grains, the composition of the silver halide grains at the time of addition, pBr and the like in the reaction vessel, an aqueous solution of potassium iodide, an iodide ion releasing agent, or fine silver iodide particles is used. The number of dislocation lines can be controlled by increasing or decreasing the amount of addition, but a specific amount of addition is preferably 0.2 to 10 mol% of the total silver amount of the grains.
0.5 to 5 mol% is more preferable. Further, by appropriately selecting the method of introducing dislocation lines, the composition of the surface of the silver halide grain, the pBr in the reaction vessel, or the like, or a material having adsorptivity to the silver halide grain, for example, general crystal habit control It is also possible to control the position where the dislocation line is formed by using an agent or the like. The position at which dislocations are introduced is preferably between 50 and 95% of the total grains, and more preferably between 60 and 80%.

In the tabular silver halide grain of the present invention, the difference between the silver iodide content of the outermost layer of the host grain before the introduction of dislocation lines and the silver iodide content of the first coating layer for coating the host grain. Is 5
It is at most mol%, more preferably at most 3 mol%. The volume fraction of each layer in the silver halide grains is 5% or more, preferably 10% or more.

When the content of silver iodide is continuously changed before and after the introduction of dislocation lines, the average silver iodide content of the portion occupying 5% in the volume fraction of the whole grain from the position where the dislocation lines are introduced is contained. Indicates the rate.

Of the layers before and after the introduction of the dislocation lines, the silver iodide content of the layer having a smaller silver iodide content is 5 mol% or more and less than 15 mol%, more preferably 5 mol% or more. 1
It is less than 0 mol%.

The silver iodide content in the outermost layer of the host grains before the introduction of dislocation lines is preferably 5 mol% or more and less than 10 mol%,
It is more preferably 5 mol% or more and less than 8.5 mol%.

In the tabular silver halide grains contained in the silver halide photographic emulsion of the present invention, the distance between two parallel principal planes in a tomographic plane passing through the center of the tabular silver halide grains and perpendicular to the principal plane. And the distance between two opposing surfaces in the direction parallel to the main plane passing through the center of the fault plane, the silver halide photographic emulsion of the present invention is gelatinized with a proteolytic enzyme and then the silver halide is used. The tabular silver halide grains contained in the photographic emulsion were embedded in methacrylic resin and the thickness was adjusted to 80 with a diamond cutter.
It can be determined by preparing a 0Å section, observing it with a transmission electron microscope, taking a photograph of the field of view, and measuring the distance on the photograph.

Further, in the tabular silver halide grains contained in the silver halide photographic emulsion of the present invention, the average silver iodide content is well known in the art with respect to the above-mentioned section used for observation with a transmission electron microscope. An EPMA method (Electro
n Probe MicroAnalyzer method), the silver iodide contents at two points located symmetrically with respect to the center of the grain are measured and averaged, respectively.

The EPMA method used here is as follows. First, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and X-rays emitted from the sample are analyzed by irradiating with an electron beam, whereby elemental analysis of an extremely minute region irradiated with the electron beam is performed. Is a technique for doing. By this method, the silver halide composition of each grain can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each grain. The average silver iodide content referred to here is a value obtained by averaging the silver iodide content of at least 100 grains by the EPMA method. The measurement is preferably performed at a low temperature in order to prevent the sample from being damaged by the electron beam.

Regarding the silver halide composition and structure of the silver halide grains contained in the silver halide emulsion of the present invention, in addition to the EPMA method described above, powder X-ray diffraction and fluorescence X may be used.
Line, XPS method (X-ray Photoelectric
It can be confirmed by combining on Spectroscopy) analysis method and the like.

The inside of the silver halide grain of the present invention may be reduction-sensitized. For example, JP-A-7-18161
Known methods such as No. 6 can be referred to.

In the emulsion according to the present invention, silver halide grains can be prepared, if necessary, by using a nitrogen-containing heterocyclic compound as described in Japanese Patent Application No. 6-316551.

Examples of the selenium sensitizer used in the present invention include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N). , N '
-Triethylselenourea, N, N, N'-trimethyl-
N'heptafluoroselenourea, N, N, N'-trimethyl-N'heptafluoropropynylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, N, N-diphenyl Selenourea, N-ethyl-N'-thiazolyl selenourea,
N-ethyl-N'-phenylselenourea, N-methyl-
N'-pyridylselenourea, N, N, N'-triphenylselenourea, N-methyl-N '-(4-nitrophenyl) selenourea, N, N, N', N'-tetraphenylselenourea, etc. ), Selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), Selenides (eg, diethyl selenide, diethyl diselenide, triphenylphosphine selenide, triethylphosphine selenide, diethylphosphine selenide, tritoluylphosphine selenide, tri (4
-Chlorophenyl) phosphine selenide, tri (2
-Pyridyl) phosphine selenide, etc.) and the like, which are conventionally known, for example, US Pat.
4,944, 1,602,592, 1,62
3,499, JP-A-60-150046, JP-A-4
-25832, 4-109240, 4-147.
No. 250. Particularly preferred selenium sensitizers are selenoureas, selenophosphates and selenides.

Specific techniques for using these selenium sensitizers include US Pat. Nos. 1,574,944 and 1,6.
02,592, 1,623,499, 3,29
7,499, 3,297,447, 3,32
0,069, 3,408,196, 3,40
8,197, 3,442,653, 3,42
0,670, 3,591,385, Japanese Patent Publication No. 52-
34491, 52-34492, 53-295.
No. 57-22090, JP-A-59-180536.
No. 59-185330 and 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
No. 3-24537, No. 3-111838, No. 3-1
No. 16132, No. 3-148648, No. 3-2374
50, 4-16838, 4-25832, 4-32831, 4-96059, 4-109.
No. 240, No. 4-140738, No. 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-1.
95035 and other patent specifications, and H. E. FIG. Specc
er et al. Journal of Photo
graphic Science Vol. 31, 15
8 to 169 (1983) and the like can be used.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally about 10 ^{-8 to} 10 ^-4 mol per mol of silver halide, The addition method is, depending on the properties of the compound used, a method of dissolving in water or an organic solvent such as ethanol or ethyl acetate, alone or in a mixed solvent, a method of premixing with a gelatin solution and adding, JP-A-4-140739. As described above, it is added during chemical sensitization by the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

When the selenium sensitizer is used, the temperature for chemical ripening is preferably 45 ° C. or higher, more preferably 50 ° C. or higher and 80 ° C. or lower. Further, the pH is preferably 4 to 9 and the pAg is preferably 6 to 9.5.

The tellurium sensitizer and the sensitizing method of the present invention include, for example, US Pat. Nos. 1,623,499 and 3,3.
20,069, 3,772,031, 3,53
1,289, 3,655,394, British Patent 23
Nos. 5,211, 1,121,496 and 1,29
5,462, 1,396,696, Canadian Patent 8
00,958, JP-A-4-204640, and JP-A-4-3
No. 33043, etc., and examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltelluroura, tetramethyltelluroura, N-carboxyethyl N, N-dimethyltelluroureas. Etc.), phosphine telluride (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, etc.), telluroamides (eg, telluroacetamide, N, N-dimethyl tellurobenzamide, etc.), Telluroketones, telluroesters, isoteric licyanates, etc. are mentioned. The technique of using these tellurium sensitizers is similar to that of selenium sensitizers.

In the present invention, other sensitizers can be combined, and it is particularly preferable to use sulfur sensitization, gold sensitization and reduction sensitization together.

In the present invention, the silver halide emulsion is represented by Research Disclosure 308119 (hereinafter RD308).
119) can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine composition 993 IA item Production method 993 I-A item and 994 E item Crystal habit (normal crystal) 993 IA item Crystal habit (twin crystal) 993 IA Item Epitaxial 993 I-A Item Halogen composition (uniform) 993 I-B Item Halogen composition (non-uniform) 993 I-B Item Halogen conversion 994 I-C Item Halogen substitution 994 I-C Metal content 994 I-D Item Monodisperse 995 I-F Item Solvent addition 995 I-F Item Latent image forming position (surface) 995 I-G item Latent image forming position (internal) 995 I-G Item Sensitive material (negative) 995 I-H item Applied Sensitive Material (Positive) 995 I-H Item Mixed Emulsion 995 I-J Desalting Item 995 II-A The silver halide emulsion of the present invention is physically ripened, chemically ripened and spectrally sensitized. It is possible to use what was done. The additive used in such a process is Research Disclosure No. 17643, no. 18716 and no.
308119 (hereinafter referred to as RD17643, RD1
8716 and RD308119).

The places described below are shown.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, I, J Item 23 ~ 24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 IV 24-25 649 Stabilizer 998 IV 24-25 649 Known photographic additives usable in the present invention Agents are also described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubrication Agent 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matt agent 1007 XVI Developer (included in light-sensitive material) 1011 XXB Various couplers can be used in the invention, and specific examples thereof can be used. Are described in Research Disclosure above. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Additives used in the present invention Can be added by the dispersion method described in RD308119XIV.

In the present invention, the aforementioned RD17643 is used.
28 pages, RD18716 pages 647-8 and RD308
The supports described in XIX of 119 can be used.

The light-sensitive material of the present invention includes the above-mentioned RD3081.
An auxiliary layer such as a filter layer or an intermediate layer described in Section 19VII-K can be provided.

The light-sensitive material of the present invention is RD30811 described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. .

The light-sensitive material of the present invention is the above-mentioned RD17643.
Pages 28-29, RD18716 647 and RD30
The development can be performed by the usual method described in XIX of No. 8119.

[0067]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of seed crystal emulsion-1 A seed crystal emulsion was prepared as follows.

Japanese Patent Publications No. 58-58288 and 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) at the same time while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. Was added over 2 minutes to form nuclei. Subsequently, the liquid temperature was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% potassium iodide) was added over 42 minutes by the simultaneous mixing method while maintaining the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing with water were immediately performed using a usual flocculation method.

The obtained seed crystal emulsion had an average spherical equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of silver halide grains had a maximum side ratio of 1.0.
The emulsion consisted of hexagonal tabular grains of .about.2.0.
This emulsion is called seed crystal emulsion-1.

[Solution A1] Ocein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m- [CH (CH ₃ ) CH ₂ O] _19.8- (CH ₂ CH ₂ O) _n H (m + n = 9.77) (Compound A) (10% methanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 containing 0.06 mol of potassium iodide 6. With vigorous stirring, 5 l of a 0% by weight gelatin aqueous solution was added over 10 minutes with 2 l each of 7.06 mol silver nitrate aqueous solution and 7.06 mol potassium iodide aqueous solution. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles were prepared, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is called SMC-1.

Preparation of silver halide emulsion Em-1 10% of seed crystal emulsion-1 corresponding to 0.178 mol and compound A
After keeping 700 ml of 4.5% by weight inactive gelatin aqueous solution containing 0.5 ml of methanol solution at 75 ° C., adjusting pAg to 9.0 and pH to 5.0, the following was carried out by the simultaneous mixing method with vigorous stirring. Particle formation was carried out by the procedure of.

1) 0.692 mol of silver nitrate aqueous solution and 0.
297 moles of SMC-1 and potassium bromide aqueous solution,
pAg was added while maintaining pH 9.0 and pH 5.0.

2) Then, 2.295 mol of silver nitrate aqueous solution, 0.071 mol of SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 9.0 and pH at 5.0.

During the formation of particles, each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion has an average spherical equivalent diameter of 0.65.
The emulsion consisted of tabular grains having the halogen composition shown in Table 3 and having an average aspect ratio of 4.3. When the emulsion was observed with an electron microscope, no grains having dislocation lines were present.

Preparation of Silver Halide Emulsion Em-2: 0.178 mol of seed crystal emulsion-1 and 10% of Compound A
700 ml of 4.5% by weight inactive gelatin aqueous solution containing 0.5 ml of methanol solution was kept at 75 ° C., pAg was adjusted to 8.4 and pH was adjusted to 4.0, and then CDJ (controlled Double jet) (silver nitrate aqueous solution and halogen salt aqueous solution were added in the liquid) to form particles by the following procedure.

1) 2.020 mol of silver nitrate aqueous solution (3.
5N), 0.188 mol of SMC-1, and an aqueous potassium bromide solution (3.5N), pAg of 8.4 and pH of 4.
It was added while keeping it at 0.

2) Then, the solution was cooled to 60 ° C., and pAg
Was adjusted to 9.8. Then, 1.067 mol of silver nitrate aqueous solution (3.5N), 0.080 mol of SMC-1 and potassium bromide aqueous solution (3.5N), pAg of 9.8,
It was added while maintaining the pH at 4.0.

During the formation of particles, each solution was added at an optimum rate so that the formation of new nuclei and the Ostwald ripening between particles did not proceed. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had an average spherical equivalent diameter of 0.65.
The emulsion consisted of tabular grains having a micrometer and an average aspect ratio of 8.1. Observation of this emulsion with a transmission electron microscope revealed that no grains having dislocation lines were present.

Preparation of Silver Halide Emulsion Em-3 0.178 mol equivalent of seed crystal emulsion-1 and 10% of compound A
700 ml of 4.5% by weight inactive gelatin aqueous solution containing 0.5 ml of methanol solution was kept at 75 ° C, pAg was adjusted to 8.6 and pH was adjusted to 5.0. Particle formation was carried out by the procedure of.

1) 2.121 mol of silver nitrate aqueous solution and 0.
174 moles of SMC-1 and an aqueous solution of potassium bromide
The pAg was added while keeping the pH at 8.6 and the pH at 5.0.
(Formation of host particles) 2) Then, the temperature of the solution was lowered to 60 ° C., and pAg was adjusted to 9.4. Then, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes. (Introduction of dislocation line) 3) 0.959 mol of silver nitrate aqueous solution, 0.030 mol of SMC-1, and potassium bromide aqueous solution, pAg of 9.
4, added while maintaining the pH at 5.0. (Shelling of host particles) Each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles from progressing through the formation of particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had an average spherical equivalent diameter of 0.65.
The emulsion consisted of tabular grains having the halogen composition shown in Table 3 and having an average aspect ratio of 6.6. Observation of this emulsion with an electron microscope shows 80% or more (projected area)
Five or more dislocation lines were observed both in the fringe area and in the inside of the grain.

Preparation of Silver Halide Emulsion EM-4 Emulsion EM-4 was prepared in the same manner as Emulsion EM-3.
However, in steps (1) and (3), the addition amounts of the aqueous silver nitrate solution and the silver iodide fine grain emulsion SMC-1 solutions were changed as shown in Table 1 below.

[0086]

[Table 1]

Preparation of Silver Halide Emulsion EM-5 0.178 mol of seed crystal emulsion-1 and 10 of Compound A were used.
% Gelatin solution (0.5 ml), 4.5% by weight inert gelatin aqueous solution (700 ml) at 75 ° C, pAg
Was adjusted to 8.4 and the pH was adjusted to 4.0, and particles were formed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 2.020 mol of silver nitrate aqueous solution (3.
5N), 0.188 mol of SMC-1, and an aqueous potassium bromide solution (3.5N), pAg of 8.4 and pH of 4.
It was added while keeping it at 0.

2) Then, the solution was cooled to 60 ° C., and pAg
Was adjusted to 9.8. Then 0.067 mol SMC
-1 was added and aging was performed for 2 minutes.

3) 1.004 mol of silver nitrate aqueous solution (3.
5N), 0.076 mol of SMC-1, and an aqueous potassium bromide solution (3.5N), pAg of 9.8 and pH of 4.
It was added while keeping it at 0.

During the formation of particles, each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had an average spherical equivalent diameter of 0.65.
The emulsion consisted of tabular grains having a micrometer and an average aspect ratio of 8.1. Observation of this emulsion with a transmission electron microscope revealed that 80% or more (projected area) of grains having 5 or more dislocation lines were present.

Preparation of Silver Halide Emulsions EM-6 to EM-8 Emulsions EM-6 to EM-8 were prepared in the same manner as Emulsion EM-5. However, in steps (1) and (3), the addition amounts of the aqueous silver nitrate solution and the silver iodide fine grain emulsion SMC-1 solutions were changed as shown in Table 2 below.

[0094]

[Table 2]

The characteristics of each emulsion thus obtained are shown in Table 3 below.

[0096]

[Table 3]

The following sensitizing dyes S-1, S-2, S-3, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to each of the above emulsions Em-1 to Em-8, and the emulsion was prepared according to a conventional method.
Chemical sensitization was performed so that the fog-sensitivity relationship was optimal.

The following stabilizers ST-1 and antifoggants AF-1 were added to each emulsion. The amount of ST-1 added was 1 g per mole of silver halide, and the amount of AF-1 was 15 mg per mole of silver halide.

To each of the obtained emulsions, the following cyan coupler C-1 dissolved in ethyl acetate and dioctyl phthalate was added, and further an emulsified dispersion, a general photographic additive such as a spreader and a hardener were added. To prepare coating solutions, each of which was applied onto the undercoated cellulose triacetate support by a conventional method and dried to obtain Sample No. 101 to 108 were produced.

These samples were subjected to wedge exposure through a Toshiba glass filter Y-48 using a 5400K light source according to a conventional method, and developed according to the following processing steps.

These samples were tested at a temperature of 45.degree.
The sample after being left for 7 days in the atmosphere of% RH was similarly exposed and developed.

Further, in order to evaluate the magnitude of pressure desensitization, these samples were subjected to 2 atmosphere in an atmosphere of 23 ° C. and 55% RH.
After allowing to stand for 4 hours to make the water content of each sample uniform, a 5g load is applied to a needle having sapphire with a radius of curvature of 0.025mmφ at the tip under the same atmosphere, and each sample is pulled at a speed of 1cm / sec. It was

Each compound used is shown below.

[0104]

Embedded image

(Treatment Step) Treatment Step Treatment Time Treatment Temperature Replenishment Amount Color Development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 C 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Dry 1 min 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

The sensitivity of each sample was such that the red density was fog +0.
The sample N
o. The value was shown as a relative value with the value of 101 of the immediate sample as 100.

Regarding the magnitude of pressure desensitization, the fog +
The width of decrease in density due to the scratching of the needle at the point of giving a density of 0.4 was evaluated. Specifically, a value obtained by normalizing the concentration decrease width −ΔD by the maximum concentration value Dmax of the sample −ΔD / D
The max was evaluated as the pressure desensitization width.

The results are shown in Table 4.

[0109]

[Table 4]

Example 2 Preparation of Silver Halide Emulsion EM-9 In the preparation of emulsion EM-8, the addition rate of silver nitrate aqueous solution, silver iodide fine grain emulsion SMC-1 and potassium bromide aqueous solution at the time of host grain formation was 1 / Emulsion EM-9 was prepared in the same manner except that No. 3 was used.

The coefficient of variation of projected surface circle equivalent diameter of the obtained emulsion EM-9 was 33%. The coefficient of variation of the equivalent circle diameter of the emulsion EM-8 was 18%.

In the same manner as in Example 1, the emulsion Em-9 was added to the sensitizing dyes S-1, S-2, S-3, sodium thiosulfate,
Chloroauric acid and potassium thiocyanate were added, and chemical sensitization was performed according to a conventional method so that the fog-sensitivity relationship was optimized. Stabilizer ST-1 and antifoggant A were added to each emulsion.
F-1 was added.

Preparation of Silver Halide Emulsion EM-10 Except that 40% of sodium thiosulfate was replaced with equimolar selenium sensitizer (triphenylphosphine selenide) during chemical sensitization of Emulsion EM-8. Similarly Emulsion E
M-10 was prepared.

Preparation of Silver Halide Emulsion EM-11 During chemical sensitization of Emulsion EM-8, 40% of sodium thiosulfate was added to equimolar tellurium sensitizer (n-propyl-di-i).
-Propylphosphine telluride) was used, and Emulsion EM-11 was prepared in the same manner.

To each of the obtained emulsions, the above-mentioned cyan coupler C-1 dissolved in ethyl acetate and dioctyl phthalate was added, and further a general photographic additive such as an emulsion-dispersed dispersion, a spreader and a hardener was added. To prepare a coating solution, which was then coated on the undercoated cellulose triacetate support by a conventional method and dried to prepare Sample No. 109-111 were produced. These samples were exposed and developed in the same manner as in Example 1 to evaluate their sensitivity and pressure resistance.

However, regarding the sensitivity, the sample No. The value was shown as a relative value with the value of 101 of the immediate sample as 100. Table 5 shows the results.

[0117]

[Table 5]

From Table 5, it can be seen that the samples of the present invention have no increase in fog, high sensitivity, little deterioration of stored samples, and low pressure desensitization range.

[0119]

According to the present invention, a silver halide photographic emulsion having high sensitivity and excellent pressure desensitization and improved storage stability under high humidity and a silver halide color photographic light-sensitive material using the same can be obtained. It was

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[Submission date] January 16, 1997

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Claims (4)

[Claims] 1. 50% of the projected area of all silver halide grains
The above is formed by forming five or more dislocation lines on the host grain, and the silver iodide content of the outermost layer of the host grain and the silver iodide content of the first coating layer coating the host grain are The difference is 5 mol% or less, and the layer having a smaller silver iodide content among the layers is a tabular silver halide grain having a silver iodide content of 5 mol% or more and less than 15 mol%. Characteristic silver halide photographic emulsion. 2. The silver halide photographic emulsion according to claim 1, which is selenium-sensitized or tellurium-sensitized. 3. The variation coefficient of the circle conversion diameter of the tabular grain projection surface is 20% or less.
A silver halide photographic emulsion as described above. 4. A photosensitive silver halide emulsion layer is provided on a support, and the silver halide photographic emulsion according to claim 1, 2 or 3 is contained in at least one of the silver halide emulsion layers. A silver halide color photographic light-sensitive material characterized by: