JPH02298935A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the AgX emulsion which can improve sensitivity, image quality and development progressability by applying the AgX emulsion which is sufficiently controlled in the position and number/cm<2> of chemical sensitizing nuclei. CONSTITUTION:This emulsion has the twin faces parallel with each other at >=70% of the projection area of the total AgX particles, has the crystal surface of a {100} face and {111} face of at least substantially the same halogen compsn. on one AgX particle surface and is preferentially formed with the chemical sensitizing nuclei on one crystal face. Silver halide particles are the planar silver halide particles having 3 to 20 aspect ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention provides silver halide (silver halide) useful in the field of photography.
Regarding photographic emulsions (hereinafter referred to as AgX), in particular, at least a dispersion medium and at least (Lo
ot and parallel twinned AgX grains having +1111 crystal surfaces.

′−′− and that. In general, in order to produce photosensitive AgX particles with high sensitivity and high image quality, it is necessary to control the position and number/cd of chemical sensitizing nuclei, which are photosensitive centers. Regarding the method of limitation, a patent application filed in 1983
-315741 and No. 63-223'739, the present invention relates to chemical sensitization of AgX emulsion grains having crystal surfaces of at least +1001 and (1111) planes on one AgX grain surface. Nuclei position and number/c
This concerns the limitation of d.

Recently, using normal-crystal AgX emulsion grains having (1001 planes and (l l 11 planes) with at least substantially the same halogen composition on the surface of one AgX emulsion grain, A method of forming chemical sensitization preferentially on one crystal face by utilizing the difference in chemical sensitization to form a crystal plane on which the adsorbent is adsorbed at a high density (hereinafter referred to as the B-plane) and a crystal plane on which the adsorbent is sparsely adsorbed (hereinafter referred to as the A-plane). A method has been proposed in which chemical sensitization is performed by adding an adsorbent, and chemical sensitization is preferentially formed on the crystal face where the adsorbent is sparsely adsorbed.
No., J. Phot.

Set, 23,249 (1975, especially 1986)
No. 4-74540, No. 64-62631, No. 64-4
No. 0938, Journal of the Photographic Society of Japan, Earthworks, 255 (1984
Reference may be made to FIG. 3 of the Japanese Patent Application No. 63-211445. However, the A with parallel twin planes
Tabular AgX emulsion grains with parallel twin planes, which are not known for gX grains, have many advantages as described in Japanese Patent Application No. 315741/1982. As mentioned above, it usually has the advantage that it can be freely changed in the range of 1 to 20. Therefore, in order to produce an AgX emulsion with higher sensitivity and higher image quality, it is necessary to limit the position and number/cJ of chemical sensitization in the AgX emulsion grain system having parallel twin planes. is the solution to this problem.

The purpose of the present invention is to investigate the position and number of chemical sensitization in parallel twin emulsion grains whose aspect ratio can be freely changed.
- It is an object of the present invention to provide an AgX emulsion in which sensitivity, image quality, and development progress can be improved by providing an AgX emulsion in which - is sufficiently controlled.

``1'' Il hole and the object of the present invention is that in an AgX emulsion having at least a dispersion medium and AgX particles, 70% of the projected area of all AgX particles is
% or more have twin planes parallel to each other, and one Ag
X grains have crystal surfaces of (1003 and (1111) having at least substantially the same halogen composition on the surface thereof, and chemical sensitization is preferentially formed on one crystal face. This was achieved by using an AgX emulsion.

First, the structure of the AgX particles of the present invention will be explained in detail, and then the method for producing the AgX particles will be explained in detail.

(2) A XI Discipline The AgX particles of the present invention are AgX particles having two or more, preferably two, mutually parallel twin planes in one AgX particle. When the aspect ratio is about 3 or more, the shape becomes flat. In the case of conventional tabular AgX grains, J, F,
Hamilton and L.

E. Bradyj. Appl. Phys., 35.
414 (1964), both the main plane and the outer surface of the edge part are (110) planes.# Therefore, it can be thought of as a structure in which single twin particles whose entire surface is a (111) plane are piled up. However, in the case of the tabular AgX grains of the present invention, the main plane is the (111) plane,
The AgX grains of the present invention have one A
The gX particles have at least +1001 planes and (1111 planes, but the ((1001 area)/((1001 area + (111) area) = 0.05 to 0.5, preferably 0
°1 to 0.4. This area ratio is determined by a measurement method that utilizes the adsorption dependence of the sensitizing dye on the (1111 and (100) planes) (T, Tan1. J, Imaging Sc.
i.

Earthworks, 165 (1985)]. However, the value obtained by subtracting about 7% from (1001 area%) obtained using this method is the actual (100) area%.
) surface, J-aggregate formation is difficult to occur.

In addition, the conventional edge part is (1111 plane) flat plate 41A
For gX particles, the angle between the principal plane and the edge plane is 109.5
``or 70.5@, but the angle between the main plane and the +100) edge plane of the AgX particles of the present invention is 125.3''. Therefore, the shape is not rounded or rounded and consists only of a flat outer surface. If the above (
100) Area ratio can be determined.

The AgX grains of the present invention have two or more, preferably two twin planes parallel to each other in one AgX grain, which is an ultra-thin layer (~0.1 μm thick) in the cross section of the emulsion coated film.
The section can be confirmed by observing a TEM image at low temperature (liquid nitrogen temperature or liquid He temperature).

Regarding this, see Hari, L., Black et al., The I
international East-WestSym
posiu+w II, Proceedings C-71 (1988)
You can refer to the description.

The AgX particles of the present invention have at least +1001 and +1111 crystal surfaces on the surface of one AgX particle, and
Chemical sensitization is preferentially formed on one crystal face. More preferably, chemical sensitization nuclei are preferentially formed on the 1001 planes. In the case of tabular grains, the outer surface has an area of the (+111) plane > an area of the +1001 planes. This is because the place where nuclei are generated is more limited and preferable. Also, preferential in this case means (number of chemical sensitizations on the crystal face where chemical sensitizations are preferentially formed/cd) /
(Number of chemical sensitization results/cd on crystal faces on which chemical sensitization nuclei are not preferentially formed) is 2.5 or more, preferably 5 or more. It is difficult to directly observe this ratio.

However, when the AgX emulsion coated material is exposed (1 second exposure) and developed with MAA-1 developer at 20°C for 10 minutes, the exposure gives a density of (maximum density - minimum density) x z. amount ~ its IO times the amount of exposure. This is because below this exposure amount, there are many particles that do not have inhibitory development nuclei, making it difficult to measure. The above ratio of chemical sensitization can be determined by forming a latent image, subjecting it to suppressed development, making the suppressed development nuclei visible by electron microscopy, and then counting the number of suppressed development nuclei. Regarding this method, see C. Birch et al., Jo.
urnal of Photographic Science
nce+ vol. 23, p. 249-256 (1975), and JP-A No. 64-62631.

Here, chemical sensitization refers to chemical sensitization consisting of sulfur, selenium, tellurium, gold, and Group 8 noble metal compounds alone or in combination, most preferably gold-sulfur sensitizing nuclei. They are called angry nuclei, gold-sensitized nuclei, noble metal-sensitized nuclei, and combinations thereof, and for details, the references mentioned below can be referred to.

As a further preferred embodiment of the present invention, the location where the chemical sensitization is generated is limited as described above, and the number/-
There are also limited aspects.

The halogen composition of the (1001 and (1111) crystal surface layers of the AgX particles of the present invention is substantially the same, and in the case of a moderate content, it is within 3 mol%, preferably 2 mol%. Indicates that the difference is within C
1 content indicates a difference within 10 mol%, preferably within 7 mol%, and the surface layer on the crystal surface in this case refers to 20 lattices, preferably 100 lattices.

The aspect ratio of the AgX particles of the present invention is 1 or more,
Preferably it is 3-20. The aspect ratio here is expressed as (diameter of tabular grain)/(thickness of tabular grain). Further, the diameter of a particle refers to the diameter of a circle having an area equal to the projected area of the particle when the particle is observed using an optical microscope or an electron microscope. Moreover, thickness is indicated by the distance between two parallel principal planes of a tabular grain.

Further, the inside of these particles is preferably reduction sensitized. Whether or not it has this reduction-sensitized silver nucleus is determined by
After wedge exposure and internal development using a conventional method, H-D El
! When the I-line is drawn, an inverted image of the existing internal fog is observed, so it can be easily determined. Regarding this, reference may be made to the description in Japanese Patent Application No. 63-223739.

The crystal structure inside the particle may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. The halogen composition change between the layers may be of a gradual increase type, a gradual decrease type, or a steep type, and can be selected depending on the purpose of use. Regarding this, JP-A-63-
No. 220238, No. 59-45438, No. 61-24
No. 5151, No. 60-143331, No. 63-929
The description in No. 42 can be referred to.

Further, the halogen composition change between the crystal surface layer and its interior may be of a gradual increase type, a gradual decrease type, or a steep type. is preferred.

The AgX particles referred to in the present invention include silver bromide, silver iodobromide,
These are silver chlorobromide and silver chloroiodobromide, and there is no particular restriction on the halogen composition.

The particle size distribution of the AgX particles of the present invention is preferably narrow, and the coefficient of variation is preferably 30% or less, more preferably 15% or less. However, the coefficient of variation is determined by the variation in grain size expressed by the circular diameter of the projected area of the tabular grains.
standard deviation) divided by the average particle size].

In the case of AgX particles having two mutually parallel twin planes, the shape of the main plane is a hexagon with (maximum adjacent side ratio ≦ 2), and in the case of AgX particles having three mutually parallel twin planes. In the case of , the shape of the principal plane is a triangle. The maximum adjacent side ratio herein refers to (maximum side length/minimum side length) of sides forming a hexagon in one hexagonal tabular grain. In addition, the shape may be a hexagonal shape or a triangular shape with rounded corners. Furthermore, it can also take on a more advanced circular shape.

The AgX emulsion of the present invention has at least a dispersion medium and AgX particles, and 70% or more, preferably 90% or more, more preferably 95% or more of the projected area of all the AgX particles is occupied by the AgX particles of the present invention. It is characterized by being

A typical example of the specific structure of the AgX particles of the present invention is shown in FIG. However, the embodiment of the present invention is not limited to this.

Japanese Patent Application No. 62-141112 discloses tabular AgX grains in which chemical sensitizing nuclei are preferentially formed at the edges of tabular grains, but after the grain formation, an aqueous Kl solution is added to cause halogen conversion. These particles are different from the particles of the present invention in that their edge portions and main plane portions have different halogen compositions.

Japanese Patent Application No. 63-251215 by the present inventor shows an example in which chemical sensitizing nuclei are preferentially formed at the edge portions of tabular grains. These particles have a substantially different halogen composition in the crystal surface layer of the (111) plane, and are different from the AgX particles of the present invention.

The tabular AgX grains described in JP-A-58-113928 are not grains in which (100) planes are intentionally formed in the edge portions, and are different from the AgX grains of the present invention.

ONOA xt (7)-” method Next, a method for producing AgX particles of the present invention will be described.

Conventional methods for forming tabular grains having two or more parallel twin planes are described in Japanese Patent Application Laid-open No. 58-113926-11392.
The description in No. 8 can be referred to. In addition, regarding the particle formation method of AgX particles having only two mutually parallel twin planes, the present inventor published Japanese Patent Application Laid-Open No. 63-151618.
No., Patent Application No. 63-315741, No. 63-88376
Reference may be made to the description in No. 63-153722. In addition, regarding the method for forming tabular grains with good monodispersity among these grains, and the method for forming the tabular AgX grains whose center portion has a high iodine content, the description in the above patent by the present inventor is also referred to. It can be used as a reference. Briefly, these particles are formed by a nucleation-ripening-crystal growth process. Twinning plane formation occurs during nucleation. The frequency with which twin planes are formed during nucleation depends on various condition factors (referred to as supersaturation factors) during nucleation. Therefore, by adjusting these supersaturation factors, it is sufficient to maximize the parallel double twin grain ratio in the finally produced AgX particles.

Usually, the tabular grains produced in this way have (111) planes in both the main plane and the edge plane, as described above. This can be confirmed by the method of T.Tan1 mentioned above.

In the case of parallel double twinned grains, the shape of the principal plane is a hexagon with (Il large adjacent side ratio ≦2), and in the case of parallel double twinned grains, the shape of the principal plane is a triangle. After forming such tabular grains, the AgX grains of the present invention are formed as follows.

■ When the A g
By stacking them on the supranuclear plane, the (1001 plane) appears at the edge portion.

The rate of ripening at this time depends on the particle size of the tabular grains, the pAg of the solution, the concentration of the AgX solvent, and the temperature, and the dependence can be seen in FIG. 7 of Japanese Patent Application No. 153722/1983. . fI O01 on the shaded side of the curve in the figure
Tabular grains with faces are produced. In order to obtain the AgX particles of the present invention having the desired (1001 area ratio), the (100) area ratio of the AgX particles obtained by the aging may be measured by the method of T and Tan1 above. However, conditions such as aging time, pAg, temperature, AgX solvent concentration, etc. may be changed. Generally, the lower the pAg and the more the AgX solvent concentration increases, the more the +1001 area ratio increases.

When C, D, J, AgN0ff aqueous solution and halide salt aqueous solution are added to gelatin aqueous solution, the cubic height and 14
pAg (or p
Br) region has a growing halogen composition, coexisting AgX
It depends on the amount of solvent, degree of supersaturation during growth, pH, etc. Regarding these and the formation region of cubic crystal and tetradecahedral products when normal crystal AgX particles are aged, see Mur.
ofushi et al., International Con
gress of r'hotographic 5c
ience.

Proceedings of Tokyo (1967), J. Rod.
gers.

Sya+posium Paper on Growt
h or PhotosensitiveCrysLa
ls, Cambridge (1978), T.
, G.

Bogg et al., J. Phot, Sci., 24. 8
1 (1976), P. Glafkides,
Chimie eL Physique P
hoLographiques.

Fifth Edition, Edition de
Iousine Nouvelle.

Paris (1987), patent application 1986-2114
The description in No. 45 can be referred to. For example, AgB
At a supersaturation level of 50 to 80% of the critical growth rate at r, the cubic crystal formation region has a pAg of 7.4 or less, and the tetradecahedral product formation region has a pAg of 7.85 to 7.degree.

Generally, the shape of the tabular grains obtained by the above ripening changes as the AgX solvent concentration increases during ripening, and the lower the pAg
As the grain size increases, the hexagonal or triangular corners of the tabular grains melt and become closer to a circular tabular shape, becoming thicker and having a lower aspect ratio. Further, the ripening temperature can be in the range of 40 to 80°C. AgX solvent concentration is 0 to 0
．． 2 mol/1 can be used. A g
As the PI agent, those mentioned below can be used.

■ The AgX emulsion is then treated with silver salt and halide salt C, D, under pAg in the cubic or tetradecahedral product forming region.
J. Add. Regarding the 1) Ag region in this case, reference can be made to the description in the literature described in (2) above. Also in this case, as the AgX solvent concentration increases during crystal growth,
Furthermore, the lower the pAg, the greater the (1001 area ratio) and the thicker the plate becomes.
The description in No. 5 can be referred to.

■ In addition, (1001 or (
The AgX emulsion grains of the present invention can also be formed by adsorbing an adsorbent that selectively adsorbs on the 111) plane and adding a silver salt and a halide salt to cause crystal growth. Regarding the surface-selective adsorbent, reference may be made to the descriptions given below.

In this way, Ag
After gX particles are formed, chemical sensitization is performed to preferentially form chemical sensitized nuclei on one crystal face. This chemical sensitization is basically performed by any of the following four methods.

1) A surface-selective sulfur sensitizer that reacts selectively on specific crystal faces is used as the sulfur enhancer. Regarding the surface selective reactivity of this sulfur aggravating agent, Japanese Patent Application Nos. 63-211445, 64-74540, 64-62631, 6
The description in No. 4-40938 can be referred to.

For example, the emulsion conditions are pl(6,5, pAg8°5.
When aged at 50°C for 60 minutes, Hypo reacts very selectively on the (1111 face) compared to the (1001 face), forming a sulfur sensitized surface.

TrieLhyl thiourea reacts very selectively on the (1001) plane compared to the (111) plane, and
00) selectively forms a sulfur sensitized layer on the surface.

, but under other conditions, e.g. (pH 6,5, p A
g8.5.65℃, 60 minutes) aging (plr6.5,
The aging conditions (pAg 7.7, 50°C, 60 minutes) are not preferable because the selectivity is low. Including other sulfur sensitizers, its surface selectivity increases under low temperature (55-25° C.) and high pAg conditions (pAg>8.3).

In addition, in this case, if a gold sensitizer is added at the same time for chemical sensitization, the surface selective reactivity will be reduced.
The method of No. 11445 (after sulfur sensitization, washing with water,
A method of adding gold sensitizer after removing residual sulfur sensitizer,
Or after 80% or more of the added sulfur sensitizer has reacted,
(a method of adding a gold sensitizer), or a method of adding a gold sensitizer after performing sulfur sensitization, adding an additive that reacts with the unreacted sulfur sensitizer to nullify it, and then adding a gold sensitizer. It can also be used.

2) After adsorbing an adsorbent that preferentially adsorbs onto one crystal face into the AgX emulsion (hereinafter, this face will be referred to as the B-face).
, a chemical sensitizer is added, and a chemical sensitizer is preferentially formed on the crystal plane (hereinafter referred to as A-plane) to which the adsorbent is not preferentially adsorbed.

3) After adsorbing an adsorbent that preferentially adsorbs on the 8 sides of the AgX emulsion, a surface-selective sulfur sensitizer that reacts selectively on the A side is added, and Forms chemical sensitization. In this case, the chemical sensitization nucleation is controlled by the surface-selective adsorbent and the surface-selective sulfur sensitizer, so the selectivity is further improved.

4) After adsorbing the surface-selective adsorbent in steps 2) and 3), an adsorbent for limiting the number of chemical sensitizations/C11l can be further adsorbed. In this case, the adsorbent is: an adsorbent that adsorbs on both the OA surface and the 8 surface and has low selectivity; (1) an adsorbent that selectively adsorbs on the 8 surface;
An adsorbent that selectively adsorbs on the A side, but also partially (10 to 50% of the total adsorption amount) on the 8th side, can be mentioned.

Therefore, almost all conventional adsorbents such as sensitizing dyes and antifoggants can be used as adsorbents in this case.

In the above, other examples of sulfur sensitizers that chemically sensitize the (100) plane more selectively include thiourea 11, rhodanines, oxazolidines, polysulfides, and selenoureas. . More specifically, the following compound examples can be mentioned.

CHsCONHCMHl C3 Examples of adsorbents that tend to adsorb more selectively on the (1111 plane) than on the (100) plane include Br- and D-1) 3,3'-disethyl-t
hiazolino-dicarb.

cyanine bro+wide D-2) CCHt)aSOz-(C11ri gsOsNaD-3
) ClO2C1Hs I.

D-4) D-6) D-7) (CH)sSO3- etc. can be mentioned. (111) surface than (1
Examples of dyes that tend to selectively adsorb onto the 001 plane include E-1) 3.3'-bis(4-5ulfobuLy
l) 9-methyl-thiacarboxy
anineE-2) S03- 5OsNa 503- 5OsNa E-4) CIllS (Nio Its(C1
1g) s (CHx) xSO3-
5O3Na E-5) CJ
s(CIlg)! (C1lt)
aE-6) So, -SO, Na E-7) etc.

In addition, the adsorption power of sensitizing dyes and additives to silver halide is
It is known that in addition to the crystal habit and halogen composition of 5ubs Lrate, it depends on various atmospheres of the emulsion (emulsion pH, Ag, coexistence of adsorption promoters, etc.).

Therefore, using this knowledge, the adsorption strength of sensitizing dyes and additives can be adjusted.

In addition, in general, the adsorption power is strong (I see, the aggravating dye is J
A aggregates are easily formed, and J aggregates are preferable because they more effectively inhibit the formation of chemically sensitized nuclei.

Regarding these details, the above-mentioned surface-selective adsorbent, surface-selective sulfur agglomerate, and other specific examples, see JP-A-64-74540 and JP-A-64-62631.
No. 64-40938, patent application No. 63-251215
No. 63-315741, No. 63-26979, and the cited documents thereof can be referred to.

In addition, the adsorbent can also be used as a functionally separated adsorbent as described in Japanese Patent Application No. 63-26979.

Further, the content of the above sulfur sensitizer in the AgX particle phase is 10
-q~10~3 mol 1 mol AgX, preferably 10~
10 −4 mol 1 mol AgX.

In addition, in the flat 4iAgX emulsion of the present invention, the four sides are +10
As mentioned above, the 01 side is more preferable.

The amount of adsorbent used is 15% of the saturated adsorption amount.
It is preferable to use it at ~130%, preferably 20-90%.

As the gold sensitizer used in the present invention, kumquat salt (for example, US Pat. No. 2,399,083) can be preferably used. More specific examples include chloroauric acid, alkali metal chlorauric acid salts, potassium aurithiocyanate, aurithiocyanate, aurithiocyanate, sodium aurithiosulfate, and auritu-5-sulfobenzothiazole-2-sulfide chloride. The content of gold sensitizer in the AgX particle phase is 10-9 to 10-3 mol 1
mol AgX, more preferably 10-1 to 10-4 mol 1
molar AgX.

Basically, the AgX emulsion of the present invention can be produced in this manner, but the following conditions may also be mentioned as conditions for producing the AgX emulsion of the present invention.

The pi of the reaction solution during grain formation can be 2 to 10, but when introducing reduction-sensitized silver nuclei, it is 8.0 to 10.
9.5 is preferable, and Ag is added to promote crystal growth.
X solvents can be used.

The concentration of the AgX solvent can be 0 to 0.2 mol/l. As the AgX solvent, those described below can be used. The temperature during crystal growth is usually 4
0-80°C can be used. The method of adding silver ions and halogen ions during the crystal growth stage is to add a silver salt aqueous solution and a halide salt aqueous solution, and to prepare an ultrafine grain emulsion (A g
C1, AgBr, Ag! and/or a mixed crystal thereof) or a method of superimposing them can be used. Alternatively, a method can be used in which the rate of addition of silver ions and halogen ions is increased during crystal growth. Regarding these, reference may be made to the descriptions in Japanese Patent Application Nos. 63-223739, 63-151618, and 59-45438.

The silver halide grains of the present invention can be used as an emulsion by themselves, but a core/shell type direct reversal emulsion may be formed using the grains as a core and used.

Furthermore, a shallow latent type emulsion may be formed using the particles as a core.

The tabular grains can also be used in high hardness systems.

In the ripening process of the present invention, in order to promote ripening,
Further, during the crystal growth period after ripening, a halogenated solvent may be used to promote crystal growth and to adjust the degree of supersaturation during nucleation.

Examples of frequently used silver halide solvents include thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2.222°264)
No. 2,448,534, No. 3゜320.06
9), ammonia, thioether compounds (for example, U.S. Pat. No. 3,271.157, U.S. Pat. No. 3,574,6)
No. 28, No. 3,704.130, No. 4,297.
439, 4.276.347, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-8)
No. 2408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

Although the AgX emulsion of the present invention can be used as an emulsion by itself, it is usually used with the addition of a sensitizing dye and an antifogging agent.

Sensitizing dyes used as the adsorbent and spectral sensitizing dye of the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, and holopolar dyes.
Mention may be made of polymethine dyes including cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol merostyryl and streptocyanine.

Antifoggants used as adsorbents and antifoggants include, for example, tetrazaindenes, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, and bromobenzimidazole. mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitropenztriazoles, mercaptotetrazoles (especially
-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxacyrithione, and also benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives. , gallic acid derivatives, ascorbic M derivatives, and the like.

In addition, pendant dyes (compounds in which residues of a sensitizing dye and an antifoggant are organically bonded) described in Japanese Patent Application No. 63-311518 can also be preferably used.

As the sulfur sensitizer used in the present invention, Japanese Patent Application No. 62
In addition to the sulfur sensitizer of Reference Example 1 of No.-219982, U.S. Pat.
No. 2. 410. No. 689, same No. 3,189,
458, No. 3,501.313, French Patent No. 2,059,245, JP-A-63-301039, etc., or active gelatin can be used.

There are no particular restrictions on the additives that can be added from grain formation to coating of the AgX emulsion of the present invention.

Additives that can be added include dopants for AgX particles [Group 8 noble metal compounds, other metal compounds (gold, iron, lead, cadmium, etc.), chalcogen compounds, SCNCN
Chemical dispersion media, sensitizing dyes (for blue, green, red, infrared, panchromatic, ortho, etc.), supersensitizers, fogging agents (organic fogging agents such as hydrazine compounds, inorganic fogging agents) , surfactants (antifoaming agents, etc.), emulsion precipitants, soluble silver salts (AgS
CN, silver phosphate, silver acetate, etc.), emulsion precipitants, latent image stabilizers, pressure desensitization inhibitors, thickeners, hardeners, developers (hydroquinone compounds, etc.), developer modifiers, etc. For specific compound examples, usage methods, etc., the descriptions in the following documents can be referred to. Additives that are usually added after chemical sensitization to the end of the coating process include surfactants such as coating aids, hardeners, binders, and photosensitive material property improvers (plasticizers, antistatic agents, ultraviolet absorbers, etc.). agents, light scattering or absorbing materials, capping agents, lubricants, optical brighteners, dimensional stabilizers, anti-adhesion agents, etc.), photographic property improvers (development accelerators such as polyethylene oxide, contrast enhancers such as glutaraldehyde compounds) etc.), halogen acceptor dyes, etc., and can be added depending on the purpose. Specific examples of these compounds and how to use them, as well as support, microcellular support, undercoat layer, antihalation layer, surface protective layer, intermediate layer, and emulsions with high sensitivity to low sensitivity in order from the incident light side. Layer structure with two or more layers, overcoat N on the back surface to improve the back surface characteristics of the support, simultaneous multi-N coating method,
Drying method, use of hydrogen sensitization, reaction equipment for AgX emulsion production, stirring equipment, atmosphere during exposure (temperature, pressure, humidity, type of gas, etc.), exposure method (pre-exposure, high-intensity exposure, low-intensity exposure) etc.), types of light sources (natural light, laser light, etc.), photographic processing agents and processing methods, self-suppressing developers, partial particle development, waterless washing processing methods, etc., the following documents may be referred to. can.

The AgX emulsion of the present invention can be used as a color photographic material. In that case, the color image forming method, layer structure, use of color filters, color image forming materials that can be used, and color image forming agents that release photographically useful fragments such as development inhibitors and development amplifying agents during color development. or non-color image forming agents (e.g. DIR couplers, super DIR couplers, DAD? couplers, DTR compounds, etc.), as well as oxidatively cleavable DIR compounds, polymer couplers, diffusible dye-forming couplers, color masks for color images, For details on coloring dye-forming couplers and/or competing couplers, scavengers, bleaching of developed silver and omission of bleaching, image dye stabilizers, omission of yellow filter layer, etc., specific compound examples, usage, etc., see the following references: You can refer to the description.

In addition, for the AgX emulsion of the present invention, any combination structure with known techniques and known compounds described in the following documents can be used.

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GIafkides, Chimie et Phy
sique Photographiques.

Fifth HDition+ Edition d
e 1'Usine Nouvelle.

Parks, 1987, 5th Edition + Paul
Montel, Paris, 1 957
Year.

The silver halide emulsion of the present invention can be used in black and white silver halide photographic materials (e.g., (negative film, photographic paper, reversal film, direct positive color sensitive material, silver dye bleaching photograph, etc.)
It can be used for. Furthermore, it can be used in photosensitive materials for diffusion transfer (e.g., color diffusion transfer elements, silver salt diffusion transfer elements), heat-developable photosensitive materials (black and white, color), high-density digiLal recording materials, photosensitive materials for holography, etc. .

The emulsion of the present invention is Example 1 of JP-A No. 62-269958.
, Implementation of No. 63-151618 N13.14, No. 60
-95533, 59-142539, 62-253
159, Example 9 and 6 of Japanese Patent Application No. 62-203635
No. 2-141112, No. 61-109773, No. 62
-54640, 62-208241, 62-2
It can be preferably used as a constituent emulsion in the Examples of No. 63319.

The AgX particles of the present invention obtained in this way, in which the production location or production location and number/e1M of chemical sensitizing nuclei on one AgX particle are controlled, have the following characteristics. .

■ Provides photographic properties with low latent image dispersion, high sensitivity, and good development progress. This effect is especially great for AgX particles with a particle size of 1.0 μm or more, which tend to cause latent image dispersion.

■ Chemical sensitizing nuclei exist preferentially on the A side, and sensitizing dyes preferentially exist on the 8th side, so electrons and holes generated during ■-blue exposure are efficiently separated and regenerated. Coupling is prevented. ■ There is a low probability that the generated latent image will be destroyed by dye holes. ■ Even when a large amount of sensitizing dye is adsorbed, there is almost no sensitizing dye in the area where the latent image nucleus, which is the starting point of development, exists. Because there is no dye, there is little development inhibition due to the dye.
Therefore, photographic properties with high sensitivity and good development progress can be obtained.

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

A gelatin aqueous solution (1
1,01/, gelatin VB, KB with average molecular weight M = 20,000
4.5g of AgN0.r, pH 6.0) and stirred while keeping the solution temperature at 30°C. Aqueous solution [32g of AgNo in 100-M = 20,000 gelatin 0.1wt
%,'HNO! (IN) 0.17m (including) and KBr
Aqueous solution [100-23.2 g of KBr, M = 20,000 gelatin Q, 7 wt%, HNOs (IN) 0.17 m
1] were simultaneously added at 25 d/min for 66 seconds.

One minute after the addition, an aqueous gelatin solution (H!0140d1 deionized alkali treated gelatin 32 g 1 pH 6,0) was added and the temperature was raised to 75°C.

After raising the temperature and aging for 20 minutes, AgN0. Aqueous solution (
15wt% solution) was added at 6.5aZ/min to increase the m potential to +
Zero-order NH, No, aqueous solution (50 wt%
7.5d of liquid) and 7.5d of NHs aqueous solution (25wt% liquid).
5a# was added and aged for 20 minutes. Next, I(NOi
(3N) aqueous solution was added to adjust the pH to 8.0, and further KBr aqueous solution was added to bring the silver potential to -20 mV. Next, AgN0° aqueous solution (15 wt%) and KBr aqueous solution (1
1 wL%) was added to C, D, J (silver potential -20 mV
)did. Addition was made at 8-7 minutes for the first 10 minutes and at 15s7/min for the next 20 minutes. Further additions were made at 60 mV for 10 minutes at 20+n7/min. After 5 minutes, the temperature drops to 30℃
The emulsion was washed with water. The emulsion was redispersed at 40°C and the pH
6,5, pA was adjusted to 88.6.

The TEM image of the replica of the AgX particles obtained and the measurement results by the method of T and Tan1 described above were as follows.

The emulsion was chemically aggravated by the following three methods, and an antifoggant (TAI (4-hydroxy-6-set)
hyl-1.

3, 3a, 7-tetraazaindene)
) with 7XlO-', 1 mol Ag and the usual amount of thickener [
(para-sulfostyrene Na) salt homopolymer
er), a coating aid, and a hardening agent, and coated with a gelatin protective layer at 11.5 g silver/day on a TAC (cellulose triacetate) transparent base and dried.

■ The temperature of the emulsion was raised to 60°C, and a sulfur sensitizer (5-ben
zylidene-3-ethylrhodanine
) was added in an amount of 10-5 mol and 1 mol Ag. Next, after 3 minutes, the gold-thiocyanate complex f-form 0, 5 x 10-
'1 mol Ag was added and aged for 30 minutes. Next, D-3 dye was added in an amount of 75% of the saturated adsorption amount, and the temperature was lowered to 40° C. after 7 minutes.

■ The emulsion was heated to 50°C and a sulfur enhancer (Liriet
hyl thiourea) at 0.8X10-' mol 1
Only molar Ag was added. After aging for 40 minutes, gold
0.4 x 10-'mol 1 dl A'g of thiocyanate complex
75% of the saturated adsorption amount of D-3, which had been aged for 10 minutes, was added thereto in an amount of 75% of the saturated adsorption amount, and the temperature was lowered to 40°C after 7 minutes.

■ The temperature of the emulsion was raised to 50°C, and the saturated adsorption amount of D-3 was 7
Zero-order sulfur enhancer (tri) added and adsorbed in 5% amount
ethyl thiourea) was added in an amount of 0.6XlO-'mol 1 mol 8g, and after aging for 40 minutes, the gold-thiocyanate complex was added in an amount of 0.3X10-'mol 1 molAg.
Only added. After aging for 10 minutes, the temperature was lowered to 40°C.

These samples were passed through a wedge for 10-2 seconds.
I used e-exposure and -blue light. Next, E, K, prescription M
Developing with AA-1 developer at 20° C. for 10 minutes gave the results shown in Table 1. Compared to (2), which was chemically sensitized by the conventional method, the latent image forming position was limited in methods (2) and (2) of the present invention, and the effect of improving sensitivity was observed. In the case of -blue light, the effect was even greater due to the separation effect between the dye holes and the latent image, confirming the effect of the present invention.

Table 1 Large Coal L The same procedure as in Example 1 was used up to the point where the nucleus was formed and the temperature was raised.

After aging at 75° C. for 35 minutes, an aqueous A g N O 3 solution (15 wt % solution) was added at a rate of 6.5 min/min to bring the silver potential (c vs. saturated calomel electrode) to 3 mV.

Next, A g N Os aqueous solution (15 wt% liquid) and KBr
Using an aqueous solution (13 wt% liquid), the initial flow rate was 6@l/min, and the linear flow rate increase rate was 0.45aZ/min for 50 minutes.C,D
, J was added (lit potential 3 V), and +40 mV of C, D, and J were added for 5 minutes at 20 @ 1/min.5
After a few minutes, the temperature was lowered and the emulsion was washed with water at 30°C. The emulsion was redispersed at 40°C and adjusted to pH 6.5 and pAg 8.6. The results of observing the 78M image of the replica of the obtained AgX particles and the results of measurement by the method of T and Tan1 described above were as follows.

The emulsion was chemically sensitized using the same formulation as in Example 1 (1) to (2), coated, and photographic sensitivity was examined, and similar effects were observed.

1 ± 1 The same procedure was used as in Example 2 until the temperature was raised. After raising the temperature and aging for 10 minutes, a 0° AgN aqueous solution (1
5wt% liquid) 6. Added at 5a//min, +15mV
Next, an aqueous A g N Os solution was added,
The same N H4N O as in Example 2 was set to +90 mV.
s aqueous solution and N H2 aqueous solution were added and aged for 20 minutes. Next, HNOs (3N) aqueous solution was added, pH 7,
Adjusted to 5. Observing the 78M image of the replica of the emulsion grain sampled at this point, the shape was cubic.
D, J, added.

The first 5 minutes were 8-7 minutes, followed by accelerated flow addition for 40 minutes at a linear flow rate increase of 0.4 sJ/min for the first 8-7 minutes. After 5 minutes, the temperature was lowered and the emulsion was washed with water at 30°C. The emulsion was redispersed at 40°C and pH 6.

5, pAg8.6 was used. The properties of the obtained AgX particles were as follows.

The emulsion was chemically sensitized using the same formulation as in Example 1 (1) to (2), coated, and photographic sensitivity was examined, and similar effects were observed.

Aqueous gelatin solution CHI was added to a reaction vessel having a volume of 41 kg.
O1,21, M=20,000 gelatin 9゜6g, KBr2
．． Add 4g of AgNOz, pH 6.53, and stir while keeping the solution temperature at 30°C.
7wL%, containing 0.17-! of HN Os (IN)] and a halide salt aqueous solution [100-! KBr1 inside
3gSKI0.2g, M=20,000 gelatin 0.7wt%
] was simultaneously added at 48117/min for 66 seconds. After 1 minute, an aqueous gelatin solution (Ht0430aZ, 40 g of deionized alkali-treated gelatin, pH 6.5) was added and the temperature was raised to 75°C. After raising the temperature, it was aged for 15 minutes, and then a 7-gNOs aqueous solution (10 wt% liquid) was
0-order NH4N added at 7 min to bring the silver potential to 40 mV
o, aqueous solution (50 wt%) 9-1 and further N Hx aqueous solution (
25 wt%) was added to the solution, and micronization was performed for 15 minutes. Next, add HN O3 (3N) aqueous solution and adjust the pH (
I gave it a 5. Next, AgN0. Aqueous solution (15 wt%) and halide salt solution (1.47 Kl in 10Q+a7)
containing 9.57 g of g5KBr) at 20 m7/min.
C, D, and J were added for minutes (silver potential 70 mV). Next, the same AgN0° aqueous solution (20 wL%) and KBr aqueous solution (
C, D, and J were added (silver potential 40 mV) for 7 minutes at 20-7 minutes. Further, C, D for 7 minutes at 20-7 minutes.

J, added (silver potential 70 mV). After 5 minutes, the emulsion was washed with water at 30°C. The emulsion was redispersed at 40°C and adjusted to pH 6.5 and pAg 8.6. Obtained A
The characteristics of the gX particles were as follows.

The emulsion was chemically sensitized using the same formulation as in Example 1 (1) to (2), coated, and photographic sensitivity was examined, and similar effects were observed.

[Brief explanation of the drawing]

FIG. 1 schematically shows a typical example of the specific structure of AgX particles of the present invention. (a) shows a type in which the entire AgX particle is almost uniform, and (b)
) The figure shows an example of a double structure particle in which the halogen composition of the core part and 5he11 parts are different, and (C) shows the core part, middle part, and 5he11 part.
An example of a triple structure in which the halogen composition of he11 part is different is shown. Patent applicant: Fuji Photo Film Co., Ltd. Figure 1 Procedural amendment written on June 2, 1990, Title of the invention: Silver halide photographic emulsion, Relationship with the person making the amendment Patent applicant: 4, Subject of the amendment: Description The description in column 5 of "Detailed Description of the Invention" in the "Detailed Description of the Invention" section of the statement of contents of the amendment is amended as follows. 1) Correct “receptor dye” on page 33, line 20 to “receptor, dye.” 2) From page 35, line 19 “Tokukaisho” to page 37 1
Correct the line up to ``57'' as shown in the attached sheet. Attachment Research Disclosure + (Research D
isclosure)+176S (item 17643
) (December, 1978), Volume 184 (Item 18)
431) (August, 1979), Vol. 216 (Item 2172B) (May, 1982), JCIA Monthly Report 198
4th year, December issue, P, 18-27, Journal of the Photographic Society of Japan, 4
9, 7 (1986), 52, 144-166
(1989), JP-A-58-113926-113
92B, 59-90842, 59-142539,
62-25319, 62-99751, 63-1
51618, 62-6251, 62-115035
, 63-305343, 63-220238, 6
2-2773L 62-269958, 61-112
142, Special Publication No. 59-43727, Special Patent Application No. 63-223
739, 63-315741, JP-A-62-2665
38, 63-220238, 63-7846.5,
Japanese Patent Application No. 62-208241, No. 63-129226, No. 63-311518, and Japanese Patent Application No. 1983-131541. U,S
, 4,707°436, edited by James, (T, H, Ja
sxes) Theory of Photographic Process, 4th edition, Macmillan Publishing,
New York (1977), Zelikman et al.
ZcIIkman atBl, ) + Making and Coating Photographic Emulsion (Making and Coating Photo
graphic Emulsion), Focal Press, 1964, Graphic (P, Glafkides), Shimmy
Efijiku Photographic (Chimie et
Physiques Photographique
). 5th edition, Edison da Risine Nouvelle (Ed.
ition de l'Usine Nouvelle
) + Paris (1987), 2nd edition, Bowl Montel, Paris (1957), Holista (K, R, Ho1l
ister), Journal of Imaging Science (Journalof I@aging 5ci)
ence) + Volume 31, P, 148-156 (1
978), Maskasky, J.E.
) + Volume 30, P, 247-254 (1986)
, Frieser et al., eds., Fundamentals of the Silver Halide Photographic Process (Di
e Grund Iagen Der Photogr
aphischenProzesse Mit SrI
verhalogenrden>lAkademische Verlaggeselshi+7to(Akadeta+sche
VerIaggesel l5chafυ, Frankfurt (1968)

Claims (1)

[Scope of Claims] 1) In a silver halide photographic emulsion having at least a dispersion medium and silver halide grains, 70% or more of the projected area of all silver halide grains has mutually parallel twin planes, and 1)
have {100} and {111} crystal surfaces with at least substantially the same halogen composition on two silver halide grain surfaces, and chemically sensitized nuclei are preferentially formed on one crystal surface; A silver halide emulsion characterized by: 2) The silver halide emulsion according to claim 1, wherein chemically sensitized nuclei are preferentially formed on the {100} plane. 3) The silver halide emulsion according to claims 1 and 2, wherein the silver halide grains are tabular silver halide grains having an aspect ratio of 3 to 20.