JP2001255611A - Method for preparing silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a silver halide emulsion excellent in the sensitivity to granularity ratio. SOLUTION: 1) In a method for preparing silver halide emulsion grains having no twin face in the grains, seed crystals for the grains are formed in a dispersion medium solution containing 10-8 to 1.0 mol/l, in total, of one or more adsorbents selected from (i) a compound containing one or more onium salt groups in one molecule, (ii) an aromatic compound or the like having one or more iodine groups and one or more -OH groups substituted on the aromatic ring and (iii)-(viii) compounds described in the specification. 2) In a method for growing the seed crystals by adding fine silver halide grains of 0.1 to 200 nm average diameter to a silver halide emulsion with the seed crystals, the fine silver halide grains are formed in a dispersion medium solution containing 10-8 to 1.0 mol/l, in total, of one or more adsorbents selected from the compounds (i)-(viii).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing silver halide (hereinafter referred to as "AgX") emulsion grains useful in the field of photography.

[0002]

BACKGROUND ART AgX emulsions having at least AgX grains (A ₆₎ and a dispersion medium and water, was added AgX fine particles (A _7), mixed, dissolving the A _7, Ag on the surface of the A ₆ ⁺
The method of growing AgX particles, in which A ₆ is grown by depositing A ₆ and X ⁻ , has the advantage of realizing more uniform growth of A ₆ , and many ideas have been proposed for the method. I have. For example, JP-A-1-183644, JP-A-4-34544, JP-A-4-184326 to JP-A-4-184.
No. 330, U.S. Pat. No. 4,433,048, Research
Disclosure magazine, item 38957 (September 1996)
[Hereinafter, "RD (1996 years) and referred] can be the description of the reference. In this case, A ₇ is quickly disappeared after the addition, A ₆ grew rapidly, and eventually give It is preferable that the photographic sensitivity and the image quality of the resulting grains are high.The prior art has not yet sufficiently satisfied this requirement.A normal crystal grain emulsion having substantially no twin plane has a narrow grain size distribution, Particle characteristics (average AgX composition of whole particles, A in particles)
(gX composition structure, impurity doping amount, etc.) are uniform among grains, and when the emulsion is used as it is, an extremely hard image is obtained, and it is still used in many AgX photographic light-sensitive materials. These emulsions are required to be further improved in sensitivity and image quality.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an AgX emulsion having better photographic sensitivity and image quality.

[0004]

Means for Solving the Problems (I-1). The object of the present invention has been achieved by the following embodiments. (1) In a silver halide emulsion (A ₃ ) having at least silver halide grains (A ₁ ) and a dispersion medium (A ₂ ),
The A 60 to 100 _[1 has a particle number ratio (%), preferably 90 to 100, more preferably from 99 to 100, most preferably no 99.9 to 100 are two or more twin planes within the grain particles , and the 10 ^-8 to 1.0 mol per reaction solution 1.0 liters in a total amount of one or more seed crystals of the a ₁ (a ₅₎ of forming adsorbents below a1) wherein (Z ₁₎ , Preferably 1
0 ^-7 to 0.1 molar containing dispersant solution (A ₄₎ A method of manufacturing a silver halide emulsion, characterized in that the place in. a1) Compounds described in the following (i) to (viii). (I) a compound containing one or more onium bases in one molecule, (ii) an aromatic compound having an aromatic ring substituted with one or more iodo groups and one or more -OH groups, (iii) a nitrogen-containing compound. A heterocyclic compound,
One or more heterocycles containing two or more nitrogen atoms in a 4- to 7-membered ring
A compound containing at least one in the molecule, (iv) a cyanine dye, (v) a compound having a heterocyclic group containing a divalent sulfur group, (vi) a thiourea compound, (vii) an aminothioether, (viii) Organic compounds containing divalent sulfur groups and having a total carbon number of 25 or less, excluding gelatin and NH ₄ ⁺ . (2) the A 60 to 100 _[1 has a particle number ratio (%), preferably 90 to 100, more preferably from 99 to 100, most preferably no twin planes in 99.9 to 100 are within a particle grain above, wherein it is (a ₁₁₎ (1) a method of manufacturing a silver halide emulsion as claimed. (3) at least the silver halide grains (B ₁₎ and the dispersion medium (B ₂₎ and the average silver halide emulsion (B ₃₎ diameter with water (nm) is 1.0 to 200, preferably 1.0 to 10
By adding a silver halide emulsion (C ₂ ) containing 0, more preferably 1.0 to 50 silver halide fine grains (C ₁ ), dissolving C ₁ and depositing it on B ₁ ,
_{In the} method of growing silver halide grains for growing ₁ ,
C 60 to 100 _[1 has a particle number ratio (%), preferably 9
0 to 100, more preferably 99 to 100, and most preferably 99.9 to 100 are fine particles having no more than two twin planes in the particles, and C ₁ is the adsorbent (Z) described in a2) below.
₂ ) One or more of them in a total amount of 1
0 ^-8 to 1.0 mol, preferably 10 ^-7 to 0.1 molar containing dispersion medium solution (B ₄₎ A method of manufacturing a silver halide emulsion, characterized in that the place in. a2) Compounds described in the following (i) to (viii). (I) a compound containing one or more onium bases in one molecule, (ii) an aromatic compound having an aromatic ring substituted with one or more iodo groups and one or more -OH groups, (iii) a nitrogen-containing compound. A heterocyclic compound,
One or more heterocycles containing two or more nitrogen atoms in a 4- to 7-membered ring
A compound containing at least one in the molecule, (iv) a cyanine dye, (v) a compound having a heterocyclic group containing a divalent sulfur group, (vi) a thiourea compound, (vii) an aminothioether, (viii) Organic compounds containing divalent sulfur groups and having a total carbon number of 25 or less, excluding gelatin and NH ₄ ⁺ . (4) The above-mentioned ( ₁ ), wherein the C1 is a fine particle having no twin plane in the particle, in which the particle number ratio (%) is 60 to 100, preferably 90 to 100, more preferably 98 to 100. 3) The method for producing a silver halide emulsion according to the above. (5) The value of [(total number of particles having two or more twin planes in the particle) / (total number of seed crystals)] of the seed crystal is x ₁ , and the adsorbent (Z
Except that the absence of ₁₎ when the said value of the seed crystals formed by the same conditions and with _{x 2, x 1 = (0~0.9} ) x 2,
Preferably (0 to 0.5) x _2, more preferably (0
0.2) The method for producing a silver halide emulsion according to the above (1), wherein x is ₂ . (6) The value of [(total number of particles containing one or more twin planes) / (total number of seed crystals)] of the seed crystal is x ₃ , and the adsorbent (Z ₁ ) is not present. when the said value of the seed crystals formed by the same conditions and with x ₄ except, x ₃ = (0~0.9) x
_4, preferably (0 to 0.5) x _4, more preferably (0-0.2) above, wherein it is x ₄ (2) A method of manufacturing a silver halide emulsion as claimed. (7) Except that the value of [(total number of particles including two or more twin planes) / (total number of fine particles)] of C ₁ is x ₅ and the adsorbent (Z ₂ ) is not present. when the said value of the fine particles was formed in the same condition was set to _{x 6, x 5 = (0~0.9} )
x _6, preferably (0 to 0.5) x _6, more preferably (0-0.2) above, wherein it is x ₆ (3) A method of manufacturing a silver halide emulsion as claimed. (8) The value of [(total number of particles containing one or more twin planes) / (total number of fine particles)] of C ₁ is x ₇ , except that the adsorbent (Z ₂ ) is not present. when the said value of the fine particles was formed in the same condition was set to x ₈ is, x ₇ = (0~0.
9) x _8, preferably (0 to 0.5) x _8, more preferably (0-0.2) above, wherein it is x ₈ (4) A method of manufacturing a silver halide emulsion as claimed. (9) 6 of the total projected area of all silver halide grains of B ₃
0-100%, preferably 90-100%, more preferably 97-100% have an aspect ratio (diameter / thickness) of 1.6-500, preferably 2-500, more preferably 4-500, diameter ( μm) is 0.05-20, preferably 0.1-10, and the thickness (μm) is 0.005-0.
5, preferably a tabular grain of 0.005 to 0.3, more preferably 0.01 to 0.1, a coefficient of variation (standard deviation of distribution / average value) of diameter distribution and thickness distribution of the grain. Is preferably 0.01 to 0.6, more preferably 0.01 to 0.30, and still more preferably 0.01 to 0.6.
(3) or (4), which is 0.10
A method for producing a silver halide emulsion as described above. (10) The tabular grains are {111} tabular grains having a principal plane of {111} planes and having 2 to 4, preferably 2 to 3, and more preferably 2 twin planes parallel to the principal plane. The method for producing a silver halide emulsion according to the above (9), wherein (11) The main plane of the tabular grains is a {100} plane, and the outline of the main plane is a right-angled parallelogram or a shape with rounded corners, and a straight line portion of the quadrilateral or side is extended. The ratio of the adjacent sides of the formed quadrilateral [(longest side length / shortest side length) of one tabular grain] is preferably 1.0.
To 5.0, preferably 1.0 to 2.0. The method for producing a silver halide emulsion according to the above (9), wherein (12) The method for producing a silver halide emulsion according to the above (1) or (3), wherein the compounds Z ₁ and Z ₂ are compounds containing one or more pyridinium bases in one molecule. (13) that formation of the C ₁ is, 0～100M from the reaction vessel containing the B _3, which is formed preferably 0～30M, more preferably in a reaction vessel which is placed within a distance of 0~5m The method for producing a silver halide emulsion according to the above (3) or (4), wherein (14) After the C ₁ is formed, 10-1 of Z _{2 in} C ₂
00%, preferably 30-100%, more preferably 8%
0 to 100% is, after being removed from the C _2, the C ₂ is B
Wherein characterized in that added to ₃ (3) or (4)
A method for producing a silver halide emulsion as described above. (15) said C ₁ is formed in a batch type reaction vessel, Z ₂ is AgX1.0 moles per ^10-9 during the formation of C ₁ to 1.0
Mol, preferably 10 ^{-8 to} 0.1 mol, and when the molar amount of AgX in the reaction vessel becomes Z ₅ times, Z
_{2 has} a concentration of 10 ⁻³ Z ₅ to 10 ³ Z ₅ times, preferably 10
^-2 Z ₅ ^{~10 2} Z ₅ fold amount by the (3) or (4) A method of manufacturing a silver halide emulsion of, wherein a is an aspect that increases than the density before the increase. (16) During the formation of the seed crystal, Z ₁ is added in an amount of 1 per 1.0 mol of AgX.
0 ^{-9 to} 1.0 mol, preferably 10 ^{-8 to} 0.1 mol, is added. When the molar amount of AgX in the solution becomes Z ₆ times, the concentration of Z ₁ becomes 10 ^-3 Z _6. to 10 ³ Z ₆ times, preferably 10 ^-2 Z ₆ ~10 ² Z ₆ times amount corresponding, above, wherein it is an aspect to increase than the density before the increase (1) or (2) according A method for producing a silver halide emulsion. (17) AgI content: of the C ₁ (mol%) is 1.0 to 10
0, preferably 10 to 100, more preferably 30 to 1
00. The method for producing a silver halide emulsion according to the above (3) or (4), wherein (18) B ₄ methionine group content (μmol / g) or histidine group content (μmol / g) is 0 to 33, preferably 0
The silver halide according to (3) or (4), which is an aqueous solution containing 0.1 to 15, preferably 1.0 to 5 by mass of 20, more preferably 0 to 10, gelatin by mass. Emulsion manufacturing method. (19) The silver halide emulsion grains (A ₀ ) formed in the above (3) or (4) are 60 to 100%, preferably 90 to 100%, more preferably 90 to 100% of the total projected area of all silver halide grains. 97 to 100% is the aspect ratio (diameter /
Thickness) is 1.6 to 500, preferably 2 to 500, more preferably 4 to 500, and diameter (μm) is 0.05 to 2
0, preferably 0.1 to 10 and a thickness (μm) of 0.00
5 to 0.5, preferably 0.005 to 0.3, more preferably 0.01 to 0.1, and is a tabular grain having a principal plane of {111} plane or {100} plane. The coefficient of variation of the diameter distribution (standard deviation / average of the distribution) and the coefficient of variation of the thickness distribution are preferably 0.01 to 0.6, more preferably 0.01 to 0.30, and still more preferably 0.01.
The method for producing a silver halide emulsion as described in the above item (3) or (4), wherein (20) 60% to 100% of the total projected area of all silver halide grains of the A _1, preferably from 90 to 100%, more preferably from 97 to 100%, the diameter ([mu] m) is 0.01
0, preferably 0.01 to 10, and the coefficient of variation of the diameter distribution is 0.01 to 0.6, preferably 0.01 to 0.3,
The method for producing a silver halide emulsion according to the above (1) or (2), more preferably 0.01 to 0.10.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail.
You. (I-2) Description of AgX particles. (A-1) A₁ , B₁ , A₀ Common characteristics. The diameter is the diameter of a circle having an area equal to the projected area of the particle
Point to. The average AgX composition of one of the particles and the total
There is no particular limitation on the average AgX composition, and AgCl, AgB
r, AgI or a mixture of any two or more thereof in any ratio
There is a crystal. The coefficient of variation of the interparticle distribution of the composition is preferably
0-0.6, more preferably 0-0.3, even more preferably
Is 0 to 0.10. AgX composition in particles is uniform
There are composition type and heterogeneous composition type. As an example of the latter,
AgX composition between adjacent phases is AgCl content, or AgBr
Content, or 0.1 to 100, preferably AgI content, preferably
Two or more layers, preferably 2 phases, differing by 1 to 80 mol%
AgX composition between adjacent phases
Changes can be rapid, rapid or gradual (continuous,
Stepped multi-stage change type). For example, a core layer and a shell layer
Particles having a double-layered structure comprising 2 to 19 shell layers.
There is a multi-structure particle consisting of a structure. Also, certain of them
The thickness (μm) of the layer is specified to a specific value of 0.01 to 1.0.
Particles, the AgI content and the AgBr content of that particular layer.
Rate, AgCl content (mol%) of 0.1 to 99.9, preferably
Or particles defined to a specific value of 1 to 90. Particle table
Uniformly over the entire surface or at a specific location (for example, one to all
Corner or ridgeline, center of flat surface or helicopter
Part), the surface layer [surface to (from the surface to 10 nm)
AgX composition, AgBr content and AgI content
Ratio, AgCl content is 5 to 100 mol%, preferably 30
An epitaxial growth portion having a composition different from
Or particles having a mixed crystal part (generally referred to as a guest part).
Here, the priority is given to other places (the mole of the guest section).
Amount / unit area of host particle surface cm^Two ] Is 1.2 to ∞ times,
Preferably, it indicates 3.0 to ３ times. In addition, the particles
Particles obtained by laminating one or more shell layers as core particles
is there. Particles of 10^-2Moderate visible light exposure for 10 seconds
Surface latent image depending on where the latent image is preferentially formed.
Image type particles (formed preferentially in the area within 1 nm from the surface
), Shallow inner latent particles (1 to about 20 nm depth from the surface)
), Deep-inner latent particles (from the surface
(Preferentially formed inside at a distance of about 21 nm or more)
it can. Here, priority means (number of latent images to be formed / unit)
Product cm^Three ) Is 1.3 to ∞ times that of other places, preferably 3 to ∞
Points to double. The latent image forming place is formed by a chemical sensitizing nucleus (after
The above description can be used as a reference.)
In this embodiment, the chemical sensitization nucleus is preferentially formed at a specific location.
Corresponding to Preferential means [molar amount of chemical sensitization nucleus / unit
Unit volume cm^Three Is 1.3 to ∞ times, preferably 3 times,
It means that it is ~ ∞ times. For details, see Reference 1 below
Can be referred to. Other surface latent images [0.1-1
Start development when the surface is developed after appropriate exposure for 0 seconds
Formation) takes precedence over the specific location on the particle surface [other
For the location of (the number of the starting points / unit area cm^Two ) Is 1.
3 to ∞ times, preferably 1.6 to ∞ times]
Mode. For details, refer to the description in Reference 2.
You. Here, surface development means only the latent image existing in the surface area
Is developed with a surface developer. The solution contains an AgX solvent
The liquid is substantially free of liquid. Also, the liquid has a normal surface
Developer solution, its developer concentration or alkali concentration
Diluted to 0.01-90%, preferably 0.01-30%
There is a suppressed suppressing developer, which can be preferably used. The
Regarding the developing solution, the description in the following Reference 3 can be referred to. The
AgX shell layer is formed on the particles,
Latent particles can also be produced. The above-mentioned moderate is optical
When exposed through the edge and developed, (maximum density
(Minimum density) × Exposure amount giving a density of 0.5 to 10
Indicates double exposure. Dislocation lines 1 to 10 inside^Three Have a book
60% to 100% of the total number of dislocation lines
Is a particle present in the same side corner region. Average in particles
Reduced silver, silver oxide, chalcogen silver,
A metal atom among the elements of atomic numbers 11 to 92, preferably
Group 8 metal atom or its ion, metal complex (inorganic coordination
Complex with a ligand, organic ligand, or both ligands, central gold
A polynuclear complex having 2 to 20 atoms), a chalcogen element
One of element or ion, chalcogen compound and metal oxide
The concentration (mol / mol AgX) is 10^-Ten -10^-1, Good
Preferably 10^-9-10^-2Can be doped with
A_TenCalled an aspect). Preferred conditions during particle formation (p
H, pAg, addition method, time, temperature, etc. ₃₁Note
You can refer to the listing. ), Adding a reducing agent or the compound,
It can be doped into particles. CN^-, SCN^-,I
Midazole group, pyridine or bispyridine group, divalent sulfur
Coordinate one or more of one or more of the contained organic groups
The complex which is a child is preferred. Details on metal complexes and ligands
For details, see Reference 4, Research Disclosure Magazine, item 3
8957 (September 1996) [hereinafter, (R.D. 1996)]
], Dictionary of Inorganic Compounds and Complexes, Kodansha (1997
Year) can be referred to. In addition, JP-A-11-23
As described in No. 7710, an organic hole trapping agent is granulated at the above concentration.
It can be doped in the child. As an example of the heterogeneous dope
To a specific location on the particle surface or the epitaxial phase
Preferentially doped embodiment, one or more layers of the multi-structured particles
There is an embodiment in which a specific layer is preferentially doped. The guest
Parts are from 0.1 to 100%, preferably 1%, of the total surface area of the particles.
Can form on ~ 50% of the surface. [(Dissolution of host particles
Degree)-(solubility of the guest part)] is positive or negative.
is there. (Amount of silver in all guest units / Amount of silver in host unit)
Is preferably 10^-6-10, more preferably 10^-Four~
1.0. For details on particles with guest parts
References 4, 5 and (R.D. 1996) can be referred to.
You. In addition, it satisfies the provisions of (I-1) and
Examples include particles of any structure. For general details
For this purpose, the description in the following literature can be referred to. Two twin planes
One or more grains with one or more twins
(A)₁₁Regarding the structure of),
You can refer to the description. AgI particle formation conditions and the particle shape
For details, see Physical Review, 161, 848
(1967), U.S. Pat. No. 4,184,878,
Reference can be made to the description of Kaihei 59-119344. (A-2) A₁ Characteristics. A₁ 60 to 100% of the total number of AgX particles, preferably 9
0-100%, more preferably 98-100% is A₁₁so
is there. A₁ , A₁₁Surface is {111} face, {100}
Face, {kko}, {hhl} h> l, {hll} h>
l, {hko}, {hkl} alone, or
Or 2 to 7 types in any ratio,
Regarding this, the description in Reference 7 can be referred to. A₁₁Narase
Grains having 1 to 50, preferably 1 to 10 dislocation lines
Child (A₁₂) And particles (A ₁₃), And
Particles having 1 to 50 edge dislocation lines (A₁₄) And have no
No particles (A_Fifteen). A₁₁Aspect for particle shape
Non-tabular grains having a ratio (diameter / thickness) of 1.0 to 1.59
(A₁₆) And an aspect ratio of 1.6 to 500, preferably
Tabular grains having a principal plane of {100} planes (A
₁₇). A₁₆For example, cube, octahedron, 14 faces
Body, rhombic dodecahedron, rhomboid 24-hedron, 38-octahedron, 46-hedron
There is a body, a hexahedron. A₁₇For the description of the item (A-3)
You can refer to the listing. (A-3) B₁ And A₀ Description. B₁ And A₀ Are known or will be known in the future
AgX grains of the following types, tabular grains and non-tabular grains below
Classified as child. (1) Tabular grains. Aspect ratio 1.6 to 500, preferred
2 to 500, and the thickness (μm) is 0.005 to 0.5.
5, preferably 0.005 to 0.3 tabular grains.
Here, the diameter means that the main plane of the particle is parallel to the substrate surface.
Projection plane when placed on the substrate surface and observed from the vertical direction
Refers to the diameter of a circle having an area equal to the product. The thickness is tabular grain
Refers to the distance between the two main planes of the child. The particle has a major plane
{111} tabular grains that are {111} planes (B₁₁) And chief
{100} tabular grains having {100} faces (B₁₂)
being classified. The former has 2 to 4 twin planes parallel to the main plane,
Preferably, two or three, more preferably two, two adjacent
The spacing (nm) between the crystal planes is preferably 0.3 to 100,
3 to 50 are more preferred. The interval distribution or the outermost parallel twin
The coefficient of variation of the crystal plane spacing distribution is preferably 0.01 to 0.60.
And 0.01 to 0.30 is more preferable, and 0.01 to 0.3
0.10 is more preferred. [Thickness / outermost parallel twin
The crystal plane spacing (the distance between the two twin planes closest to the main plane) is
1.1 to 600 is preferable, and 1.5 to 300 is more preferable.
New As described in JP-A-3-239240,
Particles with a defined distance between the twin plane closest to the plane and the principal plane
There is. The shape of the main plane of the particle is hexagon, triangle,
There is a circle with rounded corners, said hexagon, triangle, or
Hexagon, triangle formed by extending the straight part of the side
Adjacent side ratio of shape [(long side length / short side of one tabular grain)
Is 1.0 to 3.0, preferably 1.0 to 2.0.
0 hexagon, 3.01-triangle, preferably 5- triangle
There is. The number of parallel twin planes is 2 in hexagonal tabular grains.
Are preferred, and two or three triangular tabular grains are preferred.
The shape of the main plane of the {100} tabular grains is as follows.
1) The shape described in (11) of (I-1), 2) The four sides of the right angle
Of the four corners of the shape, one to four, preferably one to three, are non-
Equivalently missing aspect [within one particle (maximum missing surface
Product / minimum missing area) = Z_Ten≧ 2.0], or
3) Z with rounded corners_Ten= 1.0-1.99
4) A curve in which four sides constituting the main plane are outwardly convex
An embodiment that is a line. Details of these are described in Reference 8 below.
You can refer to the listing. The particles are kept at a low temperature of -100 to -150C.
When observed with a transmission electron microscope at a temperature, the dislocation lines were 1 to 2
0, preferably 1 to 3 observed particles and electron beam
No dislocation lines are observed at any angle of incidence
Particles are present. The dislocation line is a spiral dislocation line
The idea is that it is a spiral dislocation line with an edge dislocation line
I have an idea. The dislocation lines are stored at 0-40 ° C for 1-60 days
Often disappear from the particles. Of {111} tabular grains
1 to 100%, preferably 5 to 50% of the total area of the side surface
Non- {111} planes (eg {100} plane, {110} plane,
｛M₁ , M_Two , M_Three {Surface}. {100} flat plate
1 to 100%, preferably 5 to 5% of the total area of the side surfaces of the particles
0% is a non- {100} plane [eg {111} plane, {11}
0｝ plane, ｛m_Four , M _Five , M₆ {Surface}. ｛M
₁ , M_Two , M_Three ｝ Surface, ｛m_Four , M_Five , M₆ ｝ Surface is AgX
Refers to the high index surface that particles can take.
it can. AgI emulsion specified in (19) of (I-1)
The tabular grains have at least one of the aforementioned properties.
Emulsions, which are tabular grains characterized by
No. (2) Non-tabular grains (B₁₃). Aspect ratio 1.0-
1.59 non-tabular grains having twin planes of 1 to 4
Particles, preferably 1 to 2 particles (B₁₄) And one
Particles without (B_Fifteen). Furthermore, they are spiral
Some particles have 1 to 50 alignment lines and some have no alignment lines.
You. Furthermore, particles having 1 to 50 edge dislocation lines
Some particles do not have any. Crystal surface of particle surface, particle shape
For the examples, the description in the section (A-2) can be referred to. (A-4) C₁ Characteristics. C₁ The characteristics of A are A except for the particle size regulation.₁ Description of characteristics of
Can be applied. Where C₁ Is preferably a spiral
All particles having no dislocations and / or edge dislocations
60 to 100%, preferably 90 to 100% of the number of particles,
More preferably, it accounts for 98 to 100%. The shape is cubic
Body, octahedron, tetrahedron and their rounded particles
(Eg, spherical particles) are preferred. C₁ The definition of the diameter of
Same as the above definition. C₁ Is a homogeneous AgX composition type
Is preferable, and the difference in the AgX composition (mo
l% difference) is 0 to 30, preferably 0 to 10.
New A specified in (20) of (I-1)₁ But also Ag
60 to 100 of the total projected area of all AgX grains of the X emulsion
%, Preferably from 90 to 100%, at least
Is a monodispersed Ag that is an AgX particle defined by
X emulsions are more preferred. Seed [A_Five , B₁ ]
Regarding the law (R.D. 1996), refer to the description in the literature below.
it can. Especially A_Five Japanese Patent Laid-Open No. 2-146033
The description of B₁₁The description of References 5 and 19₁₂
The description of Reference 8 can be referred to. (I-3) Z₁ , Z_Two Description. The compounds described in the above (i) to (viii) will be described. (I) Onium base-containing compounds. (1) O represented by the following general formulas (I-1) to (I-8)
1 or more, preferably 1 to 10 chromium bases per molecule
^Four A compound containing a group.

[0006]

Embedded image

Where R¹ ~ R^Three Are the same
May also be different, each being a hydrogen atom,
0 substituted or unsubstituted alkyl group, alkenyl
Group, aralkyl group, and aryl group. Number of hydrogen atoms
Is preferably 2 or less, more preferably 1 or less, and 0
Is more preferred. That is, a straight or branched chain having 1 to 60 carbon atoms.
A branched alkyl group, a cycloalkyl group, an alkyl group having 2 to 60 carbon atoms;
Alkenyl group, aralkyl group having 6 to 60 carbon atoms, aryl
Groups are preferred. These groups are substituted with the following substituents.
You may. Y^-Is an anion (negatively charged atom or atom
Group). For example, acid group, OH^-Group, halogen ion
And a specific example is F^-, Cl ^-, B
r^-, I^-, NO_Three ^-, 0.5SO_Four ^2-, R¹ CO
O^-, R¹ -SO_Three ^-, ClO_Three ^-Can be mentioned
You. R^Two Is R¹ Or R^Three Can form a ring closure with
You. In addition, the onium base has only one group in one molecule.
In the case of a compound or unless otherwise specified, (I-1) to
The free bond in formula (I-8) is R^Four Attached to the group. R
^Four The group is R¹ ~ R^Three Represents the same group as defined above. Replaceable
(SB) described in JP-A-10-104679
1) can be mentioned, for example, halogen atom, alkyl
Group, alkenyl group, alkynyl group, aralkyl group, ant
Group, heterocyclic group, alkoxy group, amino group, carbo group
A xy group, a sulfo group, and an ester group. These groups are
May be further substituted. There are two or more substituents
The times may be the same or different.

In the equation (I-1), R¹ ~ R^Four Is other than a hydrogen atom
In the case of the atom of⁺Is in the range of pH 1.0 to 12.0
Irrespective of pH, always N⁺Keep. But R¹ 
~ R ^Four When one or more of is a hydrogen atom,
At pH above the pKa value (Ka is the acid dissociation constant)
Hydrogen atoms dissociate as protons, not onium bases
The probability of becoming is increased. In this case, (the pKa + 0.3)
~ (The pKa-6), preferably the pKa ~ (the pKa
The compound coexists in the reaction solution under the pH condition of -5).
Point to things.

[0009] The onium base is at least two groups in the following manner:
Preferably also be coupled 3-10 ³ group. (A)
Between the free bond via a divalent linking group L or R ¹
Linked through a group. L is an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S-,
—CO—, —NR ⁵ — (R ⁵ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred are alkylene and alkenylene. (B) bonding with a polymer chain; The onium bases to be bonded may be the same or different from each other, and may be an embodiment in which two or more groups of the above formulas (I-1) to (I-8) are linked. In that case, the total of various onium groups is 2 to
10 ^four, preferably 2 to 10 ³ group.

[0010] In particular, pKa in the pH range of 1.5 to 12.0
A copolymer with a monomer having an acid dissociable group having a value (Ka is an acid dissociation constant) is preferable. In general formula, (I
-9) is represented by the equation.

[0011]

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Where R⁸ Is R¹ ~ R^Three Same substitution as
Represents a group. R⁹ Represents a substituent having the acid-dissociable group.
You. n1 is an integer of 1 to 1000, preferably 2 to 300
And n2 and n3 are integers of 0 or more, preferably 1 to
10^Four , More preferably 2 to 10^Three Represents an integer. This
In the case of, raise or lower the pH above the pKa value
By the fact, the R⁹ The degree of water solubility of the group
It is preferable because the adsorptivity of the body can be changed. For example -C
In the case of an acid group such as an OOH group, its pKa value or more is preferably used.
Or by adjusting the pH to (pKa + 0.3) or higher.
(-COOH → -COO^-+ H⁺) And the parent of the group
Desorption of the polymer adsorbed on AgX particles due to increase in water solubility
Is promoted. That is, when the polymer becomes unnecessary,
By adjusting the pH value of the reaction solution, the polymer
There is an advantage that it can be desorbed and removed from X particles. -N
H_Two In the case of a base such as a group, its pKa value or less is preferable.
Or (pKa-0.3) or less to reduce (-NH
_Two + H⁺→ -NH_Three ⁺) And the water solubility increases. The dissociation
-SO as a functional group_Three M, -SO_Two M, -OSO_Three M,-
COOM, -NH _Two , -NHR¹ , -NR¹ R^Three , -S
O_Four M, -OPO_Three M_Two , (-O)_Two Give POOM
And preferably -SO_Three M, -SO_Two M, -CO
OM, -NH_Two , -NHR¹ , -OPO_Three M_Two It is.
Where M is H, an alkali metal, or -NH_Four ⁺Represents
You.

A hydrophilic group is introduced into R ⁸ , and (n1 / n
2) It is preferable to change the ratio variously, because the adsorption characteristics of the polymer can be changed almost continuously. As the water-soluble _{group, -OH, -CN, -CONH 2,} -COOCH
_{3, - (CH 2 CH 2} O) -, - CONH- can be exemplified. Polymerizing monomers having these groups,
The compound represented by the formula (I-9) may be synthesized. The (n1 / n2) ratio and (n1 / n3) ratio are 10
^-4 to 10 ^4, preferably you can choose a preferred ratio of 10 ^-3 to 10 ³ region.

Examples of the water-soluble groups and their pKa values are as follows. _{-C 2 H 4 COOH (4.67)} , - Ph-C
OOH (4.20), - Ph- ( CH 2) 2 -COOH
_{(4.66), - C 2 H} 4 NH 2, -Ph-NH 2
(4.65), pyridine group (5.42), -Ph-OH
(9.82). Here, Ph represents a phenylene group. This method can be preferably used for the compounds (ii) to (viii). Gelatin is not included in the compound of (i).
Further, NH ₄ ⁺ and -NH ₃ ⁺ groups are preferably not included in (i). Specific examples of these compounds are (I-31) to (I-
46).

[0015]

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[0016]

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Other specific examples include a triazolium salt which is an onium embodiment of a triazole. For details of the compound, see JP-A-4-335632.
You can refer to the description of the issue. Among these, compounds containing a sulfonium base, a phosphonium base, a selenonium base, an arsonium base, a stibonium base, a stannonium base, an iodonium base, and a heterocyclic quaternary base are more preferred.

[0018]

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(2) A compound containing a heterocyclic nitrogen quaternary base. Among the onium bases described in the above (1), a compound containing a heterocyclic nitrogen quaternary base is more preferable. The base is represented by the general formulas (II-1) to (II-4). The group is 1
Compounds containing one or more, preferably 2 to 300 groups in the molecule.

[0020]

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Here, A _{1 to} A ₄ represent a group of nonmetallic atoms for completing the nitrogen-containing organic heterocycle, and they may be the same or different. It may contain O, N, and S atoms, and the benzene ring may be condensed. The hetero ring composed of A _{1 to} A ₄ may have a substituent, and the substituents may be the same or different. As the substituent, the aforementioned (SB1) can be mentioned. Preferred examples are those in which A _{1 to} A ₄ are a 5- to 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, and the like), and a more preferred example is a pyridine ring. Can be. Specific examples of the compound are shown in (II-11) to (II-16).

[0022]

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The compound (a) is more preferably a compound of the formula (II-
21) and (II-22). Where R^{twenty three},
R^{twenty four}Is R¹ , R^Two Represents the same substituent as_Five ~ A₈ 
Is A ₁ ~ A_Three To complete the nitrogen-containing heterocycle
Represents a group of non-metallic atoms.
May be. n11 represents 0 or 1;
In this case, it is 0. n12 represents 0 or 1. L is
Represents the same divalent linking group as described above. Y^-Is the same as above.
Represents Nion. Specific examples of the compound include (II-31)
(II-37).

[0024]

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[0025]

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As a more preferred example of the compound (b), a compound represented by the formula (III-1) can be further mentioned. In the formula, R ³¹ represents the same substituent as R ¹ and R ² described above, and R ^{32 to} R ³⁶ may be the same or different and each represents a hydrogen atom or a group which can be substituted with this. The above-mentioned SB1 can be mentioned as the substitutable group. ^R32 and ^R33 , ^R33 and ^R34 , ^R34 and ^R35 , ^R35 and R
³⁶ may be fused. However, it is preferably at least one of R ³² to R ³⁶ is an aryl group or an aralkyl group, it is more preferred R ³¹ is also an aryl group or an aralkyl group. Y ^- is the Y ^- is the same as. ^R32 and R
^33, R ³³ and R ^34, R ³⁴ and R ^35, R ³⁵ and R ³⁶ are condensed to quinoline ring, an isoquinoline ring, may form a acridine ring. The following (III-2) to (III-11) show specific examples of the compound.

[0027]

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[0028]

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(C) As more preferred examples of the compound,
A compound represented by the formula (I-9) and the onium base is represented by the formula (II-3) or (II-4). Further, there may be mentioned compounds containing one or more heterocyclic nitrogen quaternary bases and one or more acyclic quaternary ammonium bases in one molecule. Preferably each is 1 to 10 ⁴
Group, preferably may be mentioned compounds containing 2-10 ³ group. Specific examples of the compounds are shown in (III-21).

[0030]

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The details of the compounds (1) and (2) and the synthesis method are described in US Pat.
Nos. 078 and 4525446, European Patent No. 03920
92B1, JP-A-2-293838, JP-A-7-3064
No. 89, No. 10-104679, No. 8-29902
Nos. 2, 3-34, 8-227117 and WO 94/20551.

(Ii) one or more iodo groups on the aromatic ring
An aromatic compound substituted with at least one -OH group. The iodine group is preferably substituted with 1 to 8, preferably 2 to 5, and the hydroxy group is preferably substituted with 1 to 3 groups. Here, the aromatic compound refers to a carbocyclic compound having a benzene nucleus, and also includes a compound in which another benzene ring or a heterocyclic ring is fused to a benzene ring (for example, naphthalene, anthracene, quinoline, and indole). The aromatic ring includes the benzene nucleus, the benzene ring, and the heterocyclic ring, and preferably refers to the benzene nucleus and the benzene ring. More preferably, it is 8-hydroxyquinoline containing at least one iodo substituent [the general formula is represented by the formula (IV-1)], or isoquinolines.
2) to (IV-3). In addition, 8-hydroxy-
There is 7-iodo-5-quinolinesulfonic acid. R ⁶⁰ , R
⁶¹ can be selected from (SB1), and is preferably a polar substituent or a halo substituent. For details of the compound, reference can be made to the description in the document of US Pat. No. 5,411,852, (iii).

[0033]

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(Iii) A nitrogen-containing heterocyclic compound. One or more heterocycles containing two or more nitrogen atoms in a 4- to 7-membered ring
It is a compound containing at least one compound in the molecule, and preferably includes the following compounds. (A) Azaindenes. Preferred are tetraazaindenes, and specific examples thereof include xanthoidoids [represented by the formula (V-1), and specific examples thereof include xanthine and uric acid], and aminoazaindenes (specific examples) There are purines, adenine, guanine and kinetin). (B) Diazines (pyridazines, pyrimidines, pyrazines). Of these, substituted pyrimidines are preferred. Examples of the substituent include the aforementioned SB1, and preferably an amino group. Specific examples of compounds include uracil, cytosine, thymine, and compounds of formulas (V-2) to (V-5). For details of these compounds, see JP-B-5-40.
298, JP-A-5-265111, JP-A-5-2040
No. 77, 5-232612, JP-A-64-8325
No., The Chemical Society of Japan, New Experimental Chemistry, Vol. 14, Chapter 9,
The description of Maruzen (1978) can be referred to.

[0035]

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(Iv) Cyanine dyes. It refers to a dye having a cation structure in which two nitrogen-containing heterocycles are bonded by a methine group —CH ＝ or a chain thereof, and preferably has one or more, more preferably one or two acid groups. Here, the acid group is -S
_{^{O 3 -, -OSO 3 -,}} -COO - refers to, preferably -SO ₃ ^- refers to the group. Preferred are imidocyanine, oxacyanine, thiacyanine, selenocyanine and their composite cyanine, and more preferred are imidocyanine and oxacyanine. See Re for details on these compounds.
search Disclosure, Volume 501, Item 36544,
In September 1994 (hereinafter referred to as [RD. 1994]), the description of Reference 9 can be referred to.

(V)-(viii). In addition, JP-A-62-2
No. 99961, compounds having a divalent sulfur group-containing heterocyclic group, organic compounds containing a divalent sulfur group described in JP-A-63-41845, and JP-A-3-212.
And aminothioethers described in JP-A-639 and 4-283742, and thiourea or derivatives thereof described in JP-A-62-218959. The general formulas of these compounds are shown in the formulas (VII-1) to (VII-4).

[0038]

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For details of these compounds, reference can be made to the description of the above-mentioned literature corresponding to each compound.

In the formula, Z ⁷⁰ represents an atomic group necessary for forming a substituted or unsubstituted saturated or unsaturated heterocyclic ring together with a sulfur atom, and is an atom composed of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Group. The heterocyclic ring is a 3- to 8-membered ring, and the ring may be condensed with another ring to form a condensed ring. The heterocycle may have one or more substituents. Examples of the substituent include SB1.

X ⁷⁰ represents an amino group which may be alkyl-substituted, a quaternary alkylammonio group, or a carboxy group, and L ⁷⁰ , L ⁷¹ and L ⁷² each represent a divalent organic linking group having the same definition as L above. Represents Y ⁻ represents an anionic group and has the same definition as Y ⁻ . m is the same as the number of quaternary alkylammonio groups. The alkyl group preferably has 1 to 3 carbon atoms. M ⁷⁰ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. X ⁷¹ represents CO or SO ₂ . R ⁷⁵ represents a hydroxy group, substituted or unsubstituted (alkyl group or aryl group, or heterocyclic group, amino group, alkoxy group, aryloxy group). As the substituent, the aforementioned SB1 can be mentioned. The total number of carbon atoms in the molecule of the formula (VII-4) is preferably 30 or less, more preferably 20 or less. Z ₁ ,
For details of Z ₂ and specific compound examples, see Reference 2
0 (Japanese Unexamined Patent Application Publication No. 10-104679, Japanese Unexamined Patent Application Publication No. 11-36490)
No. 2) can be referred to. (i) to (iii) are more preferred, and (i) is most preferred. An embodiment in which an onium salt forms a π-conjugated system (Z ₁₁ ), particularly an embodiment in which a cyclic π-conjugated system such as a pyridinium quaternary base (Z ₁₂ ) (Z ₁₃ ) is more preferable, and the quaternary nitrogen atom has carbon atoms 1 to 60 embodiment containing radicals covalently attached (Z ₁₄₎ are more preferred, Z
Compounds containing ₁₄ groups (Z ₁₅ ) are preferred. In (i),
(II-32), (III-2) and (III-3)
Compounds having one or more, preferably 1 to 10 substituted or unsubstituted aryl groups in the molecule are more preferred.

The onium base is X on the surface of the AgX particles.^-Rhinoceros
Adsorbs on the surface by Coulomb interaction and exerts its action.
₁₃, Z₁₄In the embodiment of the present invention, the molecular polarizability becomes large,
It is expected that the utility will be larger. The group is absorbed on the particle surface.
By wearing, [Ag_nX _m ^-(mn)]
Promotes on-particle adsorption and promotes particle growth
You. On the other hand, if the adsorption is enhanced by the aryl group,
Due to its hydrophobicity, its desorption probability is low and particle growth
Suppress. When added in large amounts, the latter effect is dominant.
And grain growth is greatly suppressed. In the case of adding an appropriate amount,
Diameter distribution due to surface growth suppression and edge surface weak growth suppression
Thin tabular grains with narrow edges can be obtained, and edge face growth is promoted
There is also an area to be used. Converts the compound into octahedral AgX particles
Compounds that increase the ionic conductivity of the particles when adsorbed
There are compounds and compounds to reduce. Greater effect of the present invention
Many compounds reduce the compound. Circumference of the dielectric loss of the particle
In the wave number dependence measurement, the loss peak (P₁)
Is the conductive Ag on the particle surface⁺Based on the low frequency loss
(P _Two) Are interstitial silver ions (Ag_i ⁺)
Based on this, when increasing, move both to the high frequency side,
To decrease, P₁With a decrease in peak intensity
Often move the person to the lower frequency side.

In the case of a nitrogen-containing heterocyclic compound such as the purine bases and pyrimidine bases, the adsorptivity to AgX particles shows pH dependence in the above pH range. Assuming that the acid dissociation constant of the compound is Ka, the adsorptivity increases at a pH of pKa or more. Here, pKa = −log (Ka). At a pH below pKa, the adsorbability decreases due to proton addition. Therefore, the compound is preferably made to coexist in the dispersion medium solution at a pH of (pKa−0.3) or more, more preferably at a pH of pKa to (pKa + 5). Z ₁ and Z ₂ have pKa in the molecule.
= 1 to 12, preferably 2 to 10, more preferably 3 to
It is preferable to have 1 to 1000 acid dissociable groups of 9 groups.

Adsorption on AgX particles among the compounds
Strong ones promote the formation of twin planes during the formation of the grains
And produce thin tabular grains. With moderate suction power
Has the effect of suppressing the formation of twin planes. Low adsorption power
Those that are too much have no effect. Even with the same compound, the effect is
It also depends on the concentration and the temperature.
The lower the lower, the stronger the adsorption power (ie, the adsorption residence time).
Becomes longer). In addition, absorption of the coexisting dispersion medium
When the wearing strength is high or the concentration is high, Z₁ , Z_Two of
As the adsorption equilibrium concentration decreases, higher concentrations
Degree Z₁ , Z_Two Need. Therefore, the effect of the present invention is obtained.
For this purpose, the compound species and its concentration, temperature, pH, pX,
It is necessary to select a dispersion medium type and a dispersion medium concentration value.
You can refer to the description. X in the compound of (i)^-Salt compound
When used, (Cl^-The concentration is Br^-Concentration
When it is 2-∞ times, Cl^-It is preferable to use a salt compound
And the Br^-Concentration is Cl^-B when the concentration is 2-∞ times the concentration
r^-It is preferable to use a salt compound. The compound of (i)
For example, halogenated alkyl compounds
Object (Z_Three ) In an organic solvent such as isopropyl alcohol
It is obtained by reacting, usually in the form of a salt. Io
Type is Z_Three The type of halogen ion
You can choose. Or the product is Br^-Salt and I^-In the case of salt,
When this is dissolved in an aqueous solution containing AgCl particles, Br^-
And I^-Is Cl^-With halogen. Centrifuge AgX particles
From the aqueous solution separated and removed,^-Remove the salt. Or
The product was dissolved in water and electrodialyzed to a positive electrode with X^-Gather
After that, the + electrolyte is replaced with another + electrolyte. These methods
Gives X^-Seeds can be freely selected. So before
X of the above compound example^-Seeds can be freely selected. (I-4) Description of Embodiments (1) and (2) A_Three Is usually a seed crystal formation process (A_{twenty one}) And the growth process (A_{twenty two})
Formed through_{twenty one}Is usually Z₁ A exists_Four A in
g⁺Containing solution (Ag⁺Liquid) and halogen ions (X^-)
Containing a solution (X^-Liquid) while stirring and adding
It is done by doing. A_{twenty one}Period of AgX nucleation start?
A_{twenty two}Indicates the period until just before the start. Ag⁺And X^-Add
If this continues, unstable nuclei are formed first, then
To increase. Next, part of the nuclei become stable nuclei, and the rest dissolve
And the number of stable nuclei (the number of seed crystals) becomes constant. Next A_{twenty two}In the
Stable nuclei (seed crystals) grow, and the target product is obtained. Therefore A
_{twenty one}Indicates a period until the number of stable nuclei becomes constant. Z₁ Is
A_{twenty one}Can be added at any time of
It is preferred that the nucleus be present at the above concentration during the formation of the constant nucleus. Follow
Before the start of nucleation, Z₁ A_Four At the concentration
It is preferable to add them. Further Z₁ A_{twenty one}, A_{twenty two}With AgX1
10 per mole^-9~ 1.0, preferably 10^-8~ 0.1
Only moles can be added. Additional additions at once
The whole amount can be added, or it can be added continuously.
Kirishi 2-10^Three It can also be added in batches. So
Two or more of these methods can be used in combination. Added
Ag⁺Liquid and X^-One or more, preferably both, solutions 1
10 per kg^-8~ 1.0 mol can be added.
The method of addition is not only solution but also powder and powder
It can also be added in various ways. Especially A_{twenty one}Additional addition to
Using the method, Z can be used at all times during seed formation.
₁ Concentration can be optimally selected to form more preferable seed crystals.
Can be achieved. These embodiments are also applicable to the embodiment (I-5).
Applicable. Z₁ Is present at the time of nucleation,
Its modest attraction prevents twin plane formation
You. In addition, coalescence between particles is prevented, edge dislocation, spiral
Dislocation generation is also prevented. A_{twenty two}Now, for AgX particles
Prevent the generation of new nuclei with the appropriate adsorption power
Uniform growth between particles, AgX particle shape, AgX group
AgX emulsion grains having a uniform composition among grains are obtained. AgX
Introducing a dislocation line into the particles;
Forming Z₁ Exists, the dislocation line introduction location
And the number of dislocation lines,
AgX molar amount becomes uniform among the particles. Those amount of particles
The variation coefficient of the variation between the two is preferably 0.01 to 0.50
And 0.01 to 0.20 is more preferable. A_Four , B_Four of
Preferred conditions for dispersion medium solution (A_{twenty five}), More favorable conditions
(A₂₆) Is described in Table 1. Where pX = -l
og [X^-], And [X^-] Is X^-Concentration (mol / lit.)
). The most preferable combination condition area
(A₂₇It is preferred to choose Especially Ag⁺And X^-Concentration of
Absolute value of difference (mol / liter) | [Ag ⁺]-[X^-] |
0.0-10^-1.5Is preferred, and 0.0 to 10^-2Is better
Preferably, 0.0-10^-2.5Is most preferred. The condition is A
₃₁Is also preferred.

[0045]

[Table 1]

(I-5) Description of Embodiments (3) and (4)
Akira. (A-1) C_Two And the formation of C_Two To B_Three To add to
Law. Reaction vessel (A₃₀) In B_Four And Z_Two While stirring.
Ag⁺Liquid and X^-By adding the liquid into the solution,_Two 
Is obtained. The formation process (A₃₁) Preferred conditions
(A_{twenty five}, A₂₆) Are shown in Table 1. Z_Two Because there is
The formation of crystal defects such as twin planes is prevented, and the dislocation lines
Introduction is also prevented. C_Two To form B_Three Add to
There are the following methods. 1) C_Two B after desalting by the desalting method described below_Three Added to
how to. The total amount of soluble salts in the emulsion or
Z_Two The content is 0 to 95% before the treatment, preferably 0 to 5%.
It is reduced to 0%, more preferably to 0-10%. 2) C_Two 95.1 to 100% of the soluble salt in C_Two inside
As it is, B_ThreeHow to add to. 3) C_Two 1 to 100% of the total water content, preferably 20 to
After removing 100%, more preferably 60-100%
How to add to. Specific examples of the removal method are as follows. 3-
1) A method of drying in the atmosphere. 3-2) 10^-7~ 0.99
Atmospheric pressure, preferably 10^-6Evaporation of water under 0.3 atm
How to leave. Vacuum freeze-drying is also included. 3-3) Centrifugation
A method of separating and removing the supernatant. 3-4) Ultrafiltration method
How to remove moisture with. 3-6) adding a coagulating sedimentation agent,
A method of coagulating and sedimenting the emulsion and removing the supernatant. The desalination
Method and the sedimentation agent with reference to the description in (I-7).
Wear. 4) C₁ Formation in a batch reactor.
C₁ At once or 2-10^Five Divided into times B_Three To
How to add. Or a method of adding continuously. 5) C₁ And the formation of C₁ Take-out and continuous
Forming by a continuous forming method. This is B_Three Continuous
C can be added₁ Into a container
B_Three Can also be added. 6) C_Two And B_Three If the solution conditions of_Two The condition
B_Three After adjusting to or close to the conditions of_Three To
Can be added. For example, pH, pAg, temperature, dispersion
Adsorption force of the medium on AgX particles and dispersion medium concentration. pH is acid,
The pH difference is reduced to 0 to 3.0 by adding lukari, and pX is Ag.
⁺Liquid or X^-The pX difference was reduced to 0 to 3.0 by adding
Temperature by cooling or heating the reaction solution.
The temperature is adjusted to 0 to 40 ° C, preferably 0 to 15 ° C. 7) In addition, the description in Reference 10 below can be referred to. The
It is preferable to use two or more of 1) to 7) in combination.
The smaller the diameter of the fine particles, the easier they are to dissolve, but too small
And Ag⁺And X^-Approaching the ionic solution addition method of
Effect is reduced. A for forming small particles
What is necessary is just to form under conditions with low solubility of gX. For this
The temperature (° C.) is more preferably 0 to 30, further preferably 0 to 20.
preferable. Also, Ag⁺The total concentration of the complex is Ag⁺Concentration of
0-10^Two Times, preferably 0.0 to 1.0 times
Is preferred. The condition is A_{twenty one}Is also preferred. Also,
It is important not to create a low dispersion medium concentration region during particle formation.
Ag to be added⁺Liquid and X^-At least one of the liquids, preferred
Alternatively, the dispersion medium is preferably 0.01 to 15 by mass% for both.
Or 0.10 to 5.0 in a dissolved state.
You. Ag ⁺When added to the solution, use an acid (HNO_Three Etc.)
Add together [10 kg of acid per 1 kg of dispersion medium^-3-10^Two Mo
, Preferably 10^-2-10 mol), and Ag⁺
Is preferably prevented from changing to Ag. The embodiment is A_{twenty one}
Can also be preferably used. Also, the reaction solution
PH, pX, dispersion medium concentration and temperature_Five And C₁ Eyes of formation
In contrast, the most preferable combinations in the regions described in Table 1
Condition area (A₃₂It is preferred to choose Of fine particle formation
Ag for⁺Liquid and X^-If a large amount of liquid is added in a short time,
The heat of the reaction increases the temperature of the reaction solution. Suppress this
And the temperature (° C.) is 0 to 30, preferably 0 to 20,
Preferably, the following method is preferably used to maintain 0 to 10.
I can do it. 1) The Ag⁺Liquid and X^-At least one of the liquids, preferably
Cool both temperatures (° C.) to 0-25, preferably 0-20
Add after adding. This involves a) preserving the stock solution of the liquid
Cooling, b) the liquid is added through a liquid feed pipe
And the total length of the liquid sending pipe is 0.1 to 100.
%, Preferably 1 to 100% passed through the coolant
Mr. The liquid is cooled as it passes through the pipe. The sending
The smaller the outer diameter of the liquid tube, the larger the specific surface area and the cooling efficiency
Well, preferably 0.1-300mm, 0.5-50mm
More preferred. The coolant is provided for it, or
A thermostat for the reaction solution can be used. Or reactive
Liquids can also be used as coolants. Two or more of these
The above can be used together. 2) Ag⁺Liquid and X^-At the same time as adding the solution,
And / or in a thermostat) coolant (ice, solidified gas)
(Eg, dry ice), liquefied gas (eg, liquid nitrogen)
Element, liquid oxygen, liquid air)]. Pre-added amount
In preliminary experiments, the amount added and the temperature reached during or after addition
Temperature relationship and determine the temperature required to achieve the desired temperature.
Divide the amount at once, preferably 2 to 100 times,
More preferably, it is added by continuous addition. Total sum
The addition amount is 0.1 to 10 per liter of the reaction solution.^Four g is preferred
No, 0.5-10^Three g is more preferred. Cool in reaction solution
When adding a disintegrant, the solidified gas and the liquefied gas
The addition method does not increase the volume of the reaction solution compared to ice.
More preferred. C₁ Is formed for 0.01 seconds
~ 1 day, preferably 0.1 seconds to 3 hours, more preferably
B for 0.1 seconds to 40 minutes_Three Preferably added to
No. A uniformly or non-uniformly in the fine particles._TenDifferent in aspect
A seed atom or the compound can be doped. C₁ With
Z_Two 5 to 100%, preferably 20 to 100% of B_Three 
May be added. In this case, Z_Two Is B₁ Control growth
To improve monodispersity. Especially B₁ Is the tabular grain
In this case, the growth of the edge surface is suppressed
Eliminate long particles. Also, small seed crystal particles dissolve
To prevent the formation of small particles. The result
As a result, particles having a uniform size distribution can be obtained. But it
Has Z_Two Must be present at the optimal concentration. C₁ Is special
The effect is large when the AgI content is high. (I-
The tabular grains were grown in the modes of 3) and 4) of 1).
In this case, tabular grains grow uniformly between grains, and the intergranular properties are uniform.
One tabular grain is obtained. (I-6) Dispersion medium. (A-1) A_Two , A_Four , B_Two , B_Four The dispersion medium for
General description. As a dispersion medium, known natural or synthetic or natural products can be used.
A chemically modified water-soluble dispersion medium can be used, and its mass
Average molecular weight is 10^Three -10⁶ Are preferably 5000-1
0⁶ Is more preferred. The coefficient of variation of the molecular weight distribution is 0.0
1 to 0.50 is preferable, and 0.01 to 0.20 is more preferable.
More preferably, 0.01 to 0.10. Monodisperse
Examples of the dispersion medium include fractionated gelatin (for example, by ultrafiltration)
The fractionated gelatin can be referred to in Reference 18 below.
). In addition, the coefficient is 0.51 or more polydisperse.
2 or more, preferably 2 to 1
Dispersion medium with zero peaks, low molecular weight dispersion medium
1.2-10^Three Double the polymer dispersion medium of the same molecular weight
There is a dispersion medium. In this case, the low molecular weight molecule is
Surface (e.g., fine particles or thin tabular grains)
Edge surface, trough portion of {111} tabular grains]
Controlling its growth, high molecular weight molecules are macroscopic (eg,
(Main plane) to prevent aggregation between particles. That is,
It can be said that this is a multifunctional dispersion medium. When using gelatin,
Methionine group (Met) content (μmol / g) or thione
The ether group content (μmol / g) is
Can also be used. The content is thioe
Chemical modification of the ter group (this group is oxidized to give a sulfoxide group or
By converting it to a ruho group, or an alkylating agent (eg,
Alkylation with an alkyl halide)
Or thionium conversion)
it can. In general formulas, -S (O)-, -S (O_Two)-,
−S (R ⁸⁰)-, -S⁺(R⁸⁰, R⁸¹)-. Also
Via the oxidant, -SO_Three ^2-In some embodiments, The
Altered groups are not considered as such groups. H_Two O_Three Add the acid
Gelatinized gelatin is more preferred. Further, after the oxidation,
5 to 100%, preferably 20 to 100% of the oxidizing agent
Removed gelatin is preferred. To increase the group content
Is to select a dispersion medium with a high content or to contain a thioether group.
Organic compounds having 1 to 20 carbon atoms are covalently bonded to the dispersion medium molecules.
It is sufficient to combine them. Amino group and imidazole group,
The chemical modification rate (%) of the boxyl group and the hydroxyl group is 0.0 to 10
0 is preferable, and 10 to 97 is more preferable. Amino group
Chemical modification is -NH_Two Groups are secondary, tertiary or quaternary
Change to a group or deamination.
When represented by the formula, -NHR⁸⁰, -N (R⁸⁰, R⁸¹), -N (R
⁸⁰, R⁸¹, R⁸²), And as a specific example, -NHCO-R
⁸⁰, -NHSO_Two -R⁸⁰, -N⁺(CH_Three) _Three There is. This
Where R⁸⁰, R⁸¹, R⁸²Excludes hydrogen and halogen atoms
R^Four It has the same definition as the group. The quaternization of the amino group is
Rogenated organic matter (R ^Four -X, for example methyl iodide, bromide
Methyl). Amino group, i
For chemical modification of midazole, carboxyl, and -OH groups
For details, refer to Japanese Patent Application No. 11-322913, and Reference 1 below.
8 can be referred to. The dispersion medium is cystine,
When the methionine group is contained, the sulfur group is the same as the methionine group.
Can be converted to sulfino or sulfo groups
You. When containing nucleic acids, the amino group and imino group are
Similarly, it can be chemically modified. Modification rate of each
(%) Is preferably 0 to 100, more preferably 10 to 97.
New As a dispersion medium, the molecular weight, the modified species, and the modification rate
Any combination can be used. As the modified species
May be used alone or in combination of two or more. The
Gelatin having a chemical modification rate of amino groups of 10 to 100% is preferred.
It can be used well. Especially at pH 6.0 to 12.0
When the tabular grains are grown, the
Growth is suppressed, which is preferable. The adjustment of the molecular weight is based on the molecular weight.
When increasing the amount, by cross-linking between molecules with a hardener,
Enzymatic digestion, low or high pH when reducing molecular weight
It can be performed by hydrolysis method, thermal decomposition method, etc.
For details, see Reference 17 and Japanese Patent Application No. 11-322913.
You can refer to the listing. Alkaline treatment as gelatin seed, acid
Empty gelatin with processed gelatin and ionic impurities removed
Ornithine 0.1 to 100% of arginine groups
Gelatin, fractionated gelatin with controlled molecular weight distribution, nucleic acid
0.0 to 10% by mass of base content^-2, Preferably 0.0
-10^-FourThere is gelatin. Especially controlled as a source of gelatin
There is no limitation, and any animal connective tissue can be used.
Normally, bone and skin of (cow, pig, fish) are preferable,
Beef bone gelatin is more preferred. Molecular weight distribution is coefficient of variation
(Standard deviation of mass molecular weight distribution / mass average molecular weight)
01 to 0.6 is preferable, and 0.01 to 0.20 is more preferable.
Good. Adsorption of residues in gelatin adsorbed on AgX particles
The force sequence is [1) -S- group of methionine> 2) imidazole
Group >> 3) -NH_Two Group> -COOH group],
1), 2) and 3) are chemically modified and the absorption per molecule is
The arrival energy is 80 to 0.1% of the original, preferably 50 to
Gelatin reduced to 1.0% has less inhibition of tabular grain growth.
This is preferred because it allows the production of thin tabular grains.
No. The methionine groups in the gelatin are located on the surface of the AgX particles.
Ag⁺Adsorbs to sites to prevent fogging. this is
The effect is the same as that of the antifoggant. Other known photos
Dispersion medium for use as described in US Pat. No. 5,380,642.
Graft polymer of vinyl compound, gelatin and other molecules
Using a mixture of one or more of
I can do it. Regarding these dispersion media and the details of the dispersion media,
For example, the following literature and the descriptions of literatures 17 and 18 and (R.
D. 1996). A_Four Used for
The dispersion medium used is a suitable dispersion medium to form a twinless seed crystal.
It is preferable that the solvent is a medium, and the adsorbing power to AgX particles is appropriate.
Very strong dispersion media are preferred. Because of this, the histidine group
Rate (μmol / g) is 3 to 300, preferably 10 to 100
Are preferred. Met content (μmo
l / g) is preferably from 3 to 120, more preferably from 10 to 80.
New Fish as examples of gelatin with high imidazole group content,
Preferably the connective tissue (bones and
There is gelatin extracted from the skin. Conventionally known gelatin
With an organic compound having these groups to form a covalent bond
It is also possible to synthesize by making them. For example, R⁸⁰,
R⁸¹, R⁸²These groups may be contained in the compound. The molecular weight is
The higher is, the better the protective colloid property is, and the weight average molecular weight is 10
^Four -10⁶ Is preferably 10^Five -10⁶ Is more preferred
3 × 10^Five -10⁶ Is more preferred. Amino group and
And / or -COOH group content (μmol / g) is 10 to
10^Three Is preferred, and 100 to 10^Three Is more preferred. (A-2) B_Four Dispersion medium for B_Four The dispersion medium used for
A dispersion medium is preferred. But C₁ Is formed, and C_Two To B_Three 
And C₁ Is weak when the solvent dissolves
Better C₁ Is preferred because it is easily dissolved. Therefore, C₁ The shape
After the formation, it is preferable to perform an operation to weaken the adsorption power of the dispersion medium.
New The operation is C₁ After forming _Two To B_Three Added to
You can do that before you_Three After adding to
You can do it. The former has a simpler reaction system,
More preferred. The operation includes the following method. 1) Add an oxidizing agent to oxidize the adsorbing groups of the dispersion medium and adsorb it
Reduce the nature. The standard electrode potential (E₁ ) Is high
The higher the concentration of the oxidizing agent, the more the adsorbed groups are oxidized
The probability increases. The standard electrode potential of the adsorbing group is E_Two To be
And [E₁ > (E _Two -0.2)],
[(E₁ -E_Two ) = 0.0-1.2]
Good. If the value is too high, the oxidizing agent will not react with water or other groups.
This is because the oxidation efficiency of the target product decreases. The potential is
Usually, it is indicated by a value where the standard hydrogen electrode potential is 0, and this value is
Examples of compounds are described in, for example, References 11 and 12 described below.
Can be referred to. Where the unit of the potential is volts
is there. For example, adding an oxidizing agent to oxidize the thioether group
-S (O)-, -S (O_Two)-, -SO_Three Change to H group
Or -SH group to -SO_Three Change to H group.
As a result, the thioether group content (μmol / g) was
0.1-95% before, preferably 1.0-70%, more
Preferably, it is reduced to 1.0 to 30%. For example, tampa
In the case of calcium (including gelatin), the Met content (μmol /
g) using the dispersion medium of 5 to 100₁ Formed
Thereafter, the oxidizing agent (H_Two O_Two Etc.) and add time
By doing so, this aspect is realized. 2) An organic compound is covalently bonded to the adsorptive group. For example,
An alkyl halide is allowed to act on the
Nitrogenation and halogenation of nitrogen-containing heterocyclic compounds
Alkylation of the nitrogen atom by the action of
is there. 3) Cleaving and removing the adsorbing groups. For example (-NHCO- +
 H_TwoO) → (-NH_Two + -COOH). 4) Reduce the molecular weight of the dispersion medium. Acid or alkali, also
Reduces the molecular weight by hydrolyzing the main chain of the polymer with an enzyme
You. Adsorption force for particles decreases as molecular weight decreases
You. The weight average molecular weight is reduced to 10^-3~ 0.9 times, preferably
Is 10^-3Up to 0.3 times. 5) When the adsorptive power becomes weak by reducing the dispersion medium
Reduces. Regarding the details of the oxidation and reduction reagents and methods
For this purpose, the descriptions in References 11 and 12 described later can be referred to. this
The reaction temperature (° C.) is preferably 5 to 100, and 10 to 6
0 is more preferred. Reaction time (min) is 0.1 to 10^Four 
Is preferably 1 to 10.^Three Is more preferred. Reaction solution p
H is preferably 0.1 to 13, more preferably 1.0 to 12.
New This operation allows the dispersion medium to be adsorbed on the AgX particles.
The force is 0.1 to 95% of the adsorption force before the operation, preferably
1.0 to 70%, more preferably reduced to 1.0 to 30%
I do. The adsorptive power is the same for AgX particles of the same mass.
And add the same mass of dispersing medium
It can be compared by the heat of adsorption. For example, [Gelatin dispersion
The medium AgX emulsion is centrifuged, the supernatant is removed and then
Water and redisperse] 2 to 10 times
No, after removing the dispersion medium, add the relevant dispersion medium aqueous solution
And measure the total amount of heat generated before reaching the adsorption equilibrium
I do. Alternatively, comparison is made based on the amount of dispersion medium adsorbed during the adsorption equilibrium.
I can do it. For example, AgX particles at the adsorption equilibrium
Settle by natural sedimentation or centrifugation.
And the precipitate is dried. Powdering that constant mass
And mixed with KBr powder of constant mass, and its infrared absorption spectrum
Measure the vector (referred to as FTIR). Red dispersion medium
External absorption strength (500-2000cm^-1Area).
Also Ag⁺Liquid or X^-The change in silver potential when the solution is added
When writing a curve to represent, add until the inflection point is reached
Ag⁺Or X^-Can be compared by the molar amount added. The amount
The greater the number, the greater the adsorption force on the corresponding atom on the surface. C
₁ Is formed, 5 to 99% of the dispersion medium, preferably
After removing 20-99%, B_Three Can also be added to
You. Examples of the removal method include desalting, centrifugation, and the like described below.
Or a combination thereof, and C₁ And settle the supernatant liquid.
There is a way to leave. How to prevent the formation of defects such as twin planes
The adsorption strength of the dispersion medium should not be too strong, not too weak, and be moderate
Is preferred. If it is too weak, coalescence between particles occurs, and twin planes, etc.
Defects. If too strong, the dispersion medium remains adsorbed
Crystal grows as particles grow and are taken inside
Defects (for example, spiral dislocations and edge dislocations) occur. Strong minutes
If the diffusion medium is present at a high concentration, particle growth is inhibited and new nuclei
The generation period of the particles becomes long, and ultrafine particles can be obtained. But,
The emulsion was prepared as B_Three When added to the dispersion medium, the fine particles are stored in the dispersion medium.
Protected and difficult to redissolve. The dispersion medium is also B_Three Attached to
Added, it is B₁ Inhibit the growth of. Therefore weak adsorption
It is most desirable that the desired AgX fine particles are formed with a dispersion medium of force.
Is also preferred. Z_Two When formed in the presence of
Become. This enables the embodiment (18). (I-7) Desalting method and Z₁ , Z_Two Desorption, removal method. The following method is an example of the desalting method of the AgX emulsion. 1) Emulsion
Is cooled to 25 ° C. or lower, gelled, and washed with water. Wildebeest
Also called the Dell washing method. 2) Emulsion by adding flocculant
Is settled at the optimum pH and washed with water. N as a precipitant
a_TwoSO_FourAnd an inorganic precipitant (having a salting-out effect) such as
Insoluble gelatin in organic precipitants and alcohols
Organic solvents. Many organic precipitants are present in the dispersion medium molecules.
Neutralize the charge of ionic groups and reduce their hydrophilicity
Insoluble in water, insoluble and aggregated.
For example, naphthalene sulfonate, formaldehyde resin
The compound is -NH of gelatin._Three ⁺To neutralize the radical,
Solubilize. 3) A certain pH range such as phthalated gelatin
Aggregation and sedimentation by pH adjustment using a dispersion medium that aggregates in the area
Method. 4) Use of centrifugal separation method and hydrosaclone method.
5) Use of ultrafiltration or centrifugal filtration. 6) Electrodialysis
Use. PH difference from the isoelectric point pH of the dispersion medium is 0 to 3, preferably
Or 0 to 1. 7) Contact with ion exchange resin
Way. For details on these (R.D. 1996), see below.
Can be referred to. Can be used in the present invention
About acid, alkali (base), chemical handbook, basics
HNO, can be referred to the description in Chapter 10_Three , H_Three PO
_Four , H_Two SO_Four , NaOH and KOH are preferably used
Can be. A_Three The chemical sensitization, or chemical sensitization and spectral sensitization
The coated photosensitive material has a gamma value of 2.0 to 2.0.
20, preferably 3.0 to 20 in the high contrast sensitive material
Degree / granularity) ratio is excellent and preferable. Embodiment of (I-1)
After preparing an AgX emulsion as described above, at any time until immediately before coating
In between, preferably before the desalting step, Z₁ , Z_Two 1.0-1
00%, preferably 70-100%
It can be removed, removed, and removed from the system. 10
98 ° C., pH 1.0-12.5, pX = 0.5-5.0
Under the most preferable combination conditions within the range of 5 seconds to
Desorption for 10 days, preferably 1 minute to 5 hours
You can leave. Patent application for details of the desorption and removal
The description in JP-A-11-364902 can be referred to. That
In addition, for a cationic organic compound such as the onium salt,
An anionic organic compound is represented by Z₁ , Z_Two 0.0 of the abundance of
1 to 10^Five Double molar amount, preferably 0.1 to 10^Four Double mole
It can be removed by adding only a small amount, or negative by electrodialysis.
The compound can also be collected on the extreme side and removed.
Examples of the compound have a molecular weight of 100 to 10.⁶ ,Preferably
100-10^Five There is an anionic surfactant, described below
Reference 16 (R.D. 1996) can be referred to. That
In addition, the salt concentration of the emulsion was increased to increase the ionic strength from 1.2 to 10
^Four Times, preferably 2 to 10^Four By doubling,
There is a method of salting out and removing the compound (i). The compound
The material is easily salted out and consists of light element atoms.
Since the specific gravity is smaller than the specific gravity of water or the emulsion,
It is easily salted out as a suspended matter on the surface. From the emulsion
It may be removed. The method of sucking the surface, the emulsion
There is a method such as gently pulling out from the bottom and leaving the surface part in the container.
You. Regarding the soluble salt to be added, an inorganic compound / complex
The dictionary and Kodansha (1997) can be referred to. So
And X^-Salts are preferred, pX = 0.5-2.5, preferably
Or 0.7 to 2.0 for salting out.
X^-Cl as seed^-, Br^-Alone or in any ratio
Can be used together. (Onium⁺) ・
(X^-) →→ (Onium⁺) + (X^-Left) dissolution equilibrium
This is for shifting to the side. (I-8) Others. A₁ , B₁₃, Preferably A₁ , B_FifteenIs the AgI of the core
The content (mol%) is 0.1 to 40, preferably 1 to 40,
AgI content (mol%) of the shell portion is 0.0 to 20 double.
Structural particles are preferred, and the (core / shell) molar ratio = 1
/Ten^Four~Ten^Four/ 1 is preferred, 1/10^Three~Ten^Three/ 1 is more preferred
No. The particle size (μm) is preferably from 0.1 to 20.
(AgI content of core part-AgI content of shell part) (mol%)
= 0.1-40, preferably 1-40, more preferably
5-35. Furthermore, the AgX solvent concentration (mol / liter)
0-1.0, preferably 0-0.01, more preferably
0-10^-FiveParticles formed under the above are preferred. Ag⁺
And a compound with high hydrophilicity is converted to an AgX solvent.
Small compounds are used as antifoggants (A₄₀) And grains
Acts as a child deformation inhibitor. pX = 2.2 or less, preferred
Or 0.3 to 1.7, the particle surface is X^-Body and A
₄₀Can hardly be adsorbed. A₄₀Is AgXn (n is 2 or more)
Integer) Coordinating with the complex to make it hydrophilic, and as an AgX solvent
Act. Therefore, the thin tabular grains become thicker. Therefore
A at a temperature of 40 to 100 ° C. in this region₄₀Avoid using
Things are preferred. A₁ , A₀ Particles have high pH (p
H8-13) and / or reduction sensitized by a reducing agent
And reduced silver nuclei and silver oxide nuclei are 0.1 μm^Three1 per
-10⁸Pcs, preferably 5-10⁶ That there are
preferable. Photosensitive material at 40-100 ° C for 1 hour to 1 day
When stored, the nuclei in the particles move and the photographic properties of the light-sensitive material
Change. Activation energy of the change (kjoule / mol)
Is 50 to 75, preferably 57 to 67, which is small.
This is not preferred. To prevent this, during particle formation
After the step of introducing dislocation lines inside the grains, reduction sensitization was performed.
Forming the nuclei on dislocation lines,
Sometimes it forms the nucleus and the two
And stabilize the nucleus. Or of the AgX emulsion
40 to 120 ° C, preferably between application and shipping of photosensitive material
50 to 90 ° C., humidity 1 to 70, preferably 5 to 4
10% at 0%^Five Minutes, preferably 60 to 10^Four Minutes
It is preferable to save and allow the nuclei to reach chemical equilibrium.
No. Or, after grain formation, just before the addition of the chemical sensitizer,
The AgX emulsion is allowed to stand at this temperature and for the same time while stirring or stirring.
It is preferred to hold and allow the nucleus to reach chemical equilibrium.
No. AgX particles, epitaxial particles, host particles
Doping, metal complex doping, chemical sensitization, spectroscopy
Color material and layer composition for sensitization, color photosensitive material composition, development
Regarding the processing, the description of Reference 5 described later can be referred to.

The tabular grains may be used as cores to form grains having dislocation lines therein. In this regard, the description of Reference 13 below can be referred to. The particles may be used as core particles, and an AgX layer different from the core particles may be laminated to form the multi-layered particles. The details can be referred to the description in Reference 14. (Chemical sensitization) Chalcogen sensitizer [sulfur sensitizer, selenium sensitizer, tellur sensitizer], gold sensitizer alone or in combination of two or more of them in chemical sensitization of AgX emulsion Can be used. Both the total amount of the chalcogen sensitizer and the total amount of the gold sensitizer per 1.0 mol of the AgX particles were 10 ^<-9>
10 ^-2 mol is preferable, and 10 ^-7 to 10 ^-4 mol is more preferable. For details of the compound, see Reference 15, (RD1996
Year) and the description in the literature below. High AgC
For the production of 1-content tabular grain emulsion, see JP-A-8-2
27117, 9-288325, and 2-34. The high refractive index inorganic fine particles are added to and contained in the tabular grain emulsion, and when the emulsion is coated on a support to form a photosensitive material, the dispersing medium phase is substantially exposed to the photosensitive peak wavelength light of the layer. Is transparent, the refractive index value of the dispersion medium phase with respect to the light is 1.03 to 2.5 times, preferably 1.06 to 2.0 times the value when the fine particles are not contained, The vertical reflectance of the light with respect to the main plane of the tabular grains in the layer is preferably 0.1 to 97% when not contained, and more preferably 1 to 80%. In the fine particles, the fine particles are not substantially coalesced in the layer, and the molar ratio of the fine particles (7 or more, preferably 3 or more / the molar amount of all the fine particles) is 0.0 to 0.1. 2 is preferred, and 0.0 to 0.05
Is more preferred. The light-sensitive material is preferably a color light-sensitive material having at least one layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, preferably three layers, more preferably a fourth light-sensitive layer. It is preferable that the treatment is performed in a development treatment step including at least a development step and a fixing step. The emulsion containing fine particles can be used as a light-sensitive layer of all light-sensitive materials described below, preferably a color light-sensitive material. In the case of a diffusion transfer type color photosensitive material, a coloring material is added to the emulsion. Regarding the coloring materials, color formers for color photographs, additives and oils for emulsifying and dispersing (RD 1996), Japanese Patent Application No. 11-28020.
Reference can be made to the description in No. 7 and the literature described below. The fine particles may be crystalline, amorphous, or a mixture of both, and may have a (core / shell) structure or a multi-structure particle having at least one core layer and at least one shell layer. Metal oxides are preferred, and the TiO ₂ content (mol%) is preferably 10 to 100, more preferably 50 to 100. For details of these, refer to Japanese Patent Application Nos. 11-280207 and 11-212364.
You can refer to the description of the issue. Since the thickness of the particles is small, the amount of intrinsic absorption light decreases. To compensate for this, a sensitizing dye having an absorption band in the range of 350 to 530 nm is preferably adsorbed at 20 to 300%, preferably 60 to 200% of the saturated adsorption amount of the blue light sensitive emulsion.

The AgX emulsion grains produced by the method of the present invention can be used by blending with one or more other AgX emulsions, or two or more of the emulsion grains of the present invention having different particle sizes can be blended and used. Can also. The blend ratio (moles of guest AgX emulsion / moles of AgX emulsion after blending) is preferably in the range of 0.99 to 0.01, and an appropriate ratio can be appropriately selected and used. There are no particular restrictions on the additives that can be added to the emulsion of the present invention during the period from the grain formation to the coating step, and the amounts thereof can be added, and any conventionally known photographic additives can be added in optimal amounts. For example, an AgX solvent, a dopant for AgX particles (for example, a Group 8 noble metal compound, another metal compound, a chalcogen compound, an SCN compound, etc.), a dispersion medium, an antifoggant, a sensitizing dye (blue, green,
Red, infrared, panchromatic, orthophoto, etc., supersensitizers, chemical sensitizers (sulfur, selenium, tellurium, gold and Group 8 noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone and A combination of two or more thereof in any ratio), a fogging agent, an emulsion sedimenting agent, a surfactant, a hardening agent, a dye, a color image forming agent, a color photographic additive, a soluble silver salt, a latent image stabilizer, Examples include a developer (hydroquinone-based compound, etc.), a pressure desensitizing agent, a matting agent, an antistatic agent, a dimensional stabilizer, and the like.

The AgX emulsion prepared by the method of the present invention can be used for all conventionally known photographic light-sensitive materials. For example, black-and-white silver halide photographic light-sensitive materials [for example, X-ray light-sensitive materials, printing light-sensitive materials, photographic paper, negative films, microfilms, direct positive light-sensitive materials, ultrafine dry plate light-sensitive materials (for LSI photomasks, shadow masks) , Liquid crystal masks)], color photographic light-sensitive materials (eg, negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method, etc.)
Can be used. In addition, diffusion transfer photosensitive materials (eg, color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), high-density digital recording photosensitive materials,
Examples include holographic materials. A preferable value of the applied silver amount is 0.01 to 50 (g / m ² ). AgX emulsion production method (particle formation, desalting, chemical sensitization, spectral sensitization, addition method of photographic additive, etc.) and apparatus, AgX particle structure, support, undercoat layer, surface protective layer, constitution of photographic light-sensitive material (E.g., layer composition, silver / color former molar ratio, silver amount ratio between layers, etc.) and product form and storage method,
There is no limitation on the emulsification and dispersion of the photographic additive, the exposure, the development method, and the like, and any conventional or future known techniques and modes can be used. For details of these, the description of the following literature can be referred to.

Reference 20, Research Disclosure Magazine, (Item 17643)
(Dec. 1978), (RD. 1996), by Duffin, Photographic Emuls.
ion Chemistry), Focal Press, New York (1966)
Year), Bill (EJ Birr), Stabilization of Photographic Silver Hal
ide Emulsion), Focal Press,
London (1974), James (TH Jame
s), Theory of Photographic Pro
cess) 4th edition, Macmillan, New York (1977)

P. Glafkides, Chemie and Physique Photographique, 5th Edition, (Edition del, Usine Nouvelle, Paris (198)
7), 2nd edition, Paul Montell, Paris (1957)
), VLZelikman et al., Making and Coating Photographic Emu
lsion), Focal Press (1964), KR Hollister Journal of Imaging
Science (Journal of Imaging Science), Volume 31,
P. 148-156 (1987), Maskasky (J.
E. Maskasky), pp. 247-254 (198)
6 years) 32 volumes, 160-177 (1988), 3 volumes
Volume 3, 10-13 (1989),

Freezer et al., Eds., Fundamentals of the silver halide photographic process (Die Grundlagen Der Photographischen Prozesse)
Mit Silverhalogeniden) (Akademische Verlaggesell
schaft), Frankfurt (1968). JCIA Monthly Report, December 1984, p. 18-27, Journal of the Photographic Society of Japan, 49, 7-12 (1986), 52, 14
4-166 (1989), 52 volumes, 41-48 (1
989), and JP-A-58-113926 to 113928.
No. 59-90841, No. 58-111936,
Nos. 62-99751, 60-143331, and 6
No. 0-143332, No. 61-14630, No. 62-
No.6251,

JP-A-1-131541, JP-A-2-838
Nos. 8-220664, 8-227117, 2-146033, 3-155538, and 3-2
No. 00952, No. 3-246534, No. 4-3454
No. 4, 2-28638, 4-109240, 2-73346, 4-193336, Japanese Patent Application No.
No. 215513, other Japanese patents in the field of AgX photography,
US Patent, European Patent, International Publication (WO) Application, Journal of Imaging Science (Journal of Ima
ging Science), the Journal of Photographic Science,
Photographic Science and Engineering, Journal of the Photographic Society of Japan, Abstracts of the Photographic Society of Japan, Internationala
l Congress of Photographic Science and The Inter
national East-West Symposium on the Factors Influe
Collection of abstracts of ncing Photographic Sensitivity. Japanese Patent Application Nos. 6-104065 and 5-324502. The emulsion of the present invention is disclosed in JP-A-62-266538 and JP-A-63-22022.
No. 38, No. 63-305343, No. 59-14253
No. 9, 62-253159, JP-A-1-13154
No. 1, No. 1-297649, No. 2-42, No. 1-1
No. 58429, No. 3-226730, No. 4-1516
No. 49, Japanese Patent Application No. 4-179951, 11-5709
No. 7, EP 0508398 A1.

(Literature) 1. JP-A-59-133542
No. 60-95533, U.S. Pat. No. 3,206,3.
No.13, No.3,317,322, No.3,761,27
Nos. 6, 4,269,927 and 3,367,778
And JP-A-1-158429 and 1-297694.
No., (RD 1994), and references described below. 2. JP-A-63-305343, JP-A-64-62631
No. 64-40938, JP-A-2-838, 1
No. 297649, No. 2-146033, No. 1-20
Nos. 1651 and 3-121445. 3. Journal of Photographic Science, 23, 249
Page (1975). JP-A-64-62631, (RD
1996). 4. European Patent Nos. 699,944A to 699,951A
Nos. 701, 164A to 701, 165A, JP-A-5-341426, and documents described below. 5. Journal of Imaqing Science, 32, 160-1
77 (1988), Journal of Colloid and Inter
face Science, 140, 335-361 (1990
Year), RD (1994), European Patent No. 699,944 A1
No.-699,951A1, No.215,612B1,
And references described below. 6. Fundamentals of photographic engineering, silver halide photography, Chapter 3, Corona (1979). 7. Journal of Imaqing Science, Volume 30, 247-2
57 (1986). 8. JP-A-11-223895, JP-A-11-23145
No. 0, No. 11-218862, No. 11-218863
No. 11-218865, No. 6-194768,
No. 7-311431, No. 8-106137, No. 8-
No. 339044, No. 9-211761, No. 11-30
No. 5366, No. 5-313273, No. 11-2492
No. 48, 6-308648, 6-308649
issue. 9. Edited by THJames, The Theory of Photographic Proce
ss, 4th edition, Macmillan (1977). 10. JP-A-4-184326 to JP-A-184330, 4
No. 34544, No. 1-183644, No. 1-183
No. 417, No. 2-166442, No. 11-30828
Nos. 4-184330, 4-181240, 5-5966, 2-167818, and U.S. Pat. No. 5,196,300 (RD 1996). European Patent No. 3
No. 23, 215A, No. 431, 584A, No. 407,
Nos. 576A and 779, 537A. 11． 4th edition, Electrochemical Handbook, Chapters 3-6, Maruzen (19
1985), 4th revised edition, Chemical Handbook, Basics, Chapter 12, Maruzen (1993). 12． JP-A-10-104679 and JP-A-8-69069
No.15, New Experimental Chemistry Course, Oxidation and Reduction, Maruzen (19
76), edited by Minoru Imoto, Lecture on Organic Reaction Mechanisms, Vol. 10, Tokyo Kagaku Dojin (1965), edited by Yoshiro Ogata, Oxidation and Reduction of Organic Compounds, Nankodo (1963), JP-A-61-3134
No., Encyclopedia of World Sciences, "redox", "oxidation process",
"Oxidizing Agent", Kodansha (1977), Britannica Encyclopedia, "Oxidation and Reduction", TBS Britannica (1988). 13. JP-A-63-220238, U.S. Pat.
6,760, JP-A-8-62754, 7-270
No. 952, No. 6-230491, No. 4-166926
No. 6-230491. 14. JP-A-1-201651, JP-A-2-28638,
2-943, 3-121445, 5-457
No. 57, JP-A-60-143331. 15． JP-A-8-220664 and JP-A-11-65009
No. 9-197604 (RD 1996). 16． Chemical Handbook, Applied Chemistry, Chapter 16, Maruzen (1986
), Hiroshi Horiguchi, New Surfactant, Sankyo Publishing (1975)
Year), (RD 1996). 17． U.S. Patent Nos. 5,318,889 and 5,187,
259, JP-A-6-214329 and 5-2651
13, No. 1-158426, edited by Nobumasa Imura et al., Biochemistry Handbook, Chapter 20, Chapter 21, Maruzen (1984
Year). 18． U.S. Patent Nos. 4,713,320 and 4,942,
No. 120, 5,412,075, JP-A-8-828
No. 83, No. 7-31428, No. 10-10663
No., Japanese Patent Application No. 10-87535, Journal of the Photographic Society of Japan, No. 5
8, 25-30 (1995), glue and gelatin,
Chapter 4, Japan Niwa Gelatin Industry Association (1987
Year), The Science and Technology of Gelatin, 7th
Chapter, Academic Press (1977), New Chemistry Laboratory Course 1,
Protein IV, Tokyo Kagaku Dojin (1991), Applications and Markets of Water-Soluble Polymers, CMC (1984), Water-Soluble Polymers, Chemical Industry Co., Ltd. (1990 Edition), Research Dis
closure magazine, 389, item38957 (September 1996
Mon) (hereinafter referred to as "RD1996"), written by Kazutaka Tanizawa,
Chemical modification of proteins, Hirokawa Shoten (1991). 19. JP-A-2-838, JP-A-8-82883, and 10
Nos. -10663, 10-10469, 1-21
No. 3637, No. 10-142721, No. 11-650
No. 09, No. 7-98482, No. 10-293372
Nos. 5,210,013 and 5,439,
No. 787, No. 5,962,206, Japanese Patent Application No. 11-36
4902 and 11-322913.

[0055]

Next, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto. Example 1 A gelatin solution 1 [1200 g of water, 0.6 g of KBr, 10 ^-4 mol of compound 1, 10 g of gelatin 1, and pH adjusted to 6.0 with a NaOH solution] was placed in a reaction vessel, and Ag was maintained at 60 ° C. with stirring. Solution -11 [containing 1.0 g of AgNO ₃ , 0.9 g of gelatin 1 and 0.25 ml of HNO ₃ (1N) solution in 100 ml] and Solution X-11 [KBr in 100 ml
0.8 g, ^10-4 mol of compound 1 and 0.9 of gelatin 1
g, 0.25 ml of NaOH (1N) solution] at 5 ml / min for 3 minutes. Subsequently, Ag-11 solution was added at a starting flow rate of 5.0 ml / min and an accelerating flow rate of 1.5 ml / min.
Min, while maintaining the pBr at 2.37 by the silver potential control method.
Simultaneously with 11 solutions. After stirring for 1 minute, a KBr solution was added, and the mixture was adjusted to pBr1.5 and the pH to 6.0.
While maintaining the pBr at 1.5, the Ag-12 solution (containing 14 g of AgNO ₃ in 100 ml) was used as a starting flow rate of 2.0 ml /
X-12 solution [containing 10.6 g of KBr in 100 ml] at the same time for 44 minutes at an acceleration flow rate of 0.56 ml / min. Next, Ag-13 solution [28 g of AgNO _{3 in} 100 ml
Including], start flow rate 12 ml / min, acceleration flow rate 0.18 ml
X-13 solution [KBr in 100 ml / 20 ml / min.
0.5 g). After stirring for 1 minute, the following post-treatment was performed. Ag-14 solution [AgN in 100 ml
Containing 10 g of O ₃ ] to obtain pBr 2.6.
Sensitizing dye 1 was added by 85% of the saturated adsorption amount,
The temperature was raised to 0 ° C., and the mixture was stirred for 20 minutes. Next, the antifoggant (F1) was added only by (10 ⁻³ mol / mol AgX), and
Stirred for minutes. Compound 1 was desorbed by adsorbing them. Next, a coagulating sedimentation agent was added, the temperature was lowered to 30 ° C., the pH was adjusted to 4.0, and the emulsion was sedimented and desalted by a sedimentation washing method according to a conventional method. This gives 95% of compound 1.
These have been removed. Then add the gelatin solution and adjust the pH
6.4, pBr 2.6, redispersed at 40 ° C. At this time, 1 ml of the emulsion was collected, and a transmission electron micrograph (hereinafter, referred to as a “TEM image”) of the replica film of the particles was observed.
The results are shown in Table 2. Raise the temperature to 60 ° C and add the gold sensitizer
1 [Aqueous solution of chloroauric acid: NaSCN = 1: 20 molar ratio]
In the amount of Au (8 × 10 ⁻⁶ mol / mol AgX),
After 2 minutes, the chalcogenide sensitizer Sx1 was replaced with Na ₂ S ₂ O ₃
(10 ⁻⁵ mol / mol AgX) in the amount and aging for 30 minutes. This emulsion was coated according to the following coating formulation, hardened, and a cut sample was obtained. Gelatin 2, a thickener, and a coating aid were added, and the resultant was coated on a subbed cellulose triacetate transparent base together with a protective layer containing a hardener 1, followed by drying. The sample was placed in a sealed empty can, stored at 40 ° C. for 17 hours, and a hardening reaction was allowed to proceed. Next, this is taken out, cut, and the sample 1
It was set to -1. (Comparative Example 1) Sample 1-2 was prepared in the same manner as in Example 1 except that Compound 1 was not added.

[0056]

Embedded image

Example 2 Gelatin solution 2 [1200 g of water, 0.36 g of NaCl,
Compound 2 with 10^-FourMol, 30 g of gelatin 1, HNO_Three 
Solution to pH 4.5) into the reaction vessel and keep at 40 ° C.
Ag-21 solution [AgNO in 100 ml with stirring]
_Three 2.0 g, gelatin 1 0.9 g, compound 2 10 g
^-FourMole, HNO_Three(1N) solution 0.25 ml] and X-2
1 solution (0.76 g of NaCl and 100 ml of gelatin in 100 ml)
0.9 g, containing 0.25 ml of a NaOH (1N) solution].
Co-addition at 6.0 ml / min for 3 minutes. Continue with Ag-2
Start flow of one solution 6.0 ml / min, acceleration flow 2.0 ml / min
For 14 minutes and keep at pCl 2.3 by silver potential control.
It was added simultaneously with the X-21 solution. Adjust the pH to 6.0
Was. Next, Ag-22 solution [AgNO in 100 ml_Three 20
g) with a start flow of 3.1 ml / min and an acceleration flow of 0.2
ml / min for 60 minutes, while also maintaining pCl 2.0
X-22 solution (containing 7.0 g of NaCl in 100 ml)
Co-added. Next, 0.005 mol of U-5 was added with AgI.
The mixture was heated to 65 ° C. and aged for 15 minutes. Ag-14
The solution was added to make pCl 2.3, and sensitizing dye 2 was saturated
Only 85% of the applied amount was added. Raise the temperature to 65 ° C,
Stirred for minutes. Further, the antifoggant (F2) was added to (10^-3Mo
Per mole of AgX) and stirred for 15 minutes. Then
Add the precipitant, lower the temperature to 30 ° C. and adjust the pH to 4.0
The emulsion was sedimented and desalted. This allows compound 2
More than 95% was removed. Then add the gelatin solution,
Redispersed at pH 6.4, pCl 2.6, 40 ° C.
Obtain 1 ml of emulsion and observe TEM image of grain replica film
The results are shown in Table 2. Raise temperature to 55 ° C and cover
3 × 10 reducing agent (F3)^-FiveAdd mol / mol AgX only
And stirred for 15 minutes. Next, the Sx1 is replaced with Na_Two S_Two O_Three 
In quantity (2 × 10^-FiveMol / mol AgX) and after 3 minutes
And chloroauric acid in 5 × 10^-6Mol / mol AgX only,
Aged for 20 minutes. The emulsion was coated in the same manner as in Example 1,
The film was hardened and cut to obtain Sample 2-1. (Comparative Example 2) In Example 2, the addition of Compound 1 was eliminated.
Same except that U-6 is added instead of U-5
Thus, a coated sample 2-2 was obtained. Example 3 Gelatin solution 3 [1200 ml of water, 1.7 of gelatin 3
g, KBr 0.5g, HNO_Three PH 2.3 with liquid
Adjustment] into a reaction vessel, and place it in constant temperature water at a temperature of 1.0 ° C.
Ag-31 while keeping the solution temperature at 1.0 ° C.
Solution [AgNO in 100 ml_Three 6.0 g, gelatin 3
0.14 g, HNO_Three(1N) 0.2ml] and X-3
1 solution [4.29 g of KBr and gelatin 3 in 100 ml
0.14 g, containing 0.2 ml of a NaOH (1N) solution].
Simultaneous addition was performed at a rate of ml / min for 1 minute. Ag-31 solution, X-
Liquid 31 passes through a 3 mm outer diameter feed tube through the constant temperature water bath.
After cooling to about 1 ° C., it was added. 2.8 g of KBr
Add, raise temperature to 60 ° C at 3 ° C / min and ripen for 12 minutes
did. Add NaOH solution to pH 9.1, and 12 minutes
Matured. Gelatin solution 4 [25 g of gelatin 4, water 1
75 g] was added, and the pH was adjusted to 7.0. Then A
gBr fine grain emulsion (U-1) in an amount of 0.32
And a KBr solution to obtain a pBr of 1.6 and a temperature of 75.
° C. After 10 minutes, 0.32 mol of U-1 was added,
After 15 minutes, when the added fine particles have almost disappeared,
The temperature was reduced to 60 ° C. Ag-14 solution does not generate new nuclei
It was added at an addition rate to obtain pBr2.3. Sensitizing dye 1
Only 85% of the saturated adsorption amount was added, and the mixture was stirred for 20 minutes. Change
(F1) to (10^-3Mol / mol AgX) and add 1
Stir for 5 minutes. Add sedimentation agent and reduce temperature to 30 ° C
And the pH was adjusted to 4.0, and the emulsion was sedimented and desalted. this
Removed 95% or more of compound 1. Gelatin solution
Liquid 2 was added, and the mixture was re-added at 40 ° C., pH 6.4, and pBr 2.6.
Dispersed. 1 ml of the emulsion was collected, and the T
The EM image was observed, and the results are shown in Table 3. A in Table 3₅₁Is
The aspect ratio to the total projected area of the AgX grains is 2
The projection area ratio (%) of the above {111} tabular grains is shown.
You. The temperature was raised to 60 ° C. and the sensitizer Sx1 was changed to Na_Two S_Two O
_Three In quantity (2 × 10^-FiveMol / mol AgX) and add 2 minutes
Later, gold sensitizer-1 was added (8 × 10^-6Mol / mol AgX) only
Added and aged for 30 minutes. The emulsion was prepared in the same manner as in Example 1.
The sample was applied, hardened, and cut to obtain Sample 3-1. (Comparative Example 3) In Example 3, U-2 was used instead of U-1.
The procedure was the same as in Example 3 except that the coating sample 3-2 was obtained.
Was. Example 4 A gelatin solution [H_Two O1.2kg, NaCl
2.7 g, 3 × 10 of compound 3^-FourMol, 5 gelatin 1
g, pH 5.6], and kept at 30 ° C. while stirring.
Ag-41 solution [AgNO in 100 ml_Three 25.5 g
And X-41 solution [9.4 g of NaCl in 100 ml,
1 g of gelatin 3 and pH 6.0] at 30 ml / min.
For 2 minutes to form a seed crystal of twin tabular grains.
One minute later, an aqueous gelatin solution (25 g of gelatin 1, compound
4 to 10^-FourAdjusted to pH 5.6).
0 g was added to obtain pCl 1.6. Then heat up to 65 ° C
And aged for 15 minutes. Next, an AgCl fine grain emulsion (U-
3) was added in an amount of 0.2 mol, aged for 20 minutes, and then U-3
Was added and the mixture was aged for 20 minutes. Ag with U-5
After adding 0.005 mol in I amount and aging for 15 minutes, A
g-14 solution was added at an addition rate at which no new nuclei were generated.
l 2.2. 60 ° C and sensitizing dye 2 was saturated
Only 85% of the applied amount was added. Next, the antifoggant F2
(10^-3Mol / mol AgX) and stirred for 15 minutes.
After that, a precipitant was added. 30 ℃, pH 4.0
The emulsion was sedimented and desalted. This gives compound 9
More than 5% was removed. Add gelatin solution and add 40
C., pH 6.4, redispersed in pCl 2.3. Generate
The TEM image of the particles was observed, and the results are shown in Table 3. $ 1
An 11 ° tabular grain emulsion was obtained. The temperature was raised to 55 ° C and F3
To (3 × 10^-FiveMol / mol AgX) only for 15 minutes
Stirred. Next, Sx1 is changed to (2 × 10^-FiveMol / mol AgX)
And then chloroauric acid (5 × 10^-6Mol / mol Ag
X) alone and aged for 30 minutes. Lower to 40 ° C
Sample 4 was applied in the same manner as in Example 1, dried, hardened, and cut.
-1 was obtained. (Comparative Example 4) In Example 4, U-4 was used instead of U-3.
Example except that U-6 is used instead of U-5
In the same manner as in Example 4, coating sample 4-2 was obtained. Example 5 A gelatin solution 5 [H_Two O1200g, gelatin
25 g of compound 1 and 10 g of compound 2^-FourMol, NaCl 0.
8g, pH 4.3], stir at 30 ° C, and stir
Ag-51 solution [AgNO in 100 ml_Three 20
g and gelatin 1 1.0g, HNO_Three Is 5 × 10^-3Mole
And X-51 solution (7 g of NaCl in 100 ml,
1 g of latin, 5 × 10 NaOH^-350 ml)
/ Min at the same time for 30 seconds to form AgCl fine particles.
Done. After stirring for 2 minutes, X-52 solution [in 100 ml
1.5 g of KBr and 1 g of gelatin] at a rate of 60 ml / min.
Added for 30 seconds. (3 ° C./min) to 40 ° C.
Stirred for minutes. Next, 50 ml of Ag-51 solution and X-51 solution
/ Min for 1 minute. NaCl-51 liquid
16 ml of [NaCl 0.1 g / ml] was added, and NaOH was added.
The solution was adjusted to pH 5.2. Next, the temperature was raised to 70 ° C at 2 ° C / min.
And aged for 12 minutes. 0.2 mol of U-3 with AgCl
Add to pCl 1.9. After aging for 20 minutes,
0.4 mol of U-3 was added and pCl 1.9 for 30 minutes
Matured. Next, Ag-51 solution and X-53 solution [100 ml
Contains 7 g of NaCl and 2.5 g of KBr] at 5 ml / min.
For 3 minutes. Sensitizing dye 2 at 85% of the saturated adsorption amount
Was added. After stirring for 15 minutes, F2 was added to (10^-3Mol /
(Mol AgX) alone and stirred for 15 minutes. Add sedimentation agent
And the temperature was lowered to 30 ° C. to pH 4.0, and the emulsion was precipitated.
It was let down and desalted. This allows more than 95% of compound 2
Removed. Add gelatin solution, 40 ° C, pH6.
4. Redispersed in pCl 2.3. The TE of the generated particles
The M image was observed, and the results are shown in Table 3. {100} flat plate
A grain emulsion was obtained. The temperature was raised to 55 ° C., and Sx1 was changed to (2 ×
10^-FiveMol / mol AgX), and after 3 minutes, chloroauric acid
Aqueous solution (5 × 10^-6Mol / mol AgX) and add 3
Aged for 0 minutes. Reduce to 40 ° C and apply in the same manner as in Example 1.
Then, drying, hardening, and cutting were performed to obtain a sample 5-1. (Comparative Example 5) In Example 5, U-4 was used instead of U-3.
The procedure was the same as in Example 5 except that the coating sample 5-2 was obtained.
Was. The obtained sample was passed through an optical wedge for 0.1 second.
Samples 1-1, 1-2, 3-1 and 3-2 were exposed to white light.
Is MAA-1 developer [Journal of Photographic Scienc
e, vol. 23, 249-256 (1975)
At 20 ° C. for 10 minutes. On the other hand, sample 2-
1, 2-2, 4-1 and 4-2, 5-1 and 5-2 are MAA
-2 developer [Kr of MAA-1 is converted to NaCl (0.58
g / liter) at 20 ° C for 4 minutes.
Was. Next, through stop, fixing, washing, and drying steps,
Perform cytometry to determine the (sensitivity / granularity) ratio,
Relative value (A ₅₀) Are shown in Tables 2 and 3. Sensitivity is (fog
+0.2) The reverse of the exposure (looks / second) that gives a density of
The granularity is represented by the density of (fog + 0.2)
10 to give the amount of light^-2Exposure for a second and then develop
Microdensitometry using a circular opening with a diameter of 48 μm.
Measure the dispersion of the density with a heater and obtain the rms granularity σ.
I did. The details are described in Chapter 21, Section E of Reference 7.
You.

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

Embedded image

(Gelatin 1): The methionine content was about (5
μmol / g) and gelatin having a weight average molecular weight of about 10 ⁵ .
H ₂ O ₂ was added to an aqueous solution of deionized alkali-treated beef bone gelatin (EGel 1) having a molecular weight of about 10 ⁵ to oxidize the thioether group of the methionine group to a sulfoxide group, and then the remaining H ₂ O ₂ was converted to MnO ₂ The MnO ₂ powder, into which the powder was put and decomposed and removed, was removed by filtration. (Gelatin 2): The methionine content was about (43 μmol /
g), gelatin having a weight average molecular weight of about 5 × 10 ⁵ . EGe
l 1 was intermolecularly crosslinked with hardener 1 to prepare. (Gelatin 3): Gelatin having a mass average molecular weight of about 15,000 and a methionine group content (μmol / g) of 0. EGel
A solution obtained by adding an enzyme to the aqueous solution of No. 1 and decomposing it at about 40 ° C. and pH 5.5 to oxidize gelatin (LGel 1) having a reduced molecular weight in the same manner as gelatin 1. (Gelatin 4): Gelatin having a mass average molecular weight of about 30,000 and a methionine group content of 5 (μmol / g). (Gelatin 5): Gelatin in which about 50% of the amino groups of EGel 1 have been trimellitized. Preparation of AgBr fine grain emulsion (U-1): Gelatin solution 3
1 [1200 ml of water, 24 g of gelatin 4 and 3
× 10 ^-4 mol, containing 0.3 g of KBr, p with NaOH solution
H adjusted to 6.0] in a reaction vessel, placed in a thermostatic water bath, and while maintaining the solution temperature at 20 ° C, the Ag-35 solution [1
20 g of AgNO ₃ and 0.8 of gelatin 4 in 00 ml
g, containing 2.5 × 10 ^-4 mol of HNO ₃ ] and X-35 solution [14.06 g of KBr and 100 mg of gelatin 4 in 100 ml.
8 g, containing 2.5 × 10 ^-4 mol of NaOH).
It was added at 10 ml / min for 10 seconds, followed by 70 ml / min for 7 minutes. At this time, an aqueous solution of Cp-1 [compound 1 in 100 ml
3 × 10 ^-4 mol in the first 10 seconds.
ml / min, followed by co-mixing at 7 ml / min for 7 minutes. After stirring for 2 minutes, this was used as U-1 within 30 minutes. The average diameter of the formed particles (A ₅₂ ) is about 0.0
Ratio of particles having a size of 35 μm and having two or more twin planes (A ₅₃ )
Was 0.00%, and the ratio of particles containing one or more twin planes (A ₅₄ ) was also 0.0%. Preparation of (U-2): Preparation was carried out in the same manner as in preparation of U-1 except that all the addition of compound 1 was eliminated. A ₅₂ = 0.
05 μm, A ₅₃ = 2%, A ₅₄ = 8%. Preparation of (U-3): gelatin solution 41 [1200 ml of water,
24 g of gelatin 4, 3 × 10 ^-4 mol of compound 2 and Na
Containing 0.3 g of Cl and adjusted to pH 3.5 with HNO ₃ ) in a reaction vessel, and put this in a constant temperature water bath at 20 ° C., while maintaining the solution temperature at 20 ° C., Ag-35 solution and X-45 solution [ 3.5 g of NaCl and 0.8 g of gelatin 4 in 100 ml
g, containing 3 × 10 ^-4 moles of NaOH] at 30 ml / min for 10 seconds, followed by 100 ml / min for 7 minutes. At this time, an aqueous solution of Cp-2 (containing 2 × 10 ^-4 mol of compound 2 in 100 ml) was added to 3.0 ml / l for the first 10 seconds.
Min, followed by co-mixing at 10 ml / min for 7 minutes. After 2 minutes, 5 ml of H ₂ O ₂ (3.1% by mass) was added, and the mixture was homogenized and allowed to stand for 1 hour at 20 ° C., whereby the gelatin had a methionine group content (μmol / g) of 0%.
It became. After stirring, this was used as U-3. A
₅₂ = 0.04 µm, A ₅₃ = 0.0%, and A ₅₄ = 0.0%. Preparation of (U-4): Preparation was carried out in the same manner as in the preparation of U-3 except that all the addition of compound 2 was omitted. A ₅₂ = 0.
06 μm, A ₅₃ = 2.2%, A ₅₄ = 10%. Preparation of AgI fine particles (U-5): Gelatin solution 32 [1200 ml of water, 24 g of gelatin 4 and 3 × 10
^-4 mol, 0.3 g of KI, pH 6.0 with NaOH solution
Into a reaction vessel, put this in a thermostatic water bath, and while maintaining the solution temperature at 20 ° C, Ag-35 and X-35 solutions [19.6 g of KI and 0.84 of gelatin 4 in 100 ml.
g, containing 3 × 10 ⁻⁴ mol of NaOH] at 15 ml / min for 10 seconds, followed by 70 ml / min for 7 minutes. At this time, the Cp-1 aqueous solution was 1.5 times for the first 10 seconds.
ml / min, followed by co-mixing at 7 ml / min for 7 minutes. After 2 minutes, 5 ml of the H ₂ O ₂ was added, and the mixture was homogenized and mixed. After that, the mixture was allowed to stand at 20 ° C. for 1 hour to obtain U-5. A ₅₂ = 0.014 μm, A ₅₃ = 0.0%, A ₅₄ =
0.0%. Preparation of (U-6): It was prepared in the same manner as in the preparation of U-5 except that all the addition of compound 1 was omitted. A ₅₂ = 0.
025 μm, A ₅₃ = 1.8%, A ₅₄ = 9%. Note that (U-1) to (U-6) were all prepared in a mixing vessel set within 3 m from the reaction vessel to be added, adjusted to the same pH and pX as the AgX emulsion to be added, and then added. Was done. The Ag ⁺ solution, the X ^- solution, and the aqueous solutions of Z ₁ and Z ₂ were all added to the mixing box present in the reaction solution. From these results, the effect of the present invention was confirmed.

[0062]

According to the present invention, an AgX photographic light-sensitive material having an excellent (sensitivity / granularity) ratio was obtained.

Claims (4)

[Claims] (1) At least silver halide grains (A
₁ ) And the dispersion medium (A_Two(A)
_Three )₁ Is 60 to 10 in particle number ratio (%).
0 is a particle having no two or more twin planes in the particle,
A₁ Seed crystal (A _Five ) Is formed by the adsorbent (Z
₁ ) In a total amount of 1 / l of the reaction solution.
0^-8To 1.0 mol of a dispersion medium solution (A_Four Made in)
A method for producing a silver halide emulsion, characterized in that: a1) Compounds described in the following (i) to (viii). (I) Onium
A compound containing one or more bases in one molecule, (ii) aromatic
One or more iodo groups and one or more -OH groups are substituted on the aromatic ring
An aromatic compound, (iii) a nitrogen-containing heterocyclic compound,
One or more heterocycles containing two or more nitrogen atoms in a 4- to 7-membered ring
A compound containing one or more molecules in a molecule, (iv) a cyanine dye
And (v) compounds having a heterocyclic group containing a divalent sulfur group
Product, (vi) thiourea compound, (vii) aminothioether
(Viii) the total number of carbon atoms containing a divalent sulfur group is 25 or less
Gelatin and NH in organic compounds_Four ⁺Compounds excluding. 2. The composition according to claim 1, wherein said A ₁ has a particle number ratio (%) of 60 to 10%.
2. The method for producing a silver halide emulsion according to claim 1, wherein 0 is a grain having no twin plane in the grain. 3. At least silver halide grains (B₁ )When
Dispersion medium (B_Two ) And water containing silver halide emulsion (B_Three )
Silver halide fine particles having an average diameter (nm) of 1.0 to 200
Child (C₁ ) Containing silver halide fine grain emulsion (C_Two )
And add C ₁ Is dissolved and B₁ By depositing on top
R B₁ Method of growing silver halide grains
And C₁ Is the particle number ratio (%) and 60 to 100 are in the particles.
Fine particles without two or more twin planes₁ Is the following a
2) Adsorbent described (Z_Two ) In total amount
10 per liter^-8Dispersion medium solution containing ~ 1.0 mol
(B_Four Silver halide emulsion characterized by being carried out in)
Manufacturing method. a2) Compounds described in the following (i) to (viii). (I) Onium
A compound containing one or more bases in one molecule, (ii) aromatic
One or more iodo groups and one or more -OH groups are substituted on the aromatic ring
An aromatic compound, (iii) a nitrogen-containing heterocyclic compound,
One or more heterocycles containing two or more nitrogen atoms in a 4- to 7-membered ring
A compound containing one or more molecules in a molecule, (iv) a cyanine dye
And (v) compounds having a heterocyclic group containing a divalent sulfur group
Product, (vi) thiourea compound, (vii) aminothioether
(Viii) the total number of carbon atoms containing a divalent sulfur group is 25 or less
Gelatin and NH in organic compounds_Four ⁺Compounds excluding. 4. The method according to claim 1, wherein said C ₁ has a particle number ratio (%) of 60 to 10%.
4. The method for producing a silver halide emulsion according to claim 3, wherein 0 is a fine grain having no twin plane in the grain.