JP2006284751A - Silver halide emulsion, photographic sensitive material, method for growing silver halide grains, and filter material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion that gives high sensitivity and high image quality. <P>SOLUTION: The silver halide emulsion comprises at least a dispersion medium and silver halide grains (AgX), wherein the grains which occupy 60-100% of the total projected area of the silver halide grains are grains (AgX<SB>1</SB>) having an AgI content of 85-100 mol%, a grain shape of a right-angled hexahedron whose angles and/or edges are optionally roundish, and a circle-equivalent projected diameter of 0.01-20 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silver halide (hereinafter referred to as “AgX”) emulsion useful in the field of photography, a method for producing silver halide grains, and a photographic light-sensitive material (hereinafter referred to as “photosensitive material”). The present invention also relates to a filter that absorbs UV light and / or blue light.

I-1) Conventionally, the following techniques have been disclosed.
1) The presence of α-type, β-type, γ-type, and δ-type as AgI crystal structures has been confirmed from their X-ray diffraction data. You can refer to the description.
The α type has a body-centered cubic structure and exists in a high temperature range of about 150 ℃ or higher. At temperatures lower than that, there is a hexagonal structure β-type and a face-centered cubic structure γ-type (called Cubic-Phase), and it is difficult to completely separate them. The δ type has a NaCl type crystal structure and exists under special conditions of high temperature and pressure.
2) Document 6 describes tetrahedron, dodecahedron and hexagonal prism-shaped AgI particles.
3) Reference 7 describes tabular AgI particles.
4) The α-type AgI which is unstable and disappears at 27 ° C. or lower is described in Reference 3. It disappears and becomes β type and γ type. However, the material that changes at 27 ° C. or lower is not practical. The powder method X-ray diffraction pattern of the α-type AgI emulsion grains stored at 27 ° C. or higher is described in Reference 3, and the diffraction peak (β2) of the (002) plane of the β-type phase and the α-type phase The intensity ratio of the diffraction peak (α1) on the (110) plane = “α1 peak intensity / β2 peak intensity” is 0.35 or less. That is, this is an embodiment in which the α-type content is very low.
5) Regarding AgI emulsion grains having an intrinsic light absorption edge wavelength of 10 nm or more and longer wavelength than β type even at 25 ° C. or lower, it is described in Reference 10. It is described that the particles are neither α-type, β-type, γ-type nor a mixture thereof.
6) When the AgI particle formation is performed under the conditions (Ag + concentration> I−concentration), particles having a high γ content are obtained, and when the AgI particle formation is performed under the conditions (Ag + concentration <I−concentration), particles having a high β content are obtained. This is described in Document 3. The behavior when the temperature of the AgI crystal is changed is described in Reference 5.
The preparation of conventional AgI emulsion grains, their properties, and their use in photographic light-sensitive materials are described in References 1 to 10 and the references cited therein.
7) Since the light absorption in the 400 to 430 nm region of β-type and γ-type is a direct transition type, its absorption coefficient is about 100 times larger than the absorption coefficient of the region of AgBr. This has the advantage of efficiently absorbing blue-violet light. This is described in Document 8.
US Pat. No. 2,327,764 describes the use of AgI particles as a UV absorber for a color filter UV filter layer using this property.
8) An aspect has been proposed in which an epitaxial AgX portion (hereinafter abbreviated as “epi portion”) is formed on AgI particles, chemical sensitization nuclei are formed in the epi portion, and a latent image is efficiently formed there. This is described in Document 9.
9) Increasing the refractive index of the dispersion medium layer by reducing the light scattering intensity of the AgX particles by mixing high refractive index fine particles and / or one or more of atoms, molecules and ions into the dispersion medium layer of the photosensitive material. This is described in Document 11.
10) Fine particles with a high AgI content are present in the vicinity of AgX tabular grains (AgBr content is 50 mol% or more) spectrally sensitized at a high coverage, thereby suppressing the amount of dye stain generated during development processing. This is described in Document 12.
However, the above literature does not describe the right-angled hexahedral AgI particles of the present invention. There is no description regarding an emulsion having a high hexahedral grain ratio.
U.S. Pat. No. 2,327,764 US Pat. No. 4,672,026 B. L. J. et al. Byerley et al. Photographic Science, 1970, 18, 53-59 (review).

  To provide an AgX emulsion and a photographic material that give higher sensitivity and higher image quality than conventional AgX emulsions. In addition, a blue-violet light absorbing filter material having excellent blue-violet light absorption characteristics is provided.

The object of the present invention has been achieved by the following embodiments.
I-2) Embodiment.
(1) In a silver halide emulsion having at least a dispersion medium and silver halide grains (AgX ₀ ), the total projected area of the grains is 50 to 100, preferably 60 to 100, more preferably 80 to 100, still more preferably. Are particles of 90 to 100, particularly preferably 95 to 100%, and have an AgI content of 80 to 100, preferably 85 to 100, more preferably 90 to 100, still more preferably 95 to 100 mol%. Is a right-angled hexahedron (meaning a rectangular parallelepiped, including a cube), or a shape whose corners and / or edges are rounded, and a circle equivalent projected diameter (hereinafter referred to as a diameter) of the particle is A silver halide emulsion (AgX ₄ ), characterized by being grains (AgX ₁ ) of 0.01 to 20, 0.02 to 10, 0.03 to 3 μm.
(2) Side length ratio of the hexahedron = “one side of one particle indicates (longest side length / shortest side length)” or the side of the rounded particle By extending the straight part or the flat part of the surface, the side length ratio of the right-angled hexahedron formed is 1.0 to 1.4, preferably 1.0 to 1.3, more preferably 1.0. The silver halide emulsion according to (1), wherein the silver halide emulsion is -1.2, more preferably 1.0-1.1.
(3) In a photographic light-sensitive material in which one or more layers, preferably 1 to 20 layers of silver halide emulsion are coated on one or both sides of a support, at least one layer, preferably 1 to 10 layers of silver halide emulsion A photographic light-sensitive material characterized by being a silver halide emulsion described in (1).
(4) The silver halide seed crystal emulsion (AgX ₁₁ ) having at least a dispersion medium, water, and silver halide seed crystal grains (AgX ₁₀ ) has an AgI content of 80 to 100, preferably 85 to 100, more preferably A silver halide seed crystal is added by adding 90-100 mol%, more preferably 95-100 mol% of a silver halide fine grain emulsion (AgX ₁₂ ), dissolving the added fine grain, and depositing on the seed crystal grain. A method for growing silver halide seed crystal grains, characterized in that the fine grains contain AgX ₁ described in (1).

(5) The AgX ₁₂ is an embodiment of the AgX ₄ , preferably the average diameter (μm) of the AgX ₁₂ is 0.005 to 0.3, preferably 0.02 to 0.2, (4) The method for growing a silver halide seed crystal according to (4).
(6) The radius of curvature of the rounded portion is 0.01 to 20, preferably 0.05 to 10, more preferably 0.2 to 5 times the diameter of the particle. (1) The silver halide emulsion as described above.
(7) The silver halide emulsion as described in (1), wherein the angle of each face of the right-angled hexahedron is 84 to 96, preferably 86 to 94, more preferably 88 to 92 degrees. .
(8) Coefficient of variation (standard deviation / average value) = CV of the diameter distribution of the AgX ₁ particles or the AgX ₀ particles is 0.01 to 0.5, preferably 0.02 to 0.3. The silver halide emulsion according to (1), wherein the silver halide emulsion is more preferably 0.03 to 0.2, and still more preferably 0.03 to 0.15.
(9) One surface of the hexahedral particles is placed on the substrate surface parallel to the substrate surface, cooled to -100 ° C. or lower, irradiated with an electron beam from above the surface, and transmissive type When an electron microscope image is taken, 1 to 10 ⁵ lines, preferably 2 to 10 ⁴ lines, differ in contrast on both sides of the line in the diagonal direction of the right quadrilateral on the upper surface of the particle. More preferably, 2 to 10 ³ grains are observed, and the silver halide emulsion as described in (1).
(10) The silver halide emulsion as described in (9), wherein the line is a crystal defect surface.

(11) The silver halide emulsion as described in (10), wherein the defect surface is any phase interface between an α-type phase, a β-type phase and a γ-type phase of an AgI crystal.
(12) The AgX. When measuring the powder method X-ray diffraction of the particles, it has a diffraction peak (α1) between the angle of the diffraction peak (β2) of the (002) plane of the β-type phase and the diffraction peak (β3) of the (101) plane. Further, the ratio of “peak intensity of α1 / peak intensity of β3” is 1.0 to 10 ⁶ , preferably 2.0 to 10 ⁵ , more preferably 5 to 10 ⁴ , and still more preferably 10 to 10 ^3. The silver halide emulsion as described in (1) above,
(13) The peak position of α1 is (the peak angle of α1−the peak angle of β2) / (the peak angle of β3−the peak angle of β2) = 0.1 to 0.9, preferably 0 The silver halide emulsion according to (12), wherein the silver halide emulsion is in the region of 2 to 0.8, more preferably 0.3 to 0.7.
(14) The emulsion (AgX ₄ ) is stored at 25 ° C. or less, preferably 0 to 20 ° C., more preferably 0 to 10 ° C., for 2 days or more, preferably 10 days or more, more preferably 30 days or more. The silver halide emulsion of (1), wherein the peak intensity ratio of (12) is maintained.

(15) The silver halide emulsion as described in (14), wherein the storage is carried out in the form of a coated product obtained by coating the emulsion on a support and drying.
(16) The long wavelength end wavelength of intrinsic light absorption of AgX ₁ or AgX ₀ is 8 to 50, preferably 15 to 50, more preferably 25 to 45 nm, longer than the wavelength of the β-type crystal phase. (1) The silver halide emulsion as described in (1) above.
(17) The AgX ₀ contains at least the AgX ₁ and AgX ₂ particles, and the AgI content (mol%) of the AgX ₂ particles is 80 to 100, preferably 85 to 100, more preferably 90 to 100, More preferably 95-100 mol%, the particles contain a β-type crystal structure, the β-type content (mol%) is 30-100, preferably 50-100, more preferably 80-100. The silver halide emulsion as described in (1) above,
(18) The average diameter of the AgX ₂ particles is 0.5 to 5, preferably 0.7 to 2, more preferably 0.9 to 1.5 times the average diameter of the AgX ₁ particles. The silver halide emulsion as described in (17), which is characterized in that
(19) Projected area ratio of the AgX ₁ particles and AgX ₂ particles = (total projected area of the AgX ₂ particles / total projected area of the AgX ₁ particles) = A1, or a ratio of the number of particles of both (the AgX (Total number of particles of ₂ particles / total number of particles of AgX ₁ particles) = A2 is 10 ^{−5 to} 0.4, preferably 10 ^{−4 to} 0.2, more preferably 10 ^{−4 to} 0.1. The silver halide emulsion according to (17) or (18), more preferably from 10 ^{−3 to} 0.01.

(20) The silver halide emulsion as described in (17), wherein the projected area ratio of the AgX ₁ grains and AgX ₂ grains = A1, or the ratio of the number of grains = A2 is smaller than 10 ⁻⁵ .
(21) The shape of the AgX ₂ particles is a dodecahedron having 12 parallelogram-shaped outer surfaces, or a shape whose corners and / or edges are rounded, (17) Silver halide emulsion.
(22) It is characterized in that at least one face of the AgX ₂ particle is the {002} face of the β-type crystal structure and at least one face is the {101} face of the β-type crystal structure. The silver halide emulsion according to (21).
(23) The shape of the AgX ₂ particles is a tetrahedron having two hexagonal surfaces parallel to 12 trapezoidal outer surfaces, or a shape having rounded corners and / or edges, Projected area ratio = (total projected area of the AgX ₂ particles / total projected area of the AgX ₁ particles) = A1, or the ratio of the number of particles = (total of the number of particles of the AgX ₂ particles / the AgX ₁ The total number of particles) = A2 is 10 ^{−5 to} 0.4, preferably 10 ^{−4 to} 0.2, more preferably 10 ^{−4 to} 0.1, and even more preferably 10 ^{−4 to} 0.01. The silver halide emulsion as described in (17) above,
(24) The hexagonal surface of the AgX ₂ particles is the {002} plane of the β-type crystal structure, and at least one of the trapezoidal surfaces is the {101} plane of the β-type crystal structure (26) The silver halide emulsion as described in (23) above.

(25) The size of the hexagonal surface is different in one particle, and (small hexagonal area / large hexagonal area) = A3 is 0.05 to 0.90, preferably 0.00. The silver halide emulsion as described in (23), which is 1 to 0.80, more preferably 0.2 to 0.7, still more preferably 0.3 to 0.6.
(26) The silver halide emulsion as described in (23), wherein the tetradecahedral grains further have 1 to 10 troughs (basal depressions) on the grain surface.
(27) Maximum side length ratio of the hexahedron = “one particle indicates (longest side length / shortest side length)”, or a straight portion of the rounded particle side or By extending the flat portion of the surface, the maximum side length ratio of the right-angled hexahedron formed is 1.0 to 1.3, preferably 1.0 to 1.2, more preferably 1.0 to 1. 1. The silver halide emulsion as described in (1), which is preferably 1.0 to 1.05.
(28) The AgX ₂ particles are the dodecahedron and the dodecahedron particles, preferably (the number of the dodecahedron particles / the number of the dodecahedron particles) = 0.1 to 100, preferably 0.5. ~ 50,
The silver halide emulsion as described in (17), wherein the silver halide emulsion is more preferably from 1.0 to 30.
(29) (Diameter of the dodecahedron particle / diameter of the tetrahedral particle) = 0.1-5, preferably 0.2-0.9, more preferably 0.2-0.8. The silver halide emulsion as described in (28), which is characterized in that

(30) The growth method is characterized in that, in addition to the AgX ₁₂ , one or more other AgX fine particles (AgX ₁₃ ), Ag ⁺ , X ⁻ are added (4) The seed crystal grain growth method described.
(31) The method for growing seed crystal particles according to (4), wherein the AgX composition of the AgX ₁₃ is AgCl, AgBr, AgI, and a mixed crystal of any ratio of two or more thereof.
(32) The silver halide seed crystal according to (4), wherein the AgX composition of the seed crystal grain is a mixed crystal of AgCl, AgBr, AgI, and any ratio of two or more thereof. Growth method.
(33) The seed according to (4), wherein the grains grown by the method are tabular grains having an aspect ratio (projected diameter / thickness) of 2 to 1000, preferably 4 to 500 Crystal grain growth method.
(34) The tabular grains are parallel twin tabular grains having twin planes parallel to each other, or tabular grains having a {100} plane as a main plane. Seed crystal grain growth method.

(35) By the deposition, an epi part is formed on the seed crystal, and the epi part occupies 0.1 to 70, preferably 0.5 to 40% of the total area on the particle surface. (4) The method for growing seed crystal particles according to (4).
(36) The seed crystal grain growth method according to (35), wherein one or more types of crystal lattice defects are introduced into the interface with the epi portion.
(37) The seed crystal grain growth method according to (4), wherein one or more crystal lattice defects are introduced into the seed crystal by the deposition.
(38) The method for growing seed crystal grains according to (36) or (37), wherein the defect contains at least 1 to 50, preferably 2 to 30 edge dislocation lines per grain. .
(39) The method for growing seed crystal particles according to (4), wherein the diameter of the (AgX ₁₂ ) is 1 to 200, preferably 5 to 100, more preferably 10 to 50 nm.

(40) After the (AgX ₁₂ ) was formed, its 1 to 99.99, preferably 10 to 99.9, more preferably 30 to 99, and even more preferably 60 to 97% of water was removed. The seed crystal grain growth method according to (4), which is added later.
(41) The water removal is performed by any one of the methods (ultrafiltration treatment), (method of coagulating sedimentation, removing the supernatant), and (centrifuged to remove the supernatant). The method for growing seed crystal particles according to (39), wherein
(42) The AgX. When the powder method X-ray diffraction of the particles is measured, and the diffraction peak of the (100) plane of the β-type phase is (β1), the ratio of “peak intensity of α1 / peak intensity of (β1)” is 1. The silver halide emulsion according to (12), characterized in that it is from 0 to 10 ⁶ , preferably from 2.0 to 10 ⁵ , more preferably from 5 to 10 ⁴ , still more preferably from 10 to 10 ³ .
(43) The AgX. When the particle is an AgI particle, when the powder method X-ray diffraction is measured with CuKβ ray, the α1 peak position is 2θ = 22.0 to 22.7, preferably 22.1 to 22.6. The silver halide emulsion according to (12), characterized in that it is in the region of 22.15 to 22.5 degrees.

(50) The emulsion is characterized in that it is an emulsion formed by a batch method in which an Ag ⁺ salt solution and an X ^- salt solution are added to a dispersion medium solution in a reaction vessel while stirring. The silver halide emulsion according to (1).
(51) The emulsion comprises silver halide seed crystal grains having at least a dispersion medium, water, and an AgI content of 80 to 100, preferably 85 to 100, more preferably 90 to 100, and still more preferably 95 to 100 mol%. A silver halide seed emulsion (AgX ₇ ) having AgX ₆ ) having an AgI content of 80 to 100, preferably 85 to 100, more preferably 90 to 100, still more preferably 95 to 100 mol%. The silver halide emulsion according to (1), wherein the silver halide emulsion is formed by adding fine grains (AgX ₁₃ ), dissolving the added fine grains and depositing on the seed crystal grains.
(52) emulsion is a Ag ⁺ salt solution into a continuous process mixing vessel, X ^- continuous salt solution supply, is both in a mixing vessel are mixed and the mixture is continuously discharged through the liquid feed pipe The silver halide emulsion as described in (1), which is a grain formed by a production method.
(53) The Ag ⁺ salt solution and the X ^- salt solution are added into the dispersion medium solution through the hollow tube, and after the addition, both are quickly mixed, preferably 10 ^-6 to 1, more preferably 10 ^-6 to 10 ^-1, more preferably, wherein the, to be mixed between 10 ^-6 to 10 ^-2 seconds (50) or (52) halogenated according Silver emulsion.
(54) A dispersion medium is contained in at least one of the Ag ⁺ salt solution and the X ^- salt solution, preferably both in an amount of 0.01 to 10, preferably 0.1 to 7, and more preferably 0.5 to 3% by mass. The silver halide emulsion as described in any one of (50), (52) and (53),

(55) The difference between the temperature of the dispersion medium solution and the temperature of the additive solution is 0 to 20, preferably 0 to 10, more preferably 0 to 5 ° C. (50) or (52) The silver halide emulsion as described above.
(56) Addition of at least one of the Ag ⁺ salt solution and the X ^- salt solution, preferably both, is 2 to 10 ¹⁵ , preferably 6 to ^{10 10} , more preferably 10 to 10 ¹⁰ The silver halide emulsion as described in (50) or (52), which is formed using a certain porous additive system.

(60) the AgX ₁₂ is, the dispersion medium solution in the reaction vessel, while stirring, the Ag ⁺ salt solution, X ^-, wherein it is fine, which is formed in a batch method in which the double-jet addition of a salt solution (4) The method for growing silver halide seed crystal grains according to (4).
(61) the AgX ₁₂ is a Ag ⁺ salt solution into a continuous process mixing vessel, X ^- salt solution supply, both are mixed in a mixing vessel, a mixture is continuously discharged through the liquid feed pipe (4) The method for growing silver halide seed crystal grains according to (4), wherein the grains are fine grains formed by a continuous production method.
(62) A closed system in which the Ag ⁺ salt solution and the X ⁻ salt solution are supplied through a hollow tube, and the inside of the hollow tube, the mixing vessel, and the liquid feeding tube system is blocked from the outside air. The silver halide seed crystal growth method as described in (61), which is characterized in that
(63) and said Ag ⁺ salt solution X ^- at least one salt solution, preferably 0.01 to 10 both in the dispersion medium, preferably 0.1 to 7, more preferably containing 0.5 to 3 wt% (61) The method for growing silver halide seed crystal grains according to (61).
(64) The silver halide seed crystal according to (61), wherein the mixing is performed using magnetic stirring, preferably using stirring blades rotating in opposite directions. Growth method.

(71) The AgX ₁ particle according to (1) has an epi part having a halogen composition different from that of AgX ₁ on the particle surface (one or more parts of a plane, a ridge, and a corner), , I ⁻ content is different from 10 to 100, preferably 20 to 100, more preferably 30 to 100 mol%, and the epi part is 0.1 to 70, preferably 0.8, of the total area on the particle surface. The silver halide emulsion (AgX ₆ ) according to (1), characterized by occupying 5 to 40%.
(72) The silver halide emulsion as described in (71), wherein the content of AgCl (mol%) in the epi part is 0 to 100, preferably 30 to 100, more preferably 60 to 100.
(73) The silver halide emulsion as described in (71), wherein the content of AgBr (mol%) in the epi portion is from 0 to 100, preferably from 30 to 100, more preferably from 60 to 100.
(74) The ratio (AgXmol amount of the epi part / AgXmol amount of the host particles) is 10 ⁻⁵ to 2, preferably 10 ^{−4 to} 0.6, more preferably 10 ^{−3 to} 0.3. The silver halide emulsion as described in (71), which is characterized in that
(75) The AgX ₁ particle according to (1) has a shell layer (AgX ₈ ) having a halogen composition different from that of AgX ₁ on the particle surface, and the halogen composition has an I ⁻ content of 10 to 100. The silver halide emulsion (AgX ₉ ) according to (1), characterized in that the shell layer is preferably different from 20 to 100, more preferably from 30 to 100 mol%.

(76) The silver halide emulsion as described in (75), wherein the composition of the shell layer is changed stepwise or continuously.
(77) A simple substance or a compound having an atomic number of 1 to 92 other than silver and halogen, in one or more of the inside of the (AgX ₁ ) particle, the shell layer, the shell layer (AgX ₈ ), and the epi part. (1), (71), characterized by containing only 10 ⁻⁹ to 10 ⁻¹ , preferably 10 ⁻⁸ to 10 ⁻² (mol / mol AgX) as one or more kinds of dopants. (75) The silver halide emulsion according to any one of (75).
(78) The dopant is a simple substance of a metal atom “an atom on the left side of a line connecting boron B and At in the element long periodic table” or a neutral or ionic substance of the metal atom-containing compound. The silver halide emulsion as described in (77) above,
(79) The compound is a metal complex containing 1 to 3 metal atoms and 2 to 20 ligands, wherein one to all of the ligands are inorganic ligands and / or The silver halide emulsion as described in (78), which is an organic ligand containing 1 to 30 carbon atoms.

(80) The silver halide emulsion as described in (79), wherein the metal complex is a tetra- or hexa-coordination complex.
(81) The silver halide according to (79) or (80), wherein the metal complex has one or two organic ligands, and the remaining ligand is an inorganic ligand. emulsion.
(82) The doped one is a chalcogen atom (one or more of S, Se, Te), and the doping amount is 10 ⁻⁸ to 10 ⁻² , preferably 10 ⁻⁷ to 10 ⁻³ (mol / mol AgX). The silver halide emulsion according to (77), which is characterized in that
(83) The epitaxial portion formation, 10-100 saturated adsorption amount of the adsorbent other than gelatin particles, preferably 30 to 97, more preferably adsorbed by 60% to 95% state, Ag ⁺ and X ^- by adding, that are formed, and / or, X ^- a is added that is formed by halogen conversion, characterized by (71), wherein the silver halide emulsion.
(84) A silver halide emulsion according to which the adsorbent is a cyanine dye and a fog.
(85) The AgX. However, it contains 10 ⁻⁸ to 10 ⁻² , preferably 10 ⁻⁷ to 10 ⁻³ (mole / mole AgX) of reduced silver in one or more of the host grains, the epi part, and the shell layer. The silver halide emulsion as described in any one of (1), (71) and (75),

(86) When a chemical sensitizer is added to the emulsion for chemical ripening, or when a sensitizing dye is added for spectral sensitization, or when the emulsion is coated on a support, the emulsion has a pAg of 3 to 3. 11. The silver halide emulsion as described in (1), wherein the most preferable combination having a pH of 3 to 11 and a temperature of 10 to 90 ° C. is selected and used.
(87) The emulsion is an emulsion obtained by adding one or more chemical sensitizers and chemically sensitized; the chemical sensitizer is a chalcogen sensitizer (sulfur, selenium, tellurium sensitizer), a noble metal A sensitizer (gold, a Group 8 metal compound) or a reduction sensitizer is used alone or in combination of two or more thereof (addition ratio is any ratio), and each addition amount (mol / mol AgX) is preferably The silver halide according to any one of (1), (71), (75), and (83), characterized in that it is 10 ⁻⁹ to 10 ⁻² , more preferably 10 ⁻⁸ to 10 ^−3. emulsion.
(88) The emulsion is a spectrally sensitized emulsion to which one or more cyanine dyes are added, and the adsorption amount of the dye to AgX is 1 to 100, preferably 10 to 98, more preferably a saturated adsorption amount. The silver halide emulsion as described in (1), characterized in that it is 30 to 95%.
(89) A compound that lowers the interstitial silver ion (Agi ⁺ ) concentration of the grains is added to the emulsion and adsorbed on the grains, so that the concentration of grains is 0.9 to 10 before the addition, preferably The silver halide emulsion as described in (1), wherein the silver halide emulsion is reduced to 0.5 to 0.01 times.

(90) Chemical sensitization nuclei are preferentially formed in the epi part by the chemical sensitization, and the chemical sensitization nucleus ratio of (the epi part / non-epi part) is 1.2 to 10 ⁵ , preferably 2 The silver halide emulsion according to (71), wherein the silver halide emulsion is from 10 ⁴ to 10 ⁴ , more preferably from 5 to 10 ⁴ .
(91) In the production of the emulsion, the silver amount (mol / L) of the emulsion after grain formation and before the desalting step of the emulsion is 0.05 to 3, preferably 0.1 to 2. The silver halide emulsion according to (1).
(92) The silver halide emulsion as described in (75), wherein the shell layer has an AgCl content of 1 to 100, preferably 10 to 100, more preferably 60 to 100 mol%.
(93) The silver halide emulsion as described in (75), wherein the AgBr content of the shell layer is 1 to 100, preferably 10 to 100, more preferably 60 to 100 mol%.

(100) The photographic material according to (3), wherein the photographic material is a photothermographic material having a non-photosensitive organic silver salt, a heat developer, and a binder.
(101) The photosensitive material is a photothermographic material which is exposed to light and exposed to light and then developed by heating the material to 80 to 200, preferably 90 to 150 ° C. (3) ) The photosensitive material described in the above.
(102) The photographic light-sensitive material as described in (3), wherein the light-sensitive material is a light-sensitive material having a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer.
(103) The photographic light-sensitive material as described in (102), wherein the photographic material is a color light-sensitive material containing a color developer.
(104) The emulsion described in (1) is used as an ultraviolet absorber of the light-sensitive material, preferably used in a layer farther from the support than the blue-sensitive layer (3) The photographic light-sensitive material described.

(105) The emulsion described in (1) is used as a yellow filter layer (blue light removing layer) of the light-sensitive material, preferably the layer is disposed between a blue-sensitive layer and a green-sensitive layer. (3) The photographic light-sensitive material according to (3).
(106) The photographic light-sensitive material as described in (3), wherein the light-sensitive material is a light-sensitive material that is exposed and developed to give a black and white image.
(107) In the short wavelength light cut filter material in which one or more silver halide emulsions are coated on a support, at least one silver halide emulsion is the silver halide emulsion described in (1). And filter material.
(108) The filter material according to (107), wherein the short-wavelength light is 200 to 600, preferably 220 to 500, more preferably 230 to 490, and still more preferably 250 to 480 nm.
(109) The filter material according to (107), wherein the filter material is a transmitted light type filter material.
(110) The filter material according to (107), wherein the filter material is a reflected light type filter material.
(111) The filter material according to (107), wherein a color material having light absorption in the visible light region is added to the emulsion.
(112) The filter material according to (111), wherein the colorant is a cyanine dye.
(113) The filter layer (AgX ₀ ) particles are non-photosensitive to light having a short wavelength of 490 nm or less, and are not substantially developed during the development processing of the photosensitive material. The photosensitive material as described in (105), which is dissolved and removed.

  According to the present invention, an AgX emulsion and a photographic light-sensitive material giving high sensitivity and high image quality can be obtained, and a blue-violet light absorbing filter material having excellent blue-violet light absorption characteristics can be obtained.

In this specification and claims, “left numerical value” to “right numerical value” mean “left numerical value” or more and “right numerical value” or less.
(II) Next, the present invention will be described in detail.
(II-1) AgX particle structure.
An example of the particle structure of AgX is shown in the figure. FIG. 1 is a transmission electron micrograph image (hereinafter referred to as TEM image) of a carbon replica film of AgI particles having an AgI content of 100 mol%. The emulsion is centrifuged, and the particles from which gelatin has been removed are redispersed with water and then placed on an electron microscope mesh covered with a collodion film and dried. Next, it is shadowed with Au—Pd in vacuum and carbon is deposited. The collodion film was dissolved and removed, the AgX particles were removed with a fixing solution, dried, and a TEM image was taken. The corners and edges of the cubic particles are slightly rounded. All of the side length ratios of the hexahedron formed by extending the flat surface of the particle or the straight part of the edge are 1.0 to 1.05. Further, all of the maximum side length ratios are 1.0 to 1.05. The adsorbed gelatin will remain, and there will be deformation due to shrinkage of the replica film, flaking of the particles, etc., but all are approximately 1.0.
Further, the angles of the surface of the particles were all 86-94 °. There will be this deformation of the replica film, but all are approximately 90 °.
When the particles are cooled to −150 to −100 ° C. and a TEM image is taken, a striped pattern as shown in FIG. 2 is observed. When the main phase of the hexahedron is an α phase, it indicates that another crystal structure phase is included as a stacking fault on the α phase.
In many cases, the dodecahedron particles and the dodecahedron particles are mixed in the particles in the modes (19) to (23). Regarding the details of the particles, reference can be made to the description in Japanese Patent Application No. 2002-81020. These particles contain a β-type crystal structure in the form of (17). When the dodecahedron particles and the tetrahedral particles are cooled to −150 to −100 ° C. and the TEM image is taken, a striped pattern is observed.
These striped patterns are considered to be α, β, γ type, or any phase interface between the α type phase, β type phase, and γ type phase of the AgI crystal.
The circle equivalent projected diameter refers to the diameter of a circle having an area equal to the projected area when a particle is placed on a substrate and observed from directly above.

(II-2) X-ray diffraction characteristics of particles.
FIG. 3 (a) shows the results obtained by placing the AgI particles shown in FIG. 1 on a glass substrate and performing ordinary powder X-ray diffraction measurement at 25 ° C. using CuKβ characteristic X-rays (wavelength: 1.39217Å). . θ represents the angle between the incident X-ray beam and the substrate. The diffraction characteristics have the characteristics described in (12) and (13).
The particles were annealed at 180 ° C. or higher for about 1 hour, and then slowly cooled to room temperature. When the X-ray diffraction was measured, the peak intensity of α1 was greatly reduced, and the diffraction on the (002) plane of the β-type crystal structure The peak increases greatly.
FIG. 3 (b) shows a measurement result obtained by placing the particles on a flat glass substrate and increasing the number of particles having the particle surface oriented parallel to the substrate surface like the particles in FIG. It was. FIG. 3B shows a result obtained by further decreasing the particle density to be mounted and increasing the ratio of the aspect particles. Since the α1 peak is the main peak, the α1 peak is diffraction of a plane parallel to the surface of the cubic particle. The peak has a value close to the (110) plane diffraction angle of 22.1424 ° of α-type AgI.
If α1 is this, the other surface is the (100) plane, but there is no (200) plane diffraction angle = 31.941 ° of α-type AgI. α-type AgI has a strong diffraction (39.95 °) close to the (211) plane diffraction angle = 39.380 °, and the formation of cubic particles by this plane and the (110) plane has a plane angle of both. It ’s not 90 °, so it ’s not possible. Further study is needed.

(II-3) Light absorption characteristics of particles.
FIG. 4 shows the results of coating the emulsion composed of the grains shown in FIG. 1 on a colorless and transparent TAC support and measuring the light absorption spectrum thereof. A reflection plate (white Mg oxide plate) is placed on the rear surface of the sample, and its light reflection spectrum is measured using a Hitachi color analyzer. The measurement results of AgI particles having a conventionally known β-type content of 90% or more are also shown. In FIG. 4, the horizontal axis represents the wavelength of light, and the vertical axis represents% reflection. The absorption edge wavelength is shifted to the long wavelength side compared to the β type. In addition, the β-type has a hump based on the exciton peak, but AgX ₀ does not have it.

(II-4) Preparation of AgX emulsion.
(Preferably, pAg = 1 to 8, more preferably 2 to 6) dispersant aqueous solution B1 containing at least water and a dispersion medium in a aqueous solution containing Ag ⁺ (Ag ⁺ salt solution), X ^- an aqueous solution containing ( X ^- salt solution) by double jet addition to, being formed. It can be obtained by high-speed mixing and stirring in the reaction vessel, and the embodiment (53) is preferred. The following method is effective as a method of mixing Ag ⁺ and X ⁻ . 1) A method in which a small mixing box is provided in a reaction vessel, both are added to the mixing box, mixed, and then discharged into the bulk solution in the reaction vessel. 2) The number of added pores should be added using the porous addition system described in (56). In this regard, the description in Reference 23 can be referred to.
The Ag ⁺ salt aqueous solution is an aqueous solution of silver salt having a dissolution amount (molar amount) with respect to 1 L of water at 25 ° C. of 0.1 to ∞, preferably 0.3 to ∞. For example, there are silver nitrate, silver sulfate, and silver oxalate, and silver nitrate is more preferable. X ^- salt solution is a halogen salt solution mainly containing iodide salt. For example, there are NaI, KI, and NH ₄ I. Cl to ^-, Br ^- one or more salts, can be added the necessary amount.
10-70 are preferable, as for the temperature (degreeC) of this reaction container, 30-65 are more preferable, and 38-60 are still more preferable. Once the seeds of the particles are formed, subsequent growth is possible over a wider region (pAg, pH, temperature region).
In order to improve the uniformity of the temperature of the dispersion medium solution, the temperature of the addition solution is adjusted in advance, and the difference between the temperature of the reaction vessel or the dispersion medium solution and the temperature of the addition solution is changed to the mode of (55). Is preferred. The specific method is as follows. 1) The description in Document 23 can be referred to by a method in which a hollow tube for an additive solution is placed long in the dispersion medium solution and then added to the solution after passing therethrough. 2) The hollow tube of the addition system is passed through the heat retaining device until it enters the dispersion medium solution. As it passes through, the additive solution is temperature adjusted. This aspect is also effective for the aspects (60) to (64).
2-11 are preferable and, as for pH at the time of particle formation, 4-10 are more preferable. (Concentration of the Ag ⁺ salt solution / concentration of the X ⁻ salt solution) = 0.9 to 1.1 is preferable, 0.96 to 1.04 is more preferable, and 0.98 to 1.02 is still more preferable.
When the particle shape is unclear, the particle is almost the same composition as the AgX composition on the particle surface, and is highly supersaturated at a temperature of 45 to 55 ° C., pAg of 2 to 8, preferably 3 to 6 (with a critical growth rate of 20 to 100, preferably 50 to 98%), and the shape when grown to 1.1 to 3, preferably 1.3 to 2 times, shows the embodiment of (1).
Manufacturing conditions with a high ratio of (AgX ₁ ) particles can be found by the following try-and-error method. Each condition factor (temperature, pAg, homogeneity) is controlled with high accuracy, and each factor is changed finely and systematically, and particularly suitable conditions are found. 0-60 are preferable, as for the fluctuation range (mV) of the silver potential at the time of grain formation, especially the seed crystal formation, 0-30 are more preferable, and 0-10 are more preferable.

(II-5) Dispersion medium.
Any conventionally known dispersion medium can be used as the dispersion medium, and the specific examples thereof can be referred to the descriptions in Documents 1, 2, 17, 19, and 24. The weight average molecular weight of the dispersion medium is preferably 3000 to 10 ⁶ , more preferably 6000 to 300,000. The concentration (mass%) is preferably from 0.1 to 20, and more preferably from 0.3 to 10. Gelatin is preferred, and gelatin collected from cow bone, pig bone, skin, or fish bone, skin, scales can be used.
Gelatin includes alkali-treated gelatin and acid-treated gelatin. Furthermore, gelatin obtained by reducing the molecular weight using at least one of acid, alkali, and hydrolase (its weight average molecular weight is 3000 to 70,000). There are high molecular weight gelatins having a molecular weight of 100,000 to 300,000 (those having a high β chain content or those having a high molecular weight by intermolecular crosslinking with a hardener). 0.9 to 10 their content of impurities prior ^-8, preferably Empty gelatin reduced to 0.1 to 10 ^-8 times. Gelatin in which amino groups, carboxylic acid groups, imidazole groups, hydroxyl groups, and thioether groups are all chemically modified. The modification rate (%) is 1 to 100, preferably 10 to 98, more preferably 30 to 92. Gelatin chemically modified with an organic compound group (R1) having 1 to 50 carbon atoms, preferably 2 to 20 carbon atoms is preferred. For example, gelatin in which the amino group is phthalated, succinylated, trimellitated or acetylated. Esterified gelatin modified with carboxylic acid groups. Gelatin in which an alkyl group is introduced into the thioether group of methionine group (Met), and gelatin obtained by sulfonating the group. What added the oxidizing agent and changed this group into the sulfinyl group and the sulfonyl group is preferable. A Met content (μmol / g) of 0 to 100 can be used, but 0 to 30 is more preferable.
When the emulsion is applied to a heat-developable photosensitive material, the dispersion medium is preferably gelatin whose amino group is modified with R1. In addition, the description in Reference 23 can be referred to.
The target dispersion medium can be added in a necessary amount at any time from before grain formation to after grain formation to immediately before emulsion coating.

(II-6) Emulsion sensitization and the like.
Chemical sensitization can be carried out by adding a chemical sensitizer to the emulsion of the present invention. As chemical sensitizers, chalcogen sensitizers (sulfur, selenium, tellurium sensitizers), noble metal sensitizers (gold, Group 8 metal compounds), reduction sensitizers, or a combination of two or more thereof may be used. Can be used in proportion. Each addition amount (mol / mol AgX) is preferably 10 ⁻⁹ to 10 ⁻² , and more preferably 10 ⁻⁸ to 10 ⁻³ .
1 to 20 kinds of sensitizing dyes for the blue-sensitive layer can be added to the emulsion to increase the light absorption rate and further enhance the blue sensitivity, and can be used for the blue-sensitive layer. When used for a green sensitive layer, 1 to 20 kinds of sensitizing dyes for green sensitive layer are added, and when used for a red sensitive layer, 1 to 20 kinds of sensitizing dyes for red sensitive layer are added and spectrally sensitized. I can do things.
In the modes (77) to (82), a dopant can be doped. For details of the dope and the dopant, the descriptions in Documents 2 and 24 can be referred to.
Further, a compound (PA) that absorbs one photon and gives 2 to 4 electrons to AgX grains when adsorbed to emulsion grains and irradiated with light is 10 ⁻⁸ to 10 ⁻¹ , preferably 10 ⁻⁶ to The addition amount is preferably 10 ^-2 . For details of the compound, the description in Reference 13 can be referred to.
Regarding the emulsion of the present invention, the type and amount of compound used, the production method and apparatus, and the application thereof, the description in Reference 14 can be employed.
Regarding the application of the emulsion of the present invention to a heat-developable light-sensitive material, the description in Reference 15 can be adopted, and as to the application to other light-sensitive materials, the descriptions in References 7 and 10 can be adopted.
With respect to the non-photosensitive organic silver salt, thermal developer (reducing agent), binder, support and toning agent described in (100), the description in Document 15 can be employed.

(II-7) Others.
1) Crystal lattice defects according to (36) to (38). A state in which the arrangement of the crystal lattice is disturbed is called a crystal lattice defect, and there are a point defect, a line defect, a plane defect, and a volume defect. A collection of point defects is particularly called a composite defect. A line defect is a dislocation line, and includes an edge dislocation line, a screw dislocation line, and a dislocation loop. Surface defects include stacking faults, twin planes, and grain boundaries. The lattice defect refers to one to all of them, and preferably includes at least dislocation lines and edge dislocation lines, and is preferably the embodiment (38). Regarding the details of these defects, the descriptions in Documents 16 and 22 can be referred to.
2) Tabular grains according to (33). The tabular grains include the following grains.
a) Tabular grains having a NaCl-type crystal structure and a principal plane of {111} plane. Particles having 2 to 3, preferably 2 twin planes parallel to the main plane. The details can be referred to the descriptions in Documents 2, 17, and 20.
b) Tabular grains having a NaCl-type crystal structure and a main plane of {100} planes. The details can be referred to the descriptions in Documents 2, 18, and 20. AgCl, AgBr, AgBrI alone, or a mixed crystal of any ratio of two or more thereof.
c) Particles having an AgI content of 80 to 100 mol% and 2 to 300 stacking fault surfaces parallel to the main plane. The details can be referred to the descriptions in Documents 2, 7, and 19.
3) Epitaxial AgX part. When one crystal grows on the surface of another host crystal different from that with a certain orientation relationship, this state is called epitaxy, and the grown portion is called an epitaxial portion. The part in which the part is an AgX crystal is referred to as an epitaxial AgX part. The two AgX compositions differ in the content of at least one of AgCl, AgBr, and AgI by 5 to 100, preferably 10 to 100, and more preferably 20 to 100 mol%.
In the state in which the adsorbent is adsorbed on the particles, an epi part is formed on a specific part of the particle, and then chemical sensitization, the epi part is selectively chemically sensitized. The latent image forming location is limited, and high sensitivity is preferable. First, since the epi part is developed, even if the host part is difficult to develop, there is an acceptable advantage. Reference can be made to the descriptions in References 9 and 22 for the particles having the epi part.
The order of the solubility of AgX is (AgI <AgBr <AgCl), which corresponds to the order of the polarity of the molecules, and the greater the polarity, the greater the solubility. Since the AgI molecule has low polarity and is close to lipophilic organic matter, it has low solubility. For this reason, it is difficult to develop by ordinary development processing. However, the treatment with a developing solution containing an organic solvent in an amount of 1 to 100, preferably 10 to 100, more preferably 30 to 100% is preferred because the processing speed is increased.
The (AgX ₁ ) particles have higher solubility than other shaped particles. Therefore, when added in (4) and the related aspects, there is an advantage that it quickly dissolves and disappears.
In the aspect of (113), being substantially undeveloped means that the mol% of the developed particles is 0 to 20, preferably 0 to 5, more preferably 0 to 1. Further, being substantially dissolved and removed means that the mole% of particles to be removed is 80 to 100, preferably 95 to 100, more preferably 99 to 100. In order to make the particles non-photosensitive, a desensitizer may be added. It is advisable to dope a desensitizer or adsorb a desensitizing dye. Since the diameter of the particles used here is small, the dissolution rate is fast. Since the particles do not move from the layer, they do not harm other layers, which is preferable. The light absorption characteristics that are insufficient for the particles are preferably corrected by adding a coloring material in the modes (111) and (112).
One or more of AgNO ₃ , bromide salt, and chloride salt can be added to the (AgX ₄ ) emulsion to suppress excessive I ⁻ residue.

(Reference) The following references and references cited.
1. T. T. et al. H. Edited by James, The Theory of The Photographic Process, 4th edition, McCillan, New York (1077).
2. Research Disclosure, item 17643 (December 1978), item 38957 (September 1996).
3. B. L. J. et al. Byerley et al. Photographic Science, 18, 53-59 (1970). Review article.
4). JCPDS card (a collection of conventionally known powder X-ray diffraction data. In Japan, it can be purchased from Rigaku Corporation).
5. α, β, γ type AgI. S. Hoshino, J. et al. Phys. Soc. Japan, 12, 315-326 (1957). J. et al. E. Maskasky, Physical Review, B43, 5769-5772 (1991). Temperature change behavior.
6. Dodecahedron, tetrahedral particles, US Pat. No. 4,094,684, JP-A-2004-4586.
7). For AgI tabular grains having an aspect ratio of 8 or more, JP-A-59-119350, and for AgI tabular grains having a γ content of 90 mol% or more and an aspect ratio of 8 or more, JP-A-59-119344. You can refer to the description.
8). Light absorption. G. C. Farnell, J.M. Photographic Science, 22, 228-237 (1974).
9. Epi. J. et al. E. Maskasky, Photogr. Sci. Eng. 25, 96-101 (1981), U.S. Pat. Nos. 4,940,084, 4,142,900 and 4,459,353.
10. Yellow AgI particles. 25 ° C or less. U.S. Pat. No. 4,672,026.
12 U.S. Pat. No. 4,520,0098.
13. PED. Japanese Patent Application Nos. 2001-800, 2002-287293, 2000-22162, U.S. Pat. Nos. 5,747,235, 5747236, 6054260, and 5994051.
14 Compounds and the like. JP 2001-201810, JP 2001-255611, and JP 2003-172983.
15. Thermal development. JP-A Nos. 2001-33911, 2003-162025, 2004-233397, Japanese Patent Application Nos. 2001-349031, and 2001-342983.
16. Lattice defects. Riken Dictionary (Iwanami Shoten), Chemistry Dictionary (Tokyo Kagaku Doujin), Crystal Growth Handbook (Kyoritsu Publishing).
17. (111) Flat plate. U.S. Pat. Nos. 4,433,048, 5,211,013, 5,494,788, JP-A-2-838, and 8-82883. No. 8-227117, JP-A No. 2000-171928.
18. (100) Flat plate. JP-A-6-308648, JP-A-7-234470, JP-A-7-146522, JP-A-8-339044, US Pat. No. 5,908,739, and European Patent 0534395A.
19. AgI flat plate. Japanese Patent Application No. 2004-309505.
20. Fine particle addition, equipment. JP-A-4-34544, JP-A-2-222940, JP-A-2003-172983.
21. developing. T. T. et al. H. James et al., Photo. Sci. Eng. 5, 21-29 (1961).
22. Epi, dislocation line. Japanese Patent Publication Nos. 6-12404, 6-93080, U.S. Pat. Nos. 4,865,962, 4,435,501, 6,607,874B2, 6,114,105, 5,275,930, 5,695,923, European Patent Application Publication Nos. 699944-699951 (A1) No. 932077 (A2), Maskasky, J. et al. Imaging Science. 32, 160-177 (1988). Sugimoto et al., J. MoI. Colloid and Interface Science, 140, 335, 348 (1990). JP-A-11-223895, JP-A-11-184029, JP-A-62-220238, JP-A-58-108526.
23. apparatus. JP2004-305809A. Japanese Patent Application No. 2004-309505, Japanese Patent Application Laid-Open No. 4-193336.
24. Additives etc. JP2003-172983, JP200423333397, JP2004240182, JP8-101473A, JP2003-15246A.

[Example]
EXAMPLES Next, although an Example demonstrates this invention further in detail, the embodiment of this invention is not limited to this.

In a reaction vessel, put dispersion medium solution 1 (containing 1.3 g of water, 25 g of Empty-type beef bone gelatin 1 of Empty type, adjusted to pH = 6 with NaOH), keeping the temperature at 50 ° C., stirring at high speed, Ag-1 solution (AgNO ₃ 34 g / L aqueous solution) and X-1 solution (KI 33.2 g / L aqueous solution) were added quantitatively at 4.0 mL / min for 10 minutes by the simultaneous addition method.
After stirring for 2 minutes, Ag-2 solution (AgNO ₃ 10 g / L aqueous solution) and X-2 solution (KI 9.765 g / L aqueous solution) were added simultaneously while maintaining the silver potential at 180 mV. Ag-2 was added at an initial flow rate of 2.5 mL / min and an acceleration flow rate of 0.2 mL / min for 30 minutes. Next, CDJ was added to the Ag-3 solution (AgNO ₃ 200 g / L aqueous solution) and the X-3 solution (KI, 195.3 g / L aqueous solution) while maintaining the silver potential at 180 mV. Ag-3 was added at an initial flow rate of 4.2 mL / min and an acceleration flow rate of 0.12 mL / min for 65 minutes. The amplitude of silver potential was 5 mV or less. After stirring for 2 minutes, the temperature was lowered to 40 ° C., and sensitizing dye 1 was added in an amount of 90% of the saturated adsorption amount for adsorption.
2 mL of the emulsion was collected and centrifuged, and the produced particles were observed with an electron microscope. FIG. 2 shows a TEM image of the carbon replica of the particles. More than 99% of the number of particles was cubic (side length ratio: 1.0 to 1.1). Therefore, the maximum side length ratio is 1.0 to 1.1. The average particle diameter was about 0.1 μm, the CV of the AgX ₁ particles was about 0.05, and the CV of the AgX ₀ particles was about 0.06. About 1% of dodecahedron particles were present.
Further, a TEM image of the particles was taken at a low temperature of −120 ° C. or lower. This is FIG. (9) Defect lines described can be seen.
A precipitating agent was added to the emulsion, the pH was lowered to around 4.0, and the emulsion was washed with water at 30 ° C. by the coagulation sedimentation washing method to desalinate. The pH was brought to 6.4, the temperature was raised to 40 ° C. and redispersed. The pAg was adjusted to 5.5 using AgNO ₃ and KI. Chemical sensitizer 1 in a total molar amount of 5 × 10 ⁻⁴ mol and gold sensitizer 1 (aqueous solution of chloroauric acid and NaSCN in a 1:20 molar ratio) in gold amount per mol of AgX at 40 ° C. 10 ⁻⁶ mol was added, then the temperature was raised to 60 ° C. and aged for 50 minutes.

The temperature is lowered to 40 ° C., PA1 compound is added in an amount of 10 ⁻³ mol / mol AgX, then antifoggant 1 is added in an amount of 10 ⁻³ mol / mol AgX, and adjusted to pH 6.4 and pAg 5.5. And stirred for 20 minutes. The emulsion was coated on a PET base with a protective layer containing hardener 1 (0.01 g / g gelatin) and dried. It put into the airtight container and it hold | maintained at 40 degreeC for 15 hours, and accelerated the dural reaction.
The coated sample thus obtained (Example 1) was exposed to blue light (with a wavelength of 500 nm or less) for 10 ⁻² seconds or −blue (minus blue) through an optical wedge. Developed with pyrogallol developer at 40 ° C. for 50 minutes. After putting in the stop solution for 1 minute, it was fixed in a fixer (Super Fuji Fix) for 30 minutes, then washed with water and dried. The sensitometry was performed, and the result of the (sensitivity / granularity) ratio is shown in Table 1. It was confirmed that the sample of the present invention was superior in the (sensitivity / granularity) ratio with respect to the comparative sample.
Sensitivity is expressed as the reciprocal of the exposure amount (lux · second) that gives a density of (fog +0.2), and the granularity is uniform for 0.1 second with the amount of light that gives the density of (fog +0.2). Exposure, development processing was performed, the variation in microdensitometer density was measured using a circular aperture of direct line 48 μm, and rms granularity σ was obtained. Details thereof are described in Chapter 21, Section E of Document 1.

[Comparative Example 1-1]
0.2 g of dispersion medium solution 1 and KI are put in a reaction vessel, and the temperature is kept at 45 ° C., while stirring, Ag-1 solution (AgNO ₃ 34 g / L aqueous solution) and X-1 solution (KI 33.2 g). / L aqueous solution) was added at a rate of 4.0 mL / min for 10 minutes by the simultaneous addition method.
After stirring for 2 minutes, CDJ was then added to Ag-2 solution (AgNO ₃ 10 g / L aqueous solution) and X-2 solution (KI 9.765 g / L aqueous solution) while maintaining the silver potential at −50 mV. Ag-2 was added at an initial flow rate of 2.5 mL / min and an acceleration flow rate of 0.2 mL / min for 30 minutes. Next, Ag-3 solution (AgNO ₃ 20 g / L aqueous solution) and X-3 solution (KI, 19.53 g / L aqueous solution) were simultaneously added while maintaining the silver potential at −50 mV. Ag-3 was added at an initial flow rate of 4.2 mL / min and an acceleration flow rate of 0.12 mL / min for 75 minutes. All additions were made by conventional methods. After stirring for 2 minutes, the temperature was lowered to 40 ° C., and sensitizing dye 1 was added in an amount of 90% of the saturated adsorption amount for adsorption.
The emulsion was collected, and the produced grains were observed with an electron microscope. As a result, they were known tetrahedral grains. The average diameter was about 0.1 μm, and the CV of the AgX ₁ particles was about 0.06.
A precipitating agent was added to the emulsion, and thereafter the same treatment as in Example 1 was performed to obtain a coated sample (Comparative Example 1-1) having the same coating silver amount, and its photographic characteristics were obtained. The results are shown in Table 1.

[Comparative Example 1-2]
An AgI grain emulsion was prepared according to Example 1 of reference 10. From the subsequent water washing step, the same coated sample as in Example 1 was obtained (Comparative Example 1-2), and the photographic characteristics were obtained. The results are shown in Table 1.
The emulsion collected before the water washing step was further grown by adding Ag-3 solution and X-3 solution, and the cubic particle number ratio was 30% or less.

[Comparative Example 1-3]
An AgI grain emulsion was prepared by adding AgNO ₃ solution and KI solution to a gelatin solution at a temperature of 70 ° C. and a pI of 2.5 for 25 minutes according to the description in the (Experiment) section of Reference 3.
From the subsequent water washing step, a coated sample having the same coated silver amount (Comparative 1-3) was obtained in the same manner as in Example 1, and the photographic characteristics were obtained. The results are shown in Table 1.
The emulsion collected before the water washing step was further grown by adding Ag-3 solution and X-3 solution, and the cubic particle number ratio was 30% or less.

A coated sample (Example 2) was obtained in the same manner as in Example 1 except that gelatin 1 was replaced with gelatin 2. The same processing as in Example 1 was performed to obtain photographic characteristics, and the results are shown in Table 1.
Gelatin 2 = alkali-treated bovine bone gelatin with a phthalation rate of 83%.

Before the particle formation was completed in Example 1 and before the water washing step, the temperature was lowered to 40 ° C., and the Ag-3 solution and the X-4 solution (NaCl, 71 g / L aqueous solution) were kept at a silver potential of 120 mV. CDJ was added for 3 minutes. The addition rate of the Ag-3 solution is 32 mL / min. Next, the silver potential was adjusted to 90 mV with the X-4 solution. After stirring for 2 minutes, Sensitizing Dye 1 was added and adsorbed at 90% of the saturated adsorption amount.
The emulsion was collected and a TEM image of the replica of the produced grains was observed in the same manner as in Example 1. An AgCl shell layer was laminated on the cubic AgI particles to form a rounded cube. From the measurement results of X-ray diffraction and electron diffraction of the particles, it was found that they were core-shell particles composed of an AgI core and an AgCl shell. A precipitating agent was added to the emulsion, and the emulsion was washed with water at 30 ° C. by a precipitation water washing method to desalinate. The pH was brought to 6.4, the temperature was raised to 40 ° C. and redispersed. The pAg was adjusted to 6 using AgNO ₃ solution and NaCl solution. At 40 ° C., chemical sensitizer 1 was then added in a total molar amount of 5 × 10 ⁻⁴ mol / mol AgX, raised to 50 ° C. and aged for 30 minutes. PA1 compound was added in an amount of 10 ⁻³ mol / mol AgX, then antifoggant 1 was added in an amount of 10 ⁻³ mol / mol AgX, adjusted to pH 6.4 and pAg6, and stirred for 20 minutes. Thereafter, in the same manner as in Example 1, the emulsion was coated on a PET base together with a protective layer containing a hardener 1 and dried to obtain a hardened coated sample (Example 3).

Particle formation was completed in Example 1, and before entering the washing step, CD-3 was added to Ag-3 solution and X-5 solution (KBr, 142 g / L aqueous solution) for 3 minutes while maintaining the silver potential at 120 mV. The addition rate of the Ag-3 solution is 30 mL / min. After stirring for 2 minutes, Sensitizing Dye 1 was added and adsorbed at 90% of the saturated adsorption amount.
The emulsion was collected and a TEM image of the replica of the produced grains was observed in the same manner as in Example 1. An AgBr shell layer was laminated on the cubic AgI particles to form a rounded cube. From the measurement results of X-ray diffraction and electron diffraction of the particles, it was found that they were core-shell particles composed of an AgI core and an AgBr shell.
A precipitating agent was added to the emulsion, and the emulsion was washed with water at 30 ° C. by a precipitation water washing method to desalinate. The pH was brought to 6.4, the temperature was raised to 40 ° C. and redispersed. The pAg was adjusted to 7 using AgNO ₃ solution and KBr solution. Next, chemical sensitizer 1 was added in a total molar amount of 5 × 10 ⁻⁴ mol / mol AgX and aged for 40 minutes. The PED1 compound was added in an amount of 10 ⁻³ mol / mol AgX, then antifoggant 1 was added in an amount of 10 ⁻³ mol / mol AgX, adjusted to pH 6.4 and pAg7, and stirred for 20 minutes. Thereafter, in the same manner as in Example 1, the emulsion was coated on a PET base together with a protective layer containing a hardener 1 and dried to obtain a coated sample (Example 4).
Examples 3 and 4 were exposed in the same manner as in Example 1, and developed with a D-19 developer at 20 ° C. for 16 minutes. Stopping, fixing, washing and drying were carried out to obtain photographic characteristics. The results are shown in Table 1. In all cases, the (sensitivity / granularity) ratio was superior to the comparative example.

1) Formation of tabular seed grains whose main plane is the {111} plane.
Dispersion medium solution 2 (containing 1.25 L of water, 1.0 g of KBr, 2 g of alkali-treated beef bone gelatin 3 and adjusted to pH = 6 with NaOH) is put in a reaction vessel, and the temperature is kept at 20 ° C. while stirring. , Ag-6 solution (AgNO ₃ 50 g / L aqueous solution) and X-6 solution (KBr 36 g, pH 6 aqueous solution containing 1.7 g of gelatin 2 per liter) are added simultaneously, 20 mL / min for 1 minute. A fixed amount was added. While adding an aqueous solution of gelatin having a Met content of 0 and a KBr solution, the temperature was raised to 75 ° C. After aging for 12 minutes, a CDJ with a silver potential of −20 mV was added using Ag-3 solution and X-7 solution (KBr 148 g / L). The Ag-3 solution was added at a start flow rate (mL / min) of 1.6 and an acceleration flow rate of 0.1 for 10 minutes.
Next, CDJ with a silver potential of 0 mV was added using Ag-3 solution and X-8 (KBr145 g, KI2 g / L) solution. The Ag-3 solution was added at a start flow rate (mL / min) of 5.0 and an acceleration flow rate of 0.6 for 40 minutes. Next, using Ag-3 solution and X-7 solution, CDJ addition with a silver potential of 0 mV was performed for 3 minutes. The flow rate of Ag-3 liquid is 30 (mL / min).
Gelatin 3 = gelatin having a Met content of 0 μmol / g and a weight average molecular weight of 15,000.

2) Formation of dislocation tabular grains.
The temperature of the seed tabular emulsion was brought to 75 ° C., KBr solution was added, and then 0.01 mol of cubic AgI emulsion described later was added. Next, 43 mL of Ag-3 solution and 10 mL of X-7 solution were added in 15 minutes. After aging, a precipitating agent was added, washed with agglomerated sedimentation water, and adjusted to pH 6.5 and pBr 2.5 at 40 ° C. Sensitizing dye 1 is adsorbed at 90% of the saturated adsorption amount, heated to 60 ° C., and the chemical sensitizer 1 is 1 × 10 ⁻⁵ mol in total mol amount per mol of AgX. 1 was added in a gold amount of 5 × 10 ⁻⁶ mol and aged for 30 minutes. The temperature is lowered to 40 ° C., PA1 compound is added in an amount of 10 ⁻⁴ mol / mol AgX, then antifoggant 1 is added in an amount of 10 ⁻³ mol / mol AgX, and the pH is adjusted to 6.4 and pAg 5.5. And stirred for 20 minutes. Thereafter, in the same manner as in Example 1, the emulsion was coated on a PET base together with a protective layer containing a hardener 1 and dried to obtain a hardened coated sample (Example 5).
From the TEM image of the replica of the grains, tabular grains having an average diameter of 1.65 μm, a thickness of 0.11 μm, a tabular grain number ratio of 99% or more, and a coefficient of variation in diameter of 0.18 were obtained.

[Comparative Example 5a]
A coated sample (Comparative Example 5a) was prepared in the same manner as in Example 5 except that a tetrahedral AgI described later was added instead of the cubic AgI.

[Comparative Example 5b]
A coated sample (Comparative Example 5b) was prepared in the same manner as in Example 5 except that the emulsion before washing in Example 1 of Reference 10 was added instead of cubic AgI.
Example 5 and Comparative Examples 5a and 5b were exposed in the same manner as in Example 1, developed with D-19 developer at 20 ° C. for 10 minutes, stopped, fixed, washed with water, and dried to obtain photographic characteristics. It was. The results are shown in Table 2. The (sensitivity / granularity) ratio of Example 5 was superior to Comparative Examples 5a and 5b.

2) Formation of cubic AgI fine grain emulsion.
Dispersion medium solution 3 (containing 1.5 g of water and 25 g of gelatin 4 and adjusted to pH = 6 with NaOH) is put in a reaction vessel, and the temperature is kept at 40 ° C., while stirring at high speed, Ag-8 solution (AgNO ₃ 100 g / L aqueous solution) and X-8 solution (KI 97.6 g, gelatin 4 5 g / L aqueous solution) were added at a rate of 10 mL / min for 10 minutes by the simultaneous addition method. Next, CDJ with a silver potential of 180 mV was added to the Ag-8 solution and the X-8 solution. The Ag-8 solution was added at a start flow rate (mL / min) of 16 and an acceleration flow rate of 1.2 for 12 minutes.
From the TEM image of the replica of the generated particles, the diameter was about 0.04 μm, the cubic particle ratio was 98%, the dodecahedron particles were 1%, and the tetrahedral particles were 1%. The ratio is confirmed by further growing the particles at 50 ° C.
Gelatin 4 = Gelatin 1 oxidized with H ₂ O ₂ and having a Met content of 0 μmol / g.

3) Formation of a tetrahedral AgI fine grain emulsion.
Dispersion medium solution 3 (1.5 L of water, 0.12 g of KI, 25 g of gelatin 4 and adjusted to pH = 6 with NaOH) was put in the reaction vessel, and the temperature was kept at 40 ° C. while stirring at high speed. -8 solution (AgNO ₃ 100 g / L aqueous solution) and X-8 solution (KI 97.6 g, gelatin 4 5 g / L aqueous solution) were added simultaneously at 10 mL / min for 10 minutes by the simultaneous addition method. Next, CDJ with a silver potential of 180 mV was added to the Ag-8 solution and the X-8 solution. The Ag-8 solution was added at a start flow rate (mL / min) of 16 and an acceleration flow rate of 1.2 for 12 minutes.
From the TEM image of the replica of the generated particles, the diameter was about 0.04 μm, and the tetrahedral particles accounted for 90% or more. The ratio is confirmed by further growing the particles at 50 ° C.

In Example 5, the process up to the addition of 10 minutes was the same. Next, a CDJ with a silver potential of −20 mV was added using the Ag-3 solution and the X-7 solution. The Ag-3 solution was added at a start flow rate (mL / min) of 15 and an acceleration flow rate of 0.6 for 40 minutes. At this time, the cubic AgI emulsion was added in parallel addition. The addition rate is the rate at which AgBrI (1 mol%) is formed, (AgI addition rate / AgNO ₃ addition rate) = 0.01 molar ratio.
Next, using the Ag-3 solution and the X-7 solution, a coating sample was obtained in the same manner as in Example 5 except that CDJ was added at a silver potential of 0 mV.
From a TEM image of the replica of the grains, tabular grains having an average diameter of 1.7 μm, a thickness of 0.10 μm, a tabular grain number ratio of 99% or more, and a coefficient of variation in diameter of 0.16 were obtained.

[Comparative Example 6a]
A comparative sample was prepared in the same manner as in Example 6 except that the tetrahedral emulsion was added instead of the cubic AgI emulsion.
These samples were exposed and developed in the same manner as in Example 5 to obtain photographic characteristics, and are shown in Table 2. The superiority of Example 6 over Comparative Example 6a was confirmed.

[Comparative Example 6b]
A comparative sample was prepared in the same manner as in Example 6 except that the emulsion before washing in Example 1 of Reference 10 was added instead of the cubic AgI emulsion.
These samples were exposed and developed in the same manner as in Example 5 to obtain photographic characteristics, and are shown in Table 2. The superiority of Example 6 over Comparative Example 6b was confirmed.

The cubic AgI fine grain emulsion prepared in 2) of Example 5 was washed with water, gelatin was added and redispersed at pH 6.4. In the coated sample described in Example 3 of JP-A-2003-15246, the yellow filter layer was the same except that the redispersed emulsion was replaced. Exposure, development, and density measurement were performed in the same manner, and the results are shown in Table 3. The applied silver amount of this layer is 0.7 g / m ² .
[Comparative Example 7-1]
The tetrahedral AgI fine grain emulsion prepared in 3) of Example 5 was washed with water, gelatin was added and redispersed at pH 6.4. In the coated sample described in Example 3 of JP-A-2003-15246, the yellow filter layer was the same except that the redispersed emulsion was replaced. Exposure, development, and density measurement were performed in the same manner, and the results are shown in Table 3. The coating silver amount of this layer is 1 g / m ² .
Here, the degree of color separation = (green-sensitive layer density / blue-sensitive layer density) when developing with blue light. The smaller the value, the better the performance of the yellow filter. The sample of Example 7 had better filter performance.

In addition, AgI particle | grain formation of the Example was always performed under highly uniform stirring. The quantitative additions of (Ag ⁺ salt aqueous solution) and (X ^- salt aqueous solution) were both added with a high-precision constant flow pump. All of the additive liquids were controlled directly at the same temperature as the dispersion medium solution, and added directly to the mixing box in the solution through a liquid feeding tube. The number of added holes was 50. CDJ addition = Controlled Double Jet addition.

The example of the TEM image showing the particle structure of hexahedral AgI particle | grains is represented. Approx. 50,000 times magnification. The example of the low-temperature TEM image showing the particle structure of a hexahedral AgI particle | grain is represented. The magnification is about 200,000 times. The X-ray-diffraction measurement figure by Cu (beta) X-ray of hexahedral AgI particle | grains is represented. 1 represents a light reflection spectrum of an AgI grain emulsion.

Claims (6)

In a silver halide emulsion having at least a dispersion medium and silver halide grains, 60 to 100% of the total projected area of the grains has an AgI content of 85 to 100 mol%, and the grain shape has a right angle of 6 Halogenation characterized in that it is a face or a particle (AgX ₁ ) having a rounded shape at its corners and / or edges and a circle equivalent projected diameter of 0.01 to 20 μm. Silver emulsion.   Side length ratio of the hexahedron “one side of one particle (the length of the longest side / the length of the shortest side)”, or the straight part or the flatness of the side of the rounded particle 2. The silver halide emulsion according to claim 1, wherein the length ratio of the right hexahedron formed by extending the part is 1.0 to 1.3.   2. A photographic light-sensitive material in which one or more silver halide emulsions are coated on one or both sides of a support, wherein at least one silver halide emulsion is the silver halide emulsion according to claim 1. Photosensitive material. To a silver halide seed crystal emulsion having at least a dispersion medium, water, and silver halide seed crystal grains (AgX ₁₀ ), silver halide fine grains (AgX ₁₂ ) having an AgI content of 85 to 100 mol% were added and added. In the method for growing silver halide grains, wherein the fine grains are dissolved and deposited on the seed crystal grains, the fine grains contain AgX _{1 according} to claim 1. Method for growing silver halide grains.   4. The photographic light-sensitive material according to claim 3, wherein the light-sensitive material is a heat-developable photographic light-sensitive material, which is exposed to light and exposed to light, and then heated to 80 to 200 [deg.] C. for development.   A short wavelength light cut filter material in which one or more silver halide emulsions are coated on a support, wherein at least one silver halide emulsion is the silver halide emulsion according to claim 1. Filter material to do.