JPH06332097A - Silver halide photographic emulsion and manufacture of same - Google Patents

Abstract

PURPOSE:To enhance an effect of improving photographic characteristics due to metal doping by specifying the distribution of a polyvalent metal compound in silver halide grains. CONSTITUTION:This silver halide photographic emulsion comprises silver halide grains uniformly distributed with the polyvalent metal compound in the >=50% of the volume of each grain, and as this metal compound, the metal compounds of Mg, Al, Ca, and the like are preferably used, and preferably selected from single salts and metal complex salts, and in the case of metal complexes, hexa-, penta-, tetra-, and di-coordinated complexes are preferable, and especially, octahedral hexacoordinated and hexacoordinated plane complexes. This emulsion can be obtained, as one example, by maintaining a dopant concentration constant at the time of growing silver halide grains by >=50 of the grain volumes, preferably, keeping the concentrations of the dopant as well as halide ions or silver ions constant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion, and more particularly to a photographic emulsion having improved photographic characteristics such as sensitivity and illuminance failure characteristic due to metal doping.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials. In order to meet such demands, in order to improve the light-sensitive properties of silver halide emulsions, a technique for controlling charge carriers (carriers) involved in the light-sensitive process in silver halide grains is required.

One of the effective means for controlling carriers is metal doping.

For example, it has been reported by Leubner that electron doping is exhibited when silver halide is doped with an Ir complex (The Journal of Photographic Science Vo.
l.31, 93 (1983)). Further, for example, a technique of using divalent iron ions as a hole trapping dopant is disclosed in JP-A-1-121844.
No.

As described above, it is known that metal doping traps carriers, such as electrons and holes, which are deeply involved in the light-sensitive process, and improves the photographic characteristics of silver halide emulsions.

Further, studies have been made to control the distribution of the dopant in the silver halide grains to sufficiently bring out the effect of metal doping. For example, Japanese Patent Application Laid-Open No. 3-15040 discloses an example in which the region where iridium ions are present is limited below the surface of the grain. Japanese Patent Application Laid-Open No. 1-121844 discloses divalent iron ions in silver halide. , An example of doping in a portion having the smallest band gap energy is shown.

A uniform dopant distribution is considered as one of the optimum dopant distribution forms.
When the dopant is included in a wide range of the particles, the uneven distribution of carriers is reduced by making the dopant distribution uniform, and the generation of specific sites where unfavorable photographic characteristics process such as recombination process occurs is reduced, and metal doping is performed. It can be expected that the effect of improving the photographic characteristics by the method can be further increased.

Conventionally, a method called a uniform addition method has been used when a dopant is contained in a wide range of silver halide grains. A method in which a metal dopant is always added at a constant ratio with respect to silver ions or halide ions added during the formation of grains, and a method in which a dopant is usually mixed in a silver solution or a halide solution is used.

Further, as disclosed in JP-A-2-234151, a method of adding a dopant to a fine silver halide emulsion is also known. However, these uniform addition methods are methods in which the dopant is uniformly added to the silver halide in terms of formulation, and the actual doping amount is not uniform.

It is known that the doping ratio (dopant addition amount / actually doped amount) of the dopant depends on various conditions at the time of grain formation, and for example, JP-A-62-260137.
It is also described in the issue.

That is, in the conventional uniform addition method, the doping rate changes due to changes in various conditions during grain formation.
It is difficult to obtain an emulsion in which the dopant is evenly distributed.

Even when conditions such as pAg, pH, and temperature that are usually controlled during grain formation are kept constant, an emulsion in which the dopant is uniformly distributed cannot be obtained due to changes in conditions such as the dopant concentration in the reaction solution.

[0013]

As described above, no emulsion having a uniform dopant distribution is known among the emulsions containing the metal dopant in a wide range in the grain. The improvement effect was also unknown.

An object of the present invention is to provide a silver halide emulsion in which the effect of improving photographic characteristics by metal doping is further improved by optimizing the distribution of metal dopant in silver halide grains.

[0015]

The above object of the present invention is achieved by a silver halide photographic emulsion characterized by comprising silver halide grains in which a polyvalent metal compound is uniformly distributed over 50% or more of the grain volume. It was

The structure of the present invention will be described in detail below.

The silver halide photographic emulsion of the present invention comprises silver halide having any halide composition, and silver iodobromide or silver bromide is preferred. Further, silver halide grains having any halide composition distribution, such as grains having a plurality of layers having different halide compositions and grains having a uniform halide composition, can be used.

In the present invention, the grain size of silver halide grains is expressed as the side length of a cube having the same volume. The grain size of the silver halide grains of the present invention is not particularly limited, but 0.1 μm to 3.0 μm
Is preferred.

The term "doping" or "doping" refers to the inclusion of substances other than silver or halide ions in the silver halide grains.

The term "dopant" refers to compounds that dope silver halide grains.

The term "metal dopant" refers to a polyvalent metal compound that is doped in silver halide grains.

Mg, Al, C as metal dopant
a, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, M
o, Tc, Ru, Rh, Pd, Cd, Sn, Ba, C
e, Eu, W, Re, Os, Ir, Pt, Hg, Tl,
Metal compounds such as Pd, Bi and In can be preferably used.

The metal compound to be doped is preferably selected from a single salt or a metal complex. When selected from metal complexes, hexacoordinate, pentacoordinate, tetracoordinate and bicoordinate complexes are preferable, octahedral hexacoordinate and planar tetracoordinate complexes are more preferable.
The complex may be a mononuclear complex or a polynuclear complex. Further, as ligands forming the complex, CN ⁻ , C
O, NO ₂ ^-, 1,10-phenanthroline, 2,2'-bipyridine, SO ₃ ^2-, ethylenediamine, NH _3, pyridine,
H ₂ O, NCS ⁻ , NCO ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , OH ⁻ ,
_{^{CO 3 2-, SSO 3 2-,}} N 3 -, S 2-, F -, Cl -, B
r ⁻ , I ^−, etc. can be used.

K as a particularly preferred metal dopant_FourF
e (CN)₆, K₃Fe (CN)₆, Pb (NO₃)₂, K₂IrCl ₆, K₂IrBr₆, InCl₃But
can give. The amount of dopant added is 1 mol of silver halide.
10 against Le^-8Mol ~ 10^-3Moles preferred, 10^-6~Ten^-Four
Molar is more preferred.

The metal dopant may be added as a mixture with another additive solution, or may be added alone as a solution or as a solid. Further, it may be added to the reaction mother liquor in advance before grain formation, or may be added during the grain formation.

A uniform distribution of polyvalent metal compound, that is, metal dopant means that the relative standard deviation of the doping amount is 30%.
It means the following. In a preferred embodiment, the relative standard deviation is 20% or less, more preferably 15% or less.

In the present invention, the relative standard deviation of the amount of dope means at least every 1 to 7% of the total grain volume from the surface of the grain toward the inside by using a silver halide grain with a solvent.
Dissolve 50% or more, use the measured dope amount for each dissolved portion as the data, and divide the standard deviation by the average value.
It is a value obtained by multiplying by 100.

However, the doping amount is the content of the metal dopant per mol of silver halide.

As the silver halide solvent, an alkali halide solution, a thiosulfate solution, an alkali thiocyanate solution, an alkali cyanide solution, an ammonia solution or the like can be used.

As the metal ion analysis method, an atomic absorption method, an ICP emission analysis method, an ICP-mass spectrometry method, a glow discharge mass spectrometry method, or the like can be used.

The emulsion grains of the present invention are characterized in that the metal dopant is uniformly distributed over 50% or more of the grain volume. In a preferred embodiment, the uniformly distributed portion of the metal dopant is 65% or more of the particle volume, more preferably 80% or more.

One of the methods for obtaining the emulsion of the present invention is to keep the metal dopant concentration [M] constant during grain formation. As one of the more excellent methods, the silver ion concentration [Ag ⁺ ] or halide ion concentration [X] during grain formation,
Product of metal dopant concentration [M] [Ag ⁺ ] [M] or [X] [M]
There is a method of keeping constant. When the doping rate is as low as several% or less, [M] can be considered to be approximately equal to the total amount of the added dopant / the total volume of the reaction solution.

A monodisperse silver halide emulsion is preferably used for the silver halide photographic emulsion of the present invention. The monodisperse silver halide emulsion refers to an emulsion in which the weight of silver halide contained in the grain size range of ± 20% around the average grain size d is 70% or more of the total weight of silver halide, and preferably It is 80% or more, more preferably 90% or more.

The monodisperse emulsion has a breadth of distribution defined by 100 times the value obtained by dividing the standard deviation of grain size by the average grain size, and is 20% or less, more preferably 15% or less. Is. The particle size in the present invention means the side length of a cube having the same volume as the particles.

The silver halide emulsion of the present invention is a cube, 14
It may be a normal crystal such as a tetrahedron or an octahedron, or may be a twin crystal. Also, a mixture of these may be used.

In the case of twins, the projected area of a grain has a ratio of the equivalent circle diameter to the grain thickness of 1 to 20 and the projected area is 60.
% Or more is preferable. Further, the ratio of the equivalent circle diameter of the projected area of the grain to the grain thickness is preferably 1.2 or more and less than 8.0, and particularly preferably 1.5 or more and less than 5.0.

Monodisperse normal crystal emulsions are described, for example, in JP-A 59-59.
-177535, 60-138538, 59-52238, 60-l
43331, 60-35726, 60-258536 and 61-14
It can be produced by referring to the method disclosed in Japanese Patent No. 636 or the like.

Monodisperse twinned emulsions are disclosed, for example, in JP-A-61-161.
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in Japanese Patent No. 14636.

For the growth of the silver halide emulsion of the present invention, the apparatus shown in JP-A-62-160128 is preferably used.

For growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by the double jet method. Further, the iodide can be supplied to the system as silver iodide. The addition rate is preferably such that new nuclei are not generated and the size distribution does not spread due to Ostwald ripening, that is, in the range of 30 to 100% of the rate at which new nuclei are generated.

As another condition for enlarging the particles, as shown on page 88 of the Annual Meeting of the Photographic Society of Japan, 1988,
A method of enlarging by adding fine silver halide grains, dissolving and recrystallizing is included.

The growth conditions for the silver halide emulsion are pA
g5 to 11, temperature 40 to 85 ° C., pH 1.5 to 12 are preferable.

The silver halide photographic emulsion of the present invention is preferably desalted by a known method after forming the silver halide grains. As a method of desalting, for example, an aggregated gelatin agent or the like may be used, or a noodle washing method performed by gelatinizing gelatin may be used, and inorganic salts composed of a polyvalent anion, such as sodium sulfate and anions. Coagulation method using organic surfactants and anionic polymers (eg polystyrene sulfonic acid), and precipitation method (flocculation method) using gelatin derivatives (eg acylated gelatin, carbamoylated gelatin) Good. The silver halide grains desalted in this way are redispersed in a gelatin solution to prepare a silver halide emulsion.

The silver halide photographic emulsion of the present invention can be preferably used in a silver halide color photographic light-sensitive material.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the silver halide emulsion used is one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure No. 17643, No. l8716 and N.
o.308119 (hereinafter referred to as RDl7643, RDl8716 and RD3081
(Abbreviated as 19)).

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer, page 996, section III-A, page 23, page 648, spectral sensitizer, page 966 IV-A, B, C, D, H, I, J Item 23-24 page 648-9 Strength sensitizer page 966 IV-AE, J Item 23-24 page 648-9 page Antifoggant page 998 IV page 24-25 page 649 Stabilizer page 998 IV page 24-25 Page 649 The above-mentioned Research Disclosure also describes known photographic additives that can be used in the construction of a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention.

[Item] [RD308119] [RD17643] [RD18716] Color turbidity inhibitor page 1002 VII-I section 25 page 650 Dye image stabilizer 1001 page VII-J section 25 whitening agent 998 page V 24 page UV Absorber page 1003 VIII-C, VIII-C pages 25 to 26 Light absorber page 1003 VIII 25 to 26 page Light scattering agent page 1003 VIII Filter dye page 1003 VIII page 25 to 26 binder 1003 page IX page 26 651 page Static Inhibitor 1006 XIII 27 Page 650 Hardener 1004 X 26 Page 651 Plasticizer 1006 XII 27 Page 650 Lubricant 1006 XII 27 Page 650 Activator / Coating Aid 1005 Page XI 26-27 Page 650 page matting agent page 1007 page XVI developer (containing in light-sensitive material) page 1011 section XX-B Further, when a color photographic light-sensitive material is formed using the silver halide photographic emulsion of the present invention, various couplers are used. Can be used, and specific examples thereof are RDl7643 and RD308119 below.
It is described in.

[Item] [RD308119] [RD17643] Yellow coupler 100 page VII-D section 25 page VII-C to G section Magenta coupler page 1001 VII-D section 25 page VII-CG section Cyan coupler 100 page VII- Item D Page 25 VII-C to G Colored coupler Page 1002 VII-G Item 25 Page VII-G DIR coupler 1001 Page VII-F Item 25 Page VII-F BAR coupler Page 1002 VII-F Other useful residues Group-releasing coupler, page 1001, item VII-F Alkali-soluble coupler, page 1001, item VII-E Additives used in constructing a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention are RD308119 1007.
It can be added by the dispersion method described in page XIV.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pages 647-8 and RD308119 page 1009, section XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention may be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned RD308119 VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention has various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item RD308119 VII-K. You can

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by color positive films and color reversal papers.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in the above-mentioned RD1764328-29, RD187616.
The development can be carried out by a usual method described on page 15 and RD308119 XIX.

[0054]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of Each Emulsion Each comparative emulsion and each emulsion of the present invention were prepared as follows. For Em-2 and 3, the conventional uniform addition method was used. In Em-4, the Pb ²⁺ concentration during grain formation was added so that in Em-5, the product of the Pb ²⁺ concentration and the halide ion concentration was also constant.

However, the Pb ²⁺ concentration was set to be substantially equal to the ratio of the amount of lead nitrate added and the total volume of the added liquid.

Preparation of Comparative Emulsion Em-1 Liquids B and C were added at a rate shown in Table 1 by using the double jet method while keeping liquid A at 70 ° C. Liquid D was not added. Further, at that time, pAg was controlled as shown in Table 1 using the E liquid. When all the solution B was added, the addition was terminated, and desalting and redispersion were carried out by a conventional method. This emulsion is designated as emulsion Em-1.

Preparation of Comparative Emulsion Em-2 Emulsion Em except that Solution D was added as in Pattern 1 of Table 1.
Emulsion Em-2 was prepared in the same manner as -1.

Preparation of Comparative Emulsion Em-3 Emulsion Em-2 except that Solution B, Solution C and Solution D were mixed in a mixer provided outside the reaction vessel and then introduced into the reaction vessel.
Emulsion Em-3 was prepared in the same manner as in.

Preparation of Emulsion Em-4 of the Present Invention 37.8 ml of D solution was added to A solution in advance and then B
Emulsion Em-4 was prepared in the same manner as emulsion Em-2, except that the addition of liquids C, D and D was started and liquid D was added as shown in pattern 2 of Table 1.

Preparation of Emulsion Em-5 of the Present Invention 47.6 ml of solution D was added to solution A in advance and then solution B was added.
Emulsion Em-5 was prepared in the same manner as emulsion Em-2, except that the addition of liquids C, D and D was started and liquid D was added as shown in pattern 3 of Table 1.

Preparation of Comparative Emulsion Em-6 Emulsion Em-6 was prepared in the same manner as Emulsion Em-2 except that Solution F was used instead of Solution E.

Preparation of Comparative Emulsion Em-7 Emulsion Em-7 was prepared in the same manner as Emulsion Em-3 except that Solution F was used instead of Solution E.

Preparation of Comparative Emulsion Em-8 Emulsion Em-8 was prepared in the same manner as Emulsion Em-4 except that Solution F was used instead of Solution E.

Preparation of Comparative Emulsion Em-6 Emulsion Em-9 was prepared in the same manner as Emulsion Em-5 except that Solution F was used instead of Solution E.

All the emulsion grains obtained as a result of electron microscopic observation were octahedral emulsions having an average grain size of 1.00 μm.

Solution A Ossein gelatin 137.0 g Polyisopropylene-polyoxyethylene-disuccinate sodium salt 10% methanol solution 20.0 ml Normal silver bromide seed emulsion (average particle size 0.275 μm) 0.1469 mol equivalent (oscein Gelatin 3.0g included) Pure water 7000.0ml B liquid Silver nitrate 1175.0g Pure water 5764.2ml C liquid Oscein gelatin 140.0g Potassium bromide 979.7g Potassium iodide 27.9g Pure water 7000.0ml D liquid 3.5N Potassium bromide 300.0 ml E liquid Lead nitrate 1.169 g Pure water 100.0 ml F liquid Lead nitrate 0.023 g Pure water 100.0 ml

[0068]

[Table 1]

Analysis of Metal Dopant After the gelatin of the emulsions 1 to 5 was decomposed by a gelatin decomposing enzyme, the particles were dissolved and the metal dopant was analyzed using a 1.0 N Na ₂ S ₂ O ₃ solution. The method of gelatin decomposition is as follows. Dissolve each emulsion by heating, remove only the precipitate by centrifugation, and precipitate the 0.1% actinavi solution by about 15
Add 20 ml to g and stir at 40 ° C to 50 ° C for about 30 minutes. Centrifugation again removes only the precipitate, and actinavi solution is again added in the same manner. After repeating this several times, washing is performed in the order of methanol → 1NHNO ₃ → ultra pure water. The washing method was performed in the order of addition of liquid → stirring → centrifugation → decantation (only the precipitate was taken). This operation was repeated 3 times for each liquid. The dissolution method is as follows: Add about 0.5 to 10 ml of 1.0N Na ₂ S ₂ O ₃ solution to about 1 g of a silver halide sample, add an appropriate amount of pure water, stir at room temperature for 30 minutes, and then solid phase. And the liquid phase are separated by centrifugation and filtration. While repeating this several times, the particle size of the particles before and after melting was measured by an electron microscope.

The solution obtained by dissolution was used as a sample for quantitative determination of metal dopant, and Ag and Pb by ICP emission spectrometry were used.
Was quantitatively analyzed. Every 3% to particle volume, particle size from 1.00 μm to 0.30 μm (about 97% of particle volume)
%), And the data of the doping amount were obtained. Volume ratio of uniform dope layer obtained from these dope amount data, and particle size 1.
Table 2 shows the relative standard deviation of the doping amount from 00 μm to 0.78 μm (corresponding to about 53% of the particle volume).

Evaluation of Sensitivity The emulsions of Em-1 to 5 were optimally chemically sensitized with hypo, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, polyvinylpyrrolidone, coating aids were used. Then, dioctyl sodium sulfosuccinate and 1,2-bis (vinylsulfonyl) ethane as hardeners were added in appropriate amounts and coated on a cellulose triacetate base to obtain a sample for sensitometry. These samples were exposed through an optical wedge and a filter under two conditions of an exposure amount of 32 CMS and an exposure time of 1/100 seconds and 8 seconds, and the following treatments were performed.

[0072] Developer Metol 2.5g L-Ascorbic acid 10.0g Sodium metaborate tetrahydrate 35.0g Potassium bromide 1.0g Pure water 1000.0ml Stop solution Acetic acid (3%) Fixer Konica Fix (Konica Corporation) Each developed The sample was subjected to concentration measurement using an optical densitometer to determine the sensitivity. Sensitivity is minimum optical density +0.1
The value was calculated as the reciprocal of the exposure amount (true value) giving the density of 1. The evaluation results of each emulsion are shown in Table 2.

As can be seen by comparing the sensitivities of 1/100 second, the photographic sensitivity was improved by increasing the uniformity of the dopant represented by the relative standard deviation of the uniform doping layer volume ratio and the doping amount.

Further, as can be seen from the 8-second sensitivity, the low illuminance failure characteristic was improved by increasing the uniformity of the dopant.

[0075]

[Table 2]

[0076]

EFFECT OF THE INVENTION By uniformly distributing the metal dopant in 50% or more of the volume of silver halide grains, a silver halide emulsion having high sensitivity and no illuminance failure can be obtained.

[Procedure amendment]

[Submission date] March 31, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

Preparation of Comparative Emulsion Em-1 Liquids B and C were added at a rate shown in Table 1 by using the double jet method while keeping liquid A at 70 ° C. Liquid E was not added. At that time, pAg was controlled as shown in Table 1 by using the D liquid. When all the solution B was added, the addition was terminated, and desalting and redispersion were carried out by a conventional method. This emulsion is designated as emulsion Em-1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

Preparation of Comparative Emulsion Em-2 Emulsion Em except that Solution E was added as shown in Pattern 1 of Table 1.
Emulsion Em-2 was prepared in the same manner as -1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

Preparation of Comparative Emulsion Em-3 Emulsion Em-2 except that Solution B, Solution C and Solution E were mixed in a mixer separately provided outside the reaction vessel and then introduced into the reaction vessel.
Emulsion Em-3 was prepared in the same manner as in.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Preparation of Emulsion Em-4 of the Present Invention 37.8 ml of D solution was added to A solution in advance and then B
Emulsion Em-4 was prepared in the same manner as Emulsion Em-2, except that the addition of Liquids C, D and D was started and E was added as shown in Pattern 2 of Table 1.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

Preparation of Emulsion Em-5 of the Present Invention 47.6 ml of solution D was added to solution A in advance and then solution B was added.
Emulsion Em-5 was prepared in the same manner as Emulsion Em-2, except that the addition of Liquids C, D and D was started and E was added as shown in Pattern 3 of Table 1.

Claims (3)

[Claims] 1. A silver halide photographic emulsion comprising silver halide grains in which a polyvalent metal compound is uniformly distributed over 50% or more of the grain volume. 2. A method for producing a silver halide emulsion, characterized in that the dopant concentration during growth of silver halide grains is kept constant over 50% or more of the grain volume. 3. A method for producing a silver halide emulsion, characterized in that the product of the dopant concentration and the halide ion concentration or the silver ion concentration during the growth of silver halide grains is kept constant over 50% or more of the grain volume. .