JPH0785165B2 - Method for producing silver halide photographic emulsion - Google Patents

Description

Detailed Description of the Invention

 [Field of Industrial Application] The method of producing the silver chlorobromoiodide photographic emulsion of the present invention will be described in more detail.
There is little fog and the sensitivity is higher than the particle size.
The present invention relates to a method for producing a dispersed silver chlorobromochloroiodide photographic emulsion. BACKGROUND OF THE INVENTION Photographic film for X-ray, color negative film, etc.
Relatively coarse as a high-speed photographic emulsion used for materials
A silver iodobromide emulsion having grains is mainly used.
Also, the silver halide grains of these emulsions are in a monodisperse state.
The so-called monodisperse emulsion is preferably used. Monodisperse
An emulsion is the grain size of the silver halide microcrystals that make up the emulsion.
A cloth is extremely narrow, and has properties other than particle size, such as
The properties and photographic properties are uniform among the particles, and high image quality is obtained.
Suitable for obtaining true performance. Various methods are known for the production of monodisperse silver halide emulsions.
For example, Japanese Patent Publication No. Sho 48-36896, JP-A No. 54-48521,
54-99419, 55-77737, 58-49938, 59-46
Although it is described in No. 640, etc.
As stated above, silver iodobromide had a low solubility and a slow grain growth rate.
Therefore, in order to obtain a large grain size emulsion, use a silver halide solvent.
It is generally practiced to use ammonia. On the other hand, for photosensitive materials for printing such as color paper
In this case, it is necessary to have the high photosensitivity of the above-mentioned photosensitive material for photography.
Rapid development processing characteristics, high contrast
Therefore, silver chlorobromide emulsions with excellent developability are mainly used.
It is used. Silver chlorobromide has a relatively high solubility and is formed into grains.
Due to its long length, a silver halide solvent should be used during grain formation.
Conventionally, there is no need to use a halide ion solution and silver nitrate.
It is manufactured by the so-called boiling method of mixing with a solution.
It was being done. [Problems to be Solved by the Invention] As described above, in the light-sensitive material such as color paper
Images with high contrast due to rapid development processing
Good developability to be obtained is required. Excellent developability
It is effective to make silver halide grains fine in order to obtain
However, the photosensitivity usually decreases as the particles become finer.
Therefore, an emulsion showing high sensitivity even with fine particles is required. It also forms an image on a reflective support such as color paper.
When using a light-sensitive material, the coloring on the white background is extremely high.
Is required as an important characteristic
In addition to using an emulsion with minimal fog, fluorescence
Various measures have been taken, such as using a whitening agent, but there are still ten
There is a need for a clearer white background, which is not enough. In addition to fog and sensitivity, stable performance during storage
And various performances such as fog increase at high temperature storage
Silver chlorobromide obtained by conventional methods, which requires further improvement
It is difficult to meet these requirements with emulsion performance.
It was The object of the present invention was difficult to obtain by conventional methods
Very little fog, and photosensitivity such as photosensitivity and storability
Silver halide emulsion with excellent properties, especially monodisperse silver chlorobromide milk
It is to provide a manufacturing method of the agent. [Means for Solving Problems] As a result of earnest studies, the present inventors have found that in the presence of protective colloids.
Mixing silver ion solution and halide ion solution,
Silver iodide 2 mol% or less, silver chloride 1 to 100 mol%, silver bromide 9
Silver halide having a silver halide composition of 9 mol% or less
Production of silver halide photographic emulsions that form and grow grains
In the method, the silver ion solution is ammoniacal silver nitrate.
It is a solution and the formation and growth of the silver halide grains are
Represented by the following general formula (I), (II), (III) or (IV)
The presence of at least one compound selected from
(110) plane or (1
10) Halogen consisting of silver halide crystals with ridges on the surface
The purpose of the present invention depends on the method for producing a silver halide photographic emulsion.
I found that I could be reached. Where R₁， R₂, And R₃Can be the same or different,
Hydrogen atom, halogen atom, hydroxyl group,
Mino group, amino group derivative, alkyl group, alkyl group
Derivatives, aryl groups, aryl group derivatives, cycloal
Kill group, cycloalkyl group derivative, mercapto group,
Derivative of rucapto group, or -CONH-R_Four(R_FourIs a hydrogen atom,
Alkyl groups, amino groups, derivatives of alkyl groups, amino groups
Derivatives, halogen atoms, cycloalkyl groups, cycloalkyl groups
Derivatives of alkyl groups, aryl groups, or derivation of aryl groups
Represents the body. ), R₁And R₂Are joined together to form a ring
Good. In the general formulas (I) to (IV), R₁~ R_FourRepresented by
Examples of the alkyl group include a methyl group, an ethyl group,
Propyl group, benzyl group, hexyl group, octyl group, a
Sopropyl group, sec-butyl group, t-butyl group, 2-carb
Examples include a rubornyl group, etc., as a derivative of an alkyl group.
Is, for example, substituted with an aromatic residue (a divalent linking group, eg
For example, —NHCO— or the like) alkyl group (for example,
Benzyl group, phenethyl group, benzhydryl group, 1-naphth
Cylmethyl group, 3-phenylbutyl group, benzoylami
Noethyl group, etc.), alkyl group substituted with an alkoxy group
(For example, methoxymethyl group, 2-methoxyethyl group, 3
-Ethoxypropyl group, 4-methoxybutyl group, etc.),
Rogen atom, hydroxy group, carboxy group, mercapto
Groups, alkoxycarbonyl groups or substituted or unsubstituted
Alkyl groups substituted with amino groups of
Cyl group, hydroxymethyl group, hydroxymethyl group, 3
-Hydroxybutyl group, carboxymethyl group, 2-cal
Voxyethyl group, 2- (methoxycarbonyl) ethyl
Group, aminomethyl group, diethylaminomethyl group, etc.),
Alkyl groups substituted by chloroalkyl groups (eg cyclo
Pentylmethyl group, etc.), represented by the above general formulas (1) to (IV)
The compound is a monovalent group with one hydrogen atom removed.
Examples include a substituted alkyl group and the like. R₁~ R_FourExamples of the aryl group represented by are phenyl
Group, 1-naphthyl group and the like, and an aryl group derivative
Are, for example, p-tolyl group, m-ethylphenyl
Group, m-cumenyl group, mesityl group, 2,3-xylyl group,
p-chlorophenyl group, o-bromophenyl group, p-hi
Droxyphenyl group, 1-hydroxy-2-naphthyl
Group, m-methoxyphenyl group, p-ethoxyphenyl
Group, p-carboxyphenyl group, o- (methoxycarbo group
Nyl) phenyl group, m- (ethoxycarbonyl) phenyl
Group, 4-carboxy-1-naphthyl group and the like.
It R₁~ R_FourExamples of the cycloalkyl group represented by
Cycloheptyl group, cyclopentyl group, cyclohexyl
Group and the like, and as the derivative of the cycloalkyl group,
Examples thereof include a methylcyclohexyl group and the like. R₁~ R_Four
Examples of the halogen atom represented by are fluorine, salt
Elemental, bromine, iodine, etc., R₁~ R_FourDerivation of amino group represented by
Examples of the body include butylamino group and diethylamino group.
Group, anilino group and the like. R₁~ R₃Is represented by
Examples of the derivative of the rucapto group include a methylthio group and an ether group.
Examples thereof include a tylthio group and a phenylthio group. Next, the general formula (I), (II), (III) or (I
Representative specific examples of the compound represented by V) are shown below. The above compound according to the present invention (hereinafter simply referred to as tetrazaindene
Compound) is added to the mother liquor when the silver halide emulsion is formed.
And the presence of silver halide grains during the formation and growth of silver halide grains.
Therefore, it is preferable to increase the addition amount. Therefore, the present invention
The tetrazaindene compound of
Genide ion solution (hereinafter referred to as halide solution) or
Is preferably added to the ammoniacal silver nitrate solution
In addition to the above liquids, the tetrazaindene formation of the present invention
Make a compound solution, and use a halide solution and / or ammoniacal
It is also preferable to inject it into the emulsion together with the silver nitrate solution.
However, it is practically added to the mixed mother liquor and halide solution.
Is the most preferable because it simplifies the process and increases productivity.
Yes. Tet to be replenished during the growth of the mixed mother liquor and silver halide grains
Halogen by changing the amount of ruzaindene compound
History of crystal habit during silver halide crystal growth and shape of final product grain (crystal
Habit) can be controlled. The amount of tetrazaindene compound added depends on the halo to be obtained.
Grain size of silver gentide grains, composition of silver halide, during emulsion preparation
Depending on the manufacturing conditions such as temperature, pH, pAg, etc.,
10 per mol of silver halide formed^-Five~ 2 x 10^-1Mole
Ranges are preferred. In the method of the present invention, the tetrazaindene as described above is used.
Halide solution and ammoniacal silver nitrate in the presence of phosphorus compounds
Mix the solutions to form a silver halide emulsion.
What is ammoniacal silver nitrate solution?
More than equivalent amount of monia was added to make a silver-ammine complex solution.
Therefore, when ammoniacal silver nitrate is used, the solution becomes
At the moment when it was added to the mixture, the silver-ammine complex
Overwhelmingly large, free silver ion concentration directly in silver nitrate solution
It is much smaller than when added and the formation of silver oxide is extremely small.
Since it decreases, it may be reduced to metallic silver.
Less, combined with the effect of the tetrazaindene compound
A strong effect of suppressing the occurrence of fog can be obtained. On the other hand, when using an ammoniacal silver nitrate solution, silver ion dissolution
A large amount of ammonia is contained in the liquid mixture of the liquid and the halide solution.
The pH of the liquid increases because it is brought in, but milk containing silver chloride
The agent will fog if its formation takes place at too high a pH.
May increase with the ammoniacal silver nitrate solution
PH of the mixed solution at the time of mixing the halide ion solution
Is preferably maintained at 10 or less, more preferably 6 to 9.5
Is desirable. To keep the pH in the above condition, ammoniacal silver nitrate
Solution that is the mother liquor of the mixture of the solution and the halide ion solution
A colloidal solution and / or halide ion solution
Method, add an appropriate amount of acid, or mix the acid solution.
Add to the mixture continuously or intermittently as the
It is possible to take such a method. Acid used to adjust pH
Examples include inorganic acids such as sulfuric acid and nitric acid, acetic acid, and
It is possible to use various acidic substances such as organic acids such as enoic acid.
You can In the method of the present invention, as described above, silver halide grains are used.
Depending on the amount of tetrazaindene compound present during child formation
The crystal habit and shape of the obtained silver halide grains change.
However, the crystal habit, grain size distribution, and shape of silver halide microcrystals are
Journal of Photographic Science
(Journal of Photographic Science) Volume 12 242-251
Page (1964), Vol. 27, pages 47-53 (1979) and many other sentences
As stated in the dedication, silver-io in the liquid during microcrystal forming
Concentration, that is, pAg. In the method of the present invention, an ammoniacal silver nitrate solution and ha
PAg of the mixed solution at the time of mixing the rogenide ion solution
It is preferable to maintain within the range of 4-9. get pAg
Crystal habit, shape, and grain size of the intended silver halide emulsion grains
Depending on the cloth etc., a constant value within the above range throughout the mixing period
May be maintained at the same time as described in JP-A-59-46640.
You can change it in the process of adding silver ion solution like
Yes. The pAg control method is as follows:
Method using mixed solution of chloride ion and water-soluble chloride ion
Method is preferred. That is, halide ions during mixing
The addition amount per unit time of is almost equal to the addition amount of silver ion.
At the same time, the water-soluble bromide ion and chloride ion
PAg control solution consisting of mixed solution at the ratio shown by the following formula
Controlling pAg value by adding pAg controllability, the resulting grains
It is preferable in terms of monodispersibility of the particles and halogen composition. Formula Y = KX In the formula, X is the Cl / Br ratio (mol
Ratio) and K are positive numbers from 40 to 1200. Further, the value of K is that of the emulsion mother liquor that forms and suspends silver halide.
Depending on the temperature, it should be within the range of the value calculated by the following formula.
And are preferred. K = (634.9-12.75t + 0.07938t²) S where t is the emulsion mother liquor that produces and suspends silver halide
Temperature (° C) and S are positive numbers of 3 to 1/3. The silver ion solution (first
The amount of halide ions is approximately the same as the amount of silver ions in the liquid).
The halide ion solution (second liquid) should be
Although the pAg control solution is added, the change in pAg at this time is sufficient.
Adjust the temperature and / or addition rate so that
It is prepared and added. The addition rate of the pAg control solution depends on the addition rate of the second solution.
When it is close to the acceleration, the concentration of the pAg control liquid is the total of the second liquid.
1/10 or less of halide ion concentration is preferable.
The addition rate can be set to 1/10 or less of the addition rate of the second liquid
In this case, even if it is equal to the halide ion concentration of the second liquid,
Good. Flow rate control techniques commonly used to control the addition rate
Is available. The preferred temperature during the production of silver halide in the present invention is 30
It is -80 ° C, and more preferably 40-70 ° C. As the protective colloid in the present invention, a water-soluble polymer
Substance, eg gelatin, or polyvinyl alcohol
Natural or synthetic polymeric substances such as
Can be used. The present invention can be used for any shape of hexahedron, octahedron, dodecahedron, etc.
Effective for producing monodisperse emulsions composed of silver genide crystals
Applicable to, but especially dodecahedron and (18) faces with (110) faces
Body, icosahedron, 26-faced body, 24 sides with (110) ridgeline
Consists of 30-, 30-, and 38-sided silver halide crystals
It is effective for producing an emulsion. Silver halide
There is a uniform composition of silver halide in the crystal.
Of course, Iwayu, of course, has a continuously changing composition.
Of emulsions consisting of discontinuous core / shell type grains
It is also effective for construction. Further, the present invention is a polydisperse crystal having a wide grain size distribution of silver halide crystals.
In the production of emulsions, of course, the grain size distribution is extremely narrow,
It is also effective in the production of monodisperse emulsions. Here simply
What is a dispersed emulsion?, The coefficient of variation is 20% or less.
From the above, those of 15% or less are more preferable. Protected when producing monodisperse emulsions by the method of the present invention
Fine halogenation prepared separately in mother liquor containing colloid
Silver crystals (so-called seed emulsion) were added in advance, and then tetra
Ammoniacal silver nitrate solution in the presence of Zaindene compounds
And halide ion solution are added to the seed emulsion grains.
It is preferable to grow to a required grain size. Used at this time
The conditions for preparing seed emulsions are not particularly limited.
There is no time. These silver halide emulsions are activated gelatin; sulfur sensitized
Agents such as allylthiocarbamide, thiourea, cystine, etc.
Sulfur sensitizers; selenium sensitizers; reduction sensitizers, for example
Salt, thiourea dioxide; polyamine, etc .; examples of noble metal sensitizers
For example, a gold sensitizer, specifically potassium aurithiocyanate
G, potassium chloroaurate, 2-aurothio-3-
Methylbenzothiazolium chloride, etc. or for example
Ruthenium, palladium, platinum, rhodium, iridium
Water-soluble salt sensitizers such as ammonium chloro
Palladate, potassium chloroplanate and natriu
Muchloroparadate (some of these are
Acts as a sensitizer or antifoggant
It ) Etc. alone or in combination as appropriate (for example, gold sensitization)
Agent and sulfur sensitizer, gold sensitizer and selenium sensitizer
Etc.) and chemically sensitized. The silver halide emulsion of the present invention contains a sulfur-containing compound.
Chemically aged, before, during, or aged this chemical
Then at least one hydroxytetrazaindene and
Fewer nitrogen-containing heterocyclic compounds containing mercapto
Both may contain one kind. The silver halide used in the present invention has a desired photosensitivity.
To impart photosensitivity in the long range, use a suitable sensitizing dye.
5 × 10 to 1 mol of silver genide^-8~ 3 x 10^-3Mole added
It may be optically sensitized. Various sensitizing dyes
Can be used, and one or two sensitizing dyes can be used.
The above can be used in combination. When the photographic emulsion of the present invention is applied for color photography,
For each color that develops in yellow, magenta and cyan
A coupler, that is, a dye that reacts with an oxidized product of a color developing agent.
A compound capable of forming can be included. The yellow cap that has been conventionally known as the above coupler
Use Ra, magenta and cyan couplers
be able to. These couplers are so-called 2-equivalent types
It may be a 4-equivalent coupler,
In combination with these couplers, diffusible dye-releasing couplers
-It is also possible to use. Include these couplers in the silver halide emulsion
When the coupler is alkali-soluble,
It may be added as a Lucari solution and is oil-soluble
The coupler in a high-boiling solvent and, if necessary, in a low-boiling solvent.
Dissolve in a combined medium and disperse in fine particles to form silver halide
It is preferably added to the emulsion. Other as needed at this time
Hydroquinone derivatives, UV absorbers, anti-fading agents, etc.
You can use it together. Also two or more couplers
It is okay to mix and use. In addition to the various functional materials described above, various types of emulsions of the present invention can be used.
Photographic additives may be included, for example Lisa
Reach Disclosure No. 17643
Antifoggant, stabilizer, UV absorber, color stain inhibitor,
Fluorescent brightener, color image fading inhibitor, antistatic agent, hardener,
Surfactants, plasticizers, wetting agents and the like can be used. The present invention will be specifically described with reference to examples below.
The embodiment of the present invention is not limited to this. [Example] (Preparation of seed emulsion) As shown in Table 1 according to the method described in JP-A No. 50-45437.
Various silver chlorobromide seed emulsions NE-1 to NE-4 were prepared. With various emulsions
It contains 1.413 mol of silver chlorobromide.Example 1 Silver chlorobromide milk having a silver bromide content of 50 mol% and an average particle size of 0.5 μm
Preparation of agents. (Preparation of Emulsion According to the Present Invention) A silver bromide content of 50 mol% was prepared by using the following five solutions.
An emulsion (EM-1) according to the present invention was prepared. Tetrazine
The exemplified compound (2) was used as the den compound. [Solution 1-A][Solution 1-B][Solution 1-C][Solution 1-D][Solution 1-E] Acetic acid 65% solution 2000 ml at 40 ° C. Shown in JP-B-85-58288 and JP-B-58-58289
Solution 1-A while stirring using the mixed stirrer
Add 1-B and solution 1-C by double jet method
did. As shown in Table 2, the addition rate changes with the addition time.
It increased linearly. During addition of each solution, solution 1-D
Control the pAg of the mixture to 8.4 (EAg value +76 mV) using
Also, adjust the pH of the mixture using Solution 1-E as shown in Table 2.
It was controlled so as to decrease with. Solution 1-B, 1-C, 1-
Addition of D and 1-E is based on a variable flow rate roller tube.
A volume pump was used. Two minutes after the addition of solution 1-B and solution 1-C was completed, solution 1-
E was added to adjust the pH value of the emulsion to 6.0. Then the following operations
The emulsion was washed with water and desalted depending on the composition. As a coagulating precipitation agent
Demol N (manufactured by Kao Atlas) 5% aqueous solution 913 ml and sulfur
Add 691 ml of 20% magnesium acid aqueous solution to flocculate the emulsion.
Let it stand and let it settle, then decant the supernatant and distill it with distilled water.
15375 ml was added and dispersed again. 20% magnesium sulfate
After adding 541 ml of aqueous solution of water to aggregate and settle the emulsion again
The supernatant is decanted, and 1000 ml of an aqueous solution of ossein gelatin is added.
Add 80g of ossein gelatin and stir at 40 ℃ for 20 minutes.
After stirring and dispersing, the total amount was adjusted to 5000 ml with distilled water.
Hereinafter this emulsion is referred to as EM-1. (Preparation of Comparative Emulsion by Ammonia Method) Exemplified compound (2) was removed from the solutions 1-A and 1-B.
All other items are the same as in ME-1 above.
A contrast emulsion was prepared by the monia method and designated as ME-2. (Preparation of Comparative Emulsion by Neutral Method) The following four solutions were prepared and prepared by the neutral method. [Solution 2-A][Solution 2-B][Solution 2-C][Solution 2-D]Shown in JP-B-85-58288 and 58-58289 at 60 ℃
Solution 2-A while stirring with a mixed stirrer
Add 2-B and solution 2-C by double jet method
did. The addition rate of Solution 2-B is as shown in Table 3
It increased linearly with time. Solution 2-C addition rate
The degree of addition of solution 2-B was 0.95 at each addition time point.
I doubled it. During addition of each solution, Solution 2-D
Was used to control the pAg of the mixture to be 6.0. Solution 2-B, 2-C, and 2-D were added with variable flow rate
A Lar tube metering pump was used. After adding solution 2-B and solution 2-C,
The emulsion was washed with water and desalted. Demonstration as a coagulating sedimentation agent
1300 ml of 5% aqueous solution of Nol (manufactured by Kao Atlas) and sulphate
Add 1300 ml of 20% aqueous gnesium to agglomerate the emulsion,
After placing and allowing to settle, the supernatant is decanted and distilled water 12300 m
l was added and dispersed again. 20% magnesium sulfate water soluble
Add 400 ml of the solution and aggregate the emulsion again to allow it to settle.
Decant, and add 800 ml of an aqueous solution of ossein gelatin.
(Including 80 g of in-gelatin) and stir at 40 ° C for 20 minutes
After dispersion, the total volume was adjusted to 5000 ml with distilled water. Below
The emulsion is designated as EM-3.The content of the three types of silver bromide obtained as described above is 50 mol%
Shape, grain size, grain size distribution (variable
The coefficient of motion is shown in Table 4.The average particle size of EM-1 in the above table was determined by the sedimentation method (Horiba
Cubic with the same volume of particle size (according to CAPA-500 manufactured by Seisakusho)
It is a value converted to the length of one side of the body. Example 2 Silver chlorobromide milk having a silver bromide content of 90 mol% and an average particle size of 1.0 μm
Preparation of agents. 90 mol% silver bromide content, average particle size
Four 1.0 μm emulsions according to the invention (EM4-7) and contrasting milk
An agent (EM-8) was prepared. As a tetrazaindene compound
The amount of the exemplified compound (2) shown in Table 5 is
used. [Solution 3-A][Solution 3-B][Solution 3-C][Solution 3-D][Solution 3-E] Acetic acid 65% solution 2000 mlFor each emulsion, at 40 ° C, Japanese Patent Publication Nos. 85-58288 and 58-5
Solution while stirring using the mixing stirrer shown in No. 8289
Solution 3-B and solution 3-C in 3-A by double jet method
Added by. The addition rate is as shown in Table 6
It increased linearly with time. In addition, each solution addition
During this period, the pAg of the mixed solution was adjusted to 8.4 (EAg value + 76 m) using Solution 3-D.
V) and display the pH of the mixture using Solution 3-E.
It was controlled so as to decrease with time as in No. 6. solution
Addition of 3-B, 3-C, 3-D and 3-E is a variable flow type low flow rate.
A Lar tube metering pump was used. Two minutes after the addition of Solution 3-B and Solution 3-C was completed, Solution 3-
E was added to adjust the pH value of the emulsion to 6.0. Then the following operations
The emulsion was washed with water and desalted depending on the composition. As a coagulating precipitation agent
Demol N (manufactured by Kao Atlas) 5% aqueous solution 913 ml and sulfur
Add 691 ml of 20% magnesium acid aqueous solution to flocculate the emulsion.
Let it stand and let it settle, then decant the supernatant and distill it with distilled water.
15375 ml was added and dispersed again. 20% magnesium sulfate
After adding 541 ml of aqueous solution of water to aggregate and settle the emulsion again
The supernatant is decanted, and 1000 ml of an aqueous solution of ossein gelatin is added.
Add 80g of ossein gelatin and stir at 40 ℃ for 20 minutes.
After stirring and dispersing, the total amount was adjusted to 5000 ml with distilled water.Example 3 Silver chlorobromide milk having a silver bromide content of 50 mol% and an average particle size of 1.0 μm
Preparation of agents. Silver bromide content 50 mol%, average particle size
1.0 μm emulsion according to the present invention (EM9-12) and contrasting milk
Agent (EM-13) was created. As a tetrazaindene compound
The amount of the exemplified compound (2) shown in Table 7 is
used. [Solution 4-A][Solution 4-B][Solution 4-C][Solution 4-D][Solution 4-E] Acetic acid 65% solution 2000 mlFor each emulsion, at 40 ° C, Japanese Patent Publication Nos. 85-58288 and 58-5
Solution while stirring using the mixing stirrer shown in No. 8289
Solution 4-B and solution 4-C in 4-A by double jet method
Added by. The addition rate is as shown in Table 8
It increased linearly with time. In addition, each solution addition
During this period, the pAg of the mixed solution was adjusted to 8.0 (EAg value + 100) using solution 4-D.
mV) and display the pH of the mixture using Solution 4-E.
It was controlled so as to decrease with time as in No. 8. solution
Addition of 4-B, 4-C, 4-D and 4-E is a variable flow type low flow rate.
A Lar tube metering pump was used. Two minutes after the addition of the solution 4-B and the solution 4-C, the solution 4-
E was added to adjust the pH value of the emulsion to 6.0. Then the following operations
The emulsion was washed with water and desalted depending on the composition. As a coagulating precipitation agent
Demol N (manufactured by Kao Atlas) 5% aqueous solution 913 ml and sulfur
Add 691 ml of 20% magnesium acid aqueous solution to flocculate the emulsion.
Let it stand and let it settle, then decant the supernatant and distill it with distilled water.
15375 ml was added and dispersed again. 20% magnesium sulfate
After adding 541 ml of aqueous solution of water to aggregate and settle the emulsion again
The supernatant is decanted, and 1000 ml of an aqueous solution of ossein gelatin is added.
Add 80g of ossein gelatin and stir at 40 ℃ for 20 minutes.
After stirring and dispersing, the total amount was adjusted to 5000 ml with distilled water.Example 4 Silver chlorobromide milk having a silver bromide content of 15 mol% and an average particle size of 1.0 μm
Preparation of agents. Silver bromide content 15 mol%, average particle size
1.0 μm emulsion according to the invention (EM14) and contrast emulsion (EM-)
15) was created. The tetrazaindene compound is as described above.
Exemplified compound (2) was used in the amounts shown in Table 9, respectively.
It was [Solution 5-A][Solution 5-B][Solution 5-C][Solution 5-D][Solution 5-E] Acetic acid 65% solution 2000 mlFor each emulsion, at 40 ° C, Japanese Patent Publication Nos. 85-58288 and 58-5
Solution while stirring using the mixing stirrer shown in No. 8289
Solution 5-B and solution 5-C in 5-A by double jet method
Added by. Addition speed is as shown in Table 10
It increased linearly with time. In addition, each solution addition
In the meantime, using the solution 5-D, the pAg of the mixed solution was 8.8 (EAg value + 52 m
V), and the pH of the mixture was adjusted using Solution 5-E.
It was controlled so as to decrease with time as in 0. solution
Addition of 5-B, 5-C, 5-D and 5-E is a variable flow type low flow rate.
A Lar tube metering pump was used. Two minutes after the addition of Solution 5-B and Solution 5-C was completed, Solution 5-
E was added to adjust the pH value of the emulsion to 6.0. Then the following operations
The emulsion was washed with water and desalted depending on the composition. As a coagulating precipitation agent
Demol N (manufactured by Kao Atlas) 5% aqueous solution 913 ml and sulfur
Add 691 ml of 20% magnesium acid aqueous solution to flocculate the emulsion.
Let it stand and let it settle, then decant the supernatant and distill it with distilled water.
15375 ml was added and dispersed again. 20% magnesium sulfate
After adding 541 ml of aqueous solution of water to aggregate and settle the emulsion again
The supernatant is decanted, and 1000 ml of an aqueous solution of ossein gelatin is added.
Add 80g of ossein gelatin and stir at 40 ℃ for 20 minutes.
After stirring and dispersing, the total amount was adjusted to 5000 ml with distilled water.To which the silver halide grains prepared as described above belong
The morphology is shown in FIGS. 1 to 17. In each figure, 1 is the (110) plane, 2 is the quasi (110) plane, and 3 is adjacent.
It is a ridgeline that intersects the quasi (110) plane. Quasi (110)
A plane is a crystal plane that is in contact with the (110) plane with the above ridgeline.
U 4 is a (100) plane and 5 is a (111) plane. Furthermore, the charge of the silver halide grains of the emulsions from EM-1 to EM-15 is
Child micrograph observation result (crystal shape, particle size distribution) and sedimentation
Table 11 shows the results of average particle diameter by the method. Average grain size is dig
The particle size obtained by the sedimentation method using the CAPA-500 manufactured by BABA
It is a value converted into one side length of a cube having the same volume. An electron micrograph showing the shape of each emulsion is shown in P-1.
It is shown in FIGS. 18 to 31 as P-14. Example 5 Next, a photographic feature using the silver halide photographic emulsion according to the present invention was used.
I checked my sex.

[Creation of photosensitive material]

Optimal chemical sensitization was performed by adding sodium thiosulfate to 0.353 mol of each of EM-1 to EM-15. Then apart from this
103 g of yellow coupler (compound below) was dissolved in a mixture of 62 g of dioctyl phthalate and 150 ml of ethyl acetate by heating at 60 ° C, and the resulting solution was added to 60 g of gelatin and 5.1 g of sodium dodecylbenzenesulfonate at 40 ° C. Ten
In addition to 00 ml, the mixture was vigorously stirred and dispersed by a homogenizer, and the whole was made up to 1500 ml with water to prepare an emulsified dispersion liquid of the coupler. 0.118 mol of each of the chemically sensitized emulsions was mixed with 500 ml of the emulsified dispersion liquid of the coupler to prepare a hardener.
1,3,5-Trichloroyl-hexahydro-triazine 3
20 ml of a% methanol solution was added and then coated on polyethylene resin-coated paper. (Trials No. 1 to No. 6) Each of the above samples was exposed to blue light through an optical wedge, and then processed as described below, followed by measurement. [Processing step] [Temperature] [Time] Color development 30 ° C 6 minutes Stop 30 ° C 1 minute Fixing 30 ° C 2 minutes Water wash 30 ° C 2 minutes Bleach fixing 30 ° C 2 minutes Water wash 30 ° C 2 minutes (Color developer) Composition of anhydrous sodium carbonate 2.6 g anhydrous sodium bicarbonate 3.5 g potassium sulfite 18 g sodium chloride 0.2 g potassium bromide 1.3 g potassium hydroxide 0.4 g hydroxyamine sulfate 2 g 4-amino-methyl-N-ethyl-N- (β- Methanesulfonamidoethyl) -aniline 5g Add water to make (1. (pH 10.2) (stop solution) 2% acetic acid aqueous solution (fixer) ammonium thiosulfate 175.0g anhydrous sodium sulfite 8.6g sodium metasulfite 2.3g Add water to 1 and adjust to pH 6.0 with acetic acid. (Bleach-fixing solution) Ammonium thiosulfate 100g Potassium sulfite 5g Na [Fe (EDTA)] 40g EDTA 4g Add water to make 1. The sensitivity and fog of each of the obtained samples are as shown in Table 12. As seen in the table, No1, No4 to 7, No9 to 12, N according to the present invention
The o14 shows excellent performance with the fog maintained at a level of 1/2 or less, even though the sensitivity is 25 to 40% higher than the comparison samples No1 to 2, No8, No13, and No15.

【The invention's effect】

The present invention makes it possible to produce a monodisperse silver chlorobromide emulsion with extremely low fog and high sensitivity.

[Brief description of drawings]

1 to 17 are explanatory views schematically showing the crystal morphology to which the silver halide grains according to the present invention belong. 18 to 31 are electron micrographs of the silver halide grains of EM-1 to 15 described above. 1 ... (110) plane, 2 ... quasi (110) plane, 3 ... quasi (11
Ridge line of 0 plane, 4 …… (100) plane, 5 …… (111) plane.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-122935 (JP, A) JP-A-58-107530 (JP, A) JP-A-60-222842 (JP, A)

Claims (2)

[Claims] 1. A silver ion solution and a halide ion solution are mixed in the presence of a protective colloid, and halogenated with silver iodide of 2 mol% or less, silver chloride of 1 to 100 mol% and silver bromide of 99 mol% or less. In the method for producing a silver halide photographic emulsion for forming and growing silver halide grains having a silver composition, the silver ion solution is an ammoniacal silver nitrate solution, and the silver halide grains are formed and grown by the following general formula ( I), (II), (III) or (IV) in the presence of at least one compound selected from the compounds represented, characterized in that the (110) plane or (110) plane ridgeline To prepare a silver halide photographic emulsion comprising the silver halide crystal having the same. [Wherein R ₁ , R ₂ and R ₃ may be the same or different,
Hydrogen atom, halogen atom, hydroxyl group, amino group, amino group derivative, alkyl group, alkyl group derivative, aryl group, aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative, or -CONH-R ₄ (R ₄ is a hydrogen atom,
It represents an alkyl group, an amino group, a derivative of an alkyl group, a derivative of an amino group, a halogen atom, a cycloalkyl group, a derivative of a cycloalkyl group, an aryl group, or a derivative of an aryl group. ), R ₁ and R ₂ may combine with each other to form a ring. ] 2. The formation and growth of the silver halide grains has a pH
The method for producing a silver halide photographic emulsion according to claim 1, which is carried out in a liquid maintained at 10 or less.