JP3496971B2 - Production method of silver halide emulsion - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide emulsion, and more particularly to a method for suppressing defoaming in a grain forming step and / or a desalting step in the step.

[0002]

2. Description of the Related Art Conventionally, when a silver halide emulsion is produced, it is remarkably foamed by stirring, moving or transferring a liquid in a grain forming step and a desalting step. Bubbles in the grain forming step cause non-uniformity in the vicinity of the liquid surface, which facilitates the formation of coarse grains called so-called coles grains and the formation of silver halide grains covered in a region where the silver ion concentration is extremely high. Bubbles in the desalting process contain a large amount of silver halide and go out of the system, which reduces the amount of raw materials. Further, the foaming phenomenon is a significant obstacle in terms of manufacturing efficiency. For example, in the particle forming step, when the production scale is increased, it is necessary to carry out high agitation in order to eliminate non-uniformity in the container. However, when the stirring rotation speed is increased, air is entrained on the liquid surface and foaming occurs. In particular, when the rotation speed is high, foaming becomes remarkable, and the foam overflows from the container together with the raw material. Furthermore, bubbles generated once in any of the steps are difficult to disappear, and it is necessary to leave the emulsion for a long time before transferring to the next step. As described above, not only is there a hindrance to the improvement of efficiency, but the manufacturing facility also needs a capacity corresponding to the amount of foam generated, which results in a large scale and is uneconomical. There is a defoaming technique as a method for solving the above-mentioned problems, and there are two methods, physical mechanical defoaming and chemical defoaming, in terms of implementation. Regarding physical mechanical defoaming due to the foaming mechanism described above, axial flow type agitators require a structure that suppresses horizontal rotational flow, while radial flow type agitators require liquid on the side of the reaction vessel. A structure that suppresses the rise of the flow is necessary. Thus, in physical mechanical defoaming, it is necessary to consider the structure depending on the type of agitator. For example, the conventional physical mechanical defoaming technology for an axial flow type agitator is disclosed in Japanese Patent Publication No. 57-92524 and Japanese Utility Model Publication No. 62-16183.
Japanese Patent Laid-Open Publication No. 2003-242242 proposes a method in which a horizontally fixed flow control plate is provided above the stirrer to convert a horizontal rotary flow into a vertical direct current to prevent V cut. Further, the conventional physical mechanical defoaming technology of the radial flow type agitator has a dimple structure or projections in which a large number of dimples or projections are aligned on at least a part of the inner wall of the reaction vessel or at least a part of the inner space of the reaction vessel. A reaction vessel with a structure has been proposed. All of the conventional methods of physical mechanical defoaming have an excellent defoaming effect from the aspect of action, but are not good at defoaming effect (shortening the disappearance time of bubbles) when stirring is stopped. Such inferior foam-breaking effect is a problem because it deteriorates production stability and efficiency. In chemical defoaming using an antifoaming agent, many things are conventionally known in various industries, and generally, for example, silicone emulsions, sorbitan fatty acid esters, higher alcohols, animal and vegetable oils, mineral oils such as paraffin, etc. , Polyoxyalkylene glycol derivatives and the like. For example, “Practice of Mixing Technology” edited by Technical Information Association (198
(9 years) It is described collectively in P121. The following defoaming agents are used in the method of producing silver halide emulsion grains. U.S. Pat. No. 5,147,771, European Patent 513723A, U.S. Pat. No. 5,147,772, and U.S. Pat. No. 5,147,73 show that a good monodisperse emulsion can be obtained by using a polyethylene oxide block copolymer. A polymer having a propylene oxide (PO) content of 80% or more is effective as an antifoaming agent. Regarding Pluronic (manufactured by BASF), for example, 31R1, 25R2, 17R2, L
101, L61, etc., and also Tetronic (BA
For SF), 1301, 901, 130R
1, 110R1 and so on. Also, Japanese Examined Japanese Patent Publication No.44-949
7, JP-B-44-26580, JP-A-59-18864
0, JP-A-59-189339, JP-A-62-2311
No. 246, for example, polypropylene oxide (PPO) and polyethylene oxide (P
It is a copolymer of EO) that defines the PPO content and includes water-soluble alkaline earth metal compounds and lower alcohols. In addition, the copolymers of PPO and acrylamide described in Japanese Patent Application No. 5-191814 and Japanese Patent Application No. 5-263128,
A polymer having a PO content of 70% or more, or a mixture of a PPO-only side chain polymer and a PEO-only side chain polymer having a PPO content of 70% or more is also effective as an antifoaming agent. Further, a silicon compound such as a silicon-based polymer having a side chain of polyalkylene oxide described in Japanese Patent Application No. Hei 5-221274 is also excellent in defoaming effect. The following precautions are generally required when using the above defoaming agent. Since many antifoaming agents usually have a small HLB value, that is, many have a high content of lipophilic groups, it is desirable to use a detergent for cleaning the reaction vessel, the stirrer and the like. Alcohols such as 2-ethylhexyl alcohol and octyl alcohol have a defoaming effect immediately after addition, but do not last long, and the defoaming effect is not good compared to the amount added. In addition, it is difficult to process the evaporated alcohol in a light-sensitive material factory which often operates in a closed room. Moreover, it is inferior in the foam suppressing effect.
The silicone compound has an excellent defoaming effect, but when an emulsion is coated on a support, it may cause a trouble called cissing and deteriorate the quality, so that sufficient caution is required.
The alkylene oxide type may impair the photographic characteristics of the silver halide photographic emulsion, so the amount used should be careful. In particular, the defoaming of a surfactant having a large HLB requires a usage amount about 10 times or more that of the defoaming of gelatin or the like. In such a case, for example, the adsorption of the sensitizer is affected,
It has a considerable effect on photographic performance such as sensitivity and fog. Pluronics also affect particle formation depending on the conditions. For example, when Pluronic TM31R1 is used for forming silver iodobromide tabular grains, the tabular thickness is increased and the aspect ratio is lowered. Further, when the silver potential is low, the silver is adsorbed on the (100) plane and the growth is hindered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to produce a large amount of silver halide emulsions with high sensitivity and low fog.

[0004]

The object of the present invention is to provide an inner diameter of 4
A flat plate with an average aspect ratio of 3 or more in a container of 0 cm or more
In producing a silver halide emulsion of grains, the HLB value is from 1 to 7 from the time when 50% of the total amount of silver nitrate added in the grain formation step is added to the time when the desalting step is finished.
It was achieved by a method for producing a silver halide emulsion characterized by adding the polyalkylene oxides of.

The present invention will be described in detail below. HLB of the present invention
The value refers to Griffin's HLB value (J. Soc. Cosm
etic Chem. 5 (1954) 294).
Further, the polyalkylene oxides of the present invention include alkylene oxides (ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide,
1,2-butylene oxide) and a copolymer structure of two or more kinds of monomers. Specific examples of the polyalkylene oxides having an HLB value of 1 to 7 used in the present invention will be given, but the present invention is not limited thereto. In addition, n shows the polymerization degree of polyalkylene oxide. -Polyoxyethylene glycer monooleate (n = 2 to
6) ・ Polyoxyethylene nonyl phenyl ether (n = 2
~ 6) ・ Polyoxyethylene oleyl ether (n = 2-6) ・ Polyoxyethylene sorbitol fatty acid ester (n
= 2 to 6) -Polypropylene oxide / polyethylene oxide / propylene oxide copolymer (ethylene oxide content 5 to 25% by weight) Preferably, polyethylene oxide / propylene oxide copolymer (ethylene oxide content 5 to 25% by weight) And more preferably a polyethylene oxide / propylene oxide block copolymer. In addition, a particularly preferable structure is represented by the general formula (I).

[0006]

[Chemical 2]

In the formula, X and Y represent the average degree of polymerization. Here, X and Y are preferably those having an average molecular weight of 1200 or more and an ethylene oxide content of 5% by weight or more and 25% by weight or less, and an average molecular weight of 2000 or more and 5000 or less,
A value that gives an ethylene oxide content of 8% by weight or more and 22% by weight or less is particularly preferable. The polyalkylene oxide of the present invention may be added at any time between the time when 50% of the total amount of silver nitrate added in the grain forming step is added and the time when the desalting step is completed, and preferably the total silver nitrate is added. This is from the time when 70% of the added amount is added to immediately before the stirring is stopped in the desalting step. The polyalkylene oxide of the present invention may be added as a solution of a solvent such as alcohol or as a dispersion in water or a gelatin solution, but it is preferably added as a solution. The addition amount of the polyalkylene oxide of the present invention preferably satisfies the formula A-1.
In the formula, p is the amount of polyalkylene oxide added (g)
And R represents the inner diameter (m) of the container. Here, the inner diameter is the equivalent circle diameter of the container cross section. Formula A-1 1 ≦ p / R 3 <80 Further, more preferably satisfies the formula A-2. Formula A-2 2 ≦ p / R ³ ≦ 25

The silver halide that can be used in the silver halide emulsion may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide, but it contains iodine. The amount is preferably 1% or less per mol of silver. The silver iodide distribution may be a high internal concentration or an external high concentration, but an external high concentration is preferable, and a surface high concentration is more preferable. Japanese Patent Application No. 5-12 describes a method for measuring the silver iodide content distribution of silver halide grains.
7328, ISS (slow ion scattering spectroscopy) described in WO92 / 10785, and the like. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together. Further, if necessary, chemical sensitization can be performed.

The majority of silver halide grains that can be used in the silver halide emulsion must be tabular. As the proportion of tabular grains contained,
The projected area of silver halide grains contained in the emulsion layer is 50% or more, preferably 70% or more. The aspect ratio of a tabular grain is given by the ratio of the diameter of a circle having an area equal to the projected area of each tabular grain and the grain thickness of each tabular grain. In the present invention, 50% or more of particles having an aspect ratio of 3 or more must be present, and 50% or more of particles having an aspect ratio of 4 or more are preferable. Also, the average value of the aspect ratio is 3
It is at least 20 and preferably at least 4 and less than 10. Furthermore, the average particle thickness is preferably 0.3 μm or less, and particularly preferably 0.2 μm or less. Tabular silver halide emulsions are disclosed in JP-A-58-127927 and JP-A-58-113.
It can be easily prepared by referring to the methods described in JP-A No. 927 and JP-A-58-113928. In addition, pBr1.
In an atmosphere of a relatively low pBr value of 3 or less, tabular grains form seed crystals in which 40% or more by weight are present, and the pBr of the same level is obtained.
It is obtained by growing seed crystals while simultaneously adding silver and a halogen solution while maintaining the value. In this growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of tabular silver halide grains can be controlled by controlling the temperature, selecting the type and amount of solvent,
It can be adjusted by controlling the addition rates of the silver salt and halide used during grain growth.

The emulsion layer of the present invention contains 1.
It is preferable to contain a thiocyanic acid compound in an amount of 0 × 10 ⁻³ mol or more and less than 2.0 × 10 ⁻² mol. The thiocyanate compound may be added in any process of grain formation, physical ripening, grain growth, chemical sensitization and coating, but addition before chemical sensitization is preferable. As the thiocyanic acid compound used during the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as a metal thiocyanate or an ammonium salt can be generally used, but in the case of a metal salt, the photographic performance is adversely affected. Care should be taken to use metal elements that do not exceed the range, with potassium and sodium salts being preferred. Also, Ag
A sparingly soluble salt such as SCN may be added in the form of fine particles. In this case, the size of the AgSCN fine particles is preferably 0.2 μm or less in diameter, and particularly preferably 0.05 μm or less.

The silver halide emulsion used in the present invention can be chemically sensitized. Examples of chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization with complex salts and polyamines, gold sensitization with gold compounds, iridium, platinum, rhodium, palladium, etc. Known methods such as metal sensitization can be used. These may be used in combination as necessary.
In particular, a compound which is adsorbed on silver halide by a sulfur sensitization method using a sulfur-containing compound, a selenium sensitization method using a selenium-containing compound, or a tellurium sensitization method using a tellurium-containing compound, alone or in combination of two or more kinds. Is preferably carried out in the presence of The compound adsorbing to silver halide as used herein means a class of spectral sensitizing dyes or photographic stabilizers, and is disclosed in JP-A-63 / 1988.
The compounds disclosed in JP-A-305343 and JP-A-1-77047 can be used.

The silver halide emulsion used in the present invention is preferably spectrally sensitized. The type of sensitizing dye can be appropriately selected depending on the intended exposure and the like. For example, an ortho-sensitizing dye is preferable for X-ray photography using an ortho-sensitizing screen. The sensitizing dye may be added in any step of the production of the light-sensitive material, but it is preferable to add the chemical sensitizer.

The apparatus for producing the emulsion of the present invention has an inner diameter of 40
It is a container of cm or more, preferably 60 cm or more and 6 m or less, and more preferably 80 cm or more and 4 m or less. If the inner diameter is small, the container becomes deep and the stirring efficiency decreases. Here, the inner diameter is the equivalent circle diameter of the container cross section. The cross-sectional shape is preferably circular. The capacity of the emulsion producing apparatus of the present invention is preferably 30 liters or more, more preferably 40 liters or more and less than 10,000 liters. The stirring method in the emulsion grain forming step of the present invention is not particularly limited,
JP-B-55-10545 and JP-A-2-275023
The stirring device described in Japanese Patent Publication No. 49-48964 is preferably used. Further, as a stirring method in the desalting step, stirring by a torsion spring or jet stirring is preferably used.

Various additives and the like used in the photographic light-sensitive material using the silver halide emulsion of the present invention are not particularly limited in addition to those described above, and for example, those described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and method for producing the same JP-A-2-68539, page 8, lower right column, line 6 to page 10, upper right column, line 12, line 3-24537 Page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, left upper column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggant, Stabilizer JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; Tokukaihei 3-94249, page 6, lower left column, line 15 to 11 Top right column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactants and antistatic agents JP-A-2-68539, page 11, upper left column, line 14 to page 12, upper left column, line 9 7) Matting agent, slipping agent, plasticizer JP-A-2-68539, page 12, upper left column, line 10 to same upper right column, line 10, page 14 lower left column 10 line to same lower right column, line 1. 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 9) Hardener JP-A-2-68539, page 12, upper right column, line 17 to page 13, upper right column, line 6 10) Support, JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover cut method JP-A-2-264944, page 4, upper right column, line 20 to page 14, upper right column. 12) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9. No. 3-24539, page 14, lower left column, to page 16, lower right column. 13) Polyhydroxybenzenes JP-A-3-39948, page 11, upper left column to page 12, lower left column, EP Patent No. 452772A. 14) Layer structure JP-A-3-198041. 15) Development method From JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 10, upper right column, line 10 16) Anti-agglomeration agent Described in Japanese Patent Application No. 5-204325 and Japanese Patent Application No. 5-27 3810.

The photographic light-sensitive material using the silver halide emulsion of the present invention is not particularly limited. Preferably used in a system for irradiating a subject such as a human body such as an X-ray film for direct photography, an X-ray film for indirect photography, a CRT film, etc. with X-rays, and converting the X-rays passing through the subject into visible light for exposure. To be Examples thereof include medical or industrial X-ray photographic materials, X-ray dupe photographic materials, medical CRT image photographic materials, and the like.

[0016]

【Example】

Example 1 (Preparation of emulsion) Water in a container having an inner diameter shown in Table 1 and a circular cross section
400 g of gelatin and 275 g of potassium bromide per liter
To the aqueous solution maintained at 63 ° C., an aqueous solution containing 98 g of silver nitrate and an aqueous solution containing 140 g of potassium bromide were added in 37 seconds by the double jet method while stirring by the method described in JP-B-55-10545. Subsequently, an aqueous solution containing 742 g of gelatin was added, and then an aqueous solution containing 352 g of silver nitrate was added to 20
The temperature was raised to 70 ° C. while adding over a period of minutes. In addition, 25
% Aqueous ammonia solution (320 ml) was added, and 10 minutes later, an aqueous solution containing 383 g of acetic acid was added. Subsequently, an aqueous solution of 5952 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the potential at pAg of 8.8. The flow rate at this time was accelerated so that the flow rate at the end of addition was 5 times the flow rate at the start of addition. After the addition was completed, 2N potassium thiocyanate solution was added to 272
0 ml was added. After that, the liquid was transferred to a container having an inner diameter of Table 1 and a circular cross section, and an aqueous solution containing 60 g of polyfumaric acid was added,
The temperature was lowered to 35 ° C., the pH was lowered to 3.9 with sulfuric acid, and soluble salts were removed by the coagulation sedimentation method. Further, water was added, the pH was adjusted to 4.1 with sulfuric acid, and the mixture was sufficiently stirred and the same operation was repeated twice. A methanol solution containing compound F-1 and polyethylene oxide (molecular weight 2000) was added as shown in Table 1, and jet stirring was used as the stirring method. After this,
The temperature was raised to 40 ° C., 1300 g of gelatin, 64 g of phenoxyethanol, and sodium polystyrene sulfonate were added, and pH was adjusted to 5.9 and pAg to 7.8 with caustic soda, potassium bromide, and a silver nitrate aqueous solution. The temperature was raised to 56 ° C., 1.3 g of sodium ethylthiosulfonate was added, and then 1.5 g of thiourea dioxide was added, and 4-hydroxy-6-methyl-1,3,3a, 7-
1 g of tetrazaindene, 16 g of compound F-2 and 60 mg of compound F-3 were added. Sodium chloride 2 after 5 minutes
After adding 5 g and 4.3 g of potassium iodide, 3 g of potassium thiocyanate, 0.6 g of chloroauric acid, and 6 of compound F-4 were added.
3 mg and 53 mg of sodium thiosulfate were added, and the mixture was aged for 40 minutes. Then, 1.3 g of compound F-5 was added and rapidly solidified to obtain emulsions F-A-1 to 10. Obtained Emulsion Obtained Emulsions F-A-1, 2, 5-8, 99% of the total projected area of all grains were composed of grains having an aspect ratio of 3 or more, and the average projected area diameter of all grains was Was 1.18 μm standard deviation 15%, the average thickness was 0.19 μm, and the average aspect ratio was 6.2. In F-A-3 and 4, 99% of the total projected area of all particles is composed of particles having an aspect ratio of 3 or more, the average projected area diameter of all particles is 1.16 μm standard deviation 10%, and the average thickness is Is 0.20
μm, the average aspect ratio is 6.2, and FA
-9 and 10 were particles containing 50% or more of the projected area of tabular grains having an aspect ratio of 5 or more, but mixed with many fine particles.

[0017]

[Chemical 3]

In a container shown in Table 1, 240 g of gelatin and 265 g of potassium bromide in 40 liters of water kept at 40 ° C. in an aqueous solution containing 153 g of silver nitrate and 226 g of potassium bromide were mixed by a double jet method.
Added in 7 seconds. Subsequently, after adding an aqueous solution containing 723 g of gelatin, the temperature was raised to 70 ° C. while adding an aqueous solution containing 377 g of silver nitrate over 20 minutes. Further, 200 ml of 25% aqueous ammonia solution was added, and after 10 minutes, 21
An aqueous solution containing 1 g acetic acid was added. Continued silver nitrate 5
An aqueous solution of 838 g and an aqueous solution of potassium bromide was added at a potential of p
While maintaining Ag 8.8, it was added in 35 minutes by the control double jet method. The flow rate at this time was accelerated so that the flow rate at the end of addition was 5 times the flow rate at the start of addition.
After the addition was completed, 2720 ml of 2N potassium thiocyanate solution was added.
Was added. Then, the solution was transferred to the container shown in Table 1, an aqueous solution containing 60 g of polyfumaric acid was added, the temperature was lowered to 35 ° C., the pH was lowered to 3.7 with sulfuric acid, and soluble salts were removed by the coagulation sedimentation method. Further, water was added, the pH was adjusted to 4.1 with sulfuric acid, and the mixture was sufficiently stirred and the same operation was repeated twice. Compound F-1,
A methanol solution containing polyethylene oxide (molecular weight 2000) was added as shown in Table 1. Thereafter, the temperature was raised to 40 ° C., 1300 g of gelatin, 64 g of phenoxyethanol, and sodium polystyrene sulfonate were added, and pH was adjusted to 5.9 and pAg to 7.8 with caustic soda, potassium bromide, and a silver nitrate aqueous solution. Temperature 56
The temperature was raised to ℃ and 1.3 g of sodium ethylthiosulfonate was added, then 1 g of thiourea dioxide was added, 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and compound F were added. -2g of 17 was added. After 5 minutes, 21 g of sodium chloride and 5.6 g of potassium iodide were added, and then 3 g of potassium thiocyanate, 0.8 g of chloroauric acid, 63 mg of compound F-4 and 106 mg of sodium thiosulfate were added, followed by aging for 60 minutes. Then, 1 g of compound F-5 was added and rapidly solidified to obtain emulsions F-B-1 to 10. The resulting emulsions F-B-1, 2, 5 to 8 consisted of grains having an aspect ratio of 3 or more in 93% of the total projected area of all grains, and the average projected area diameter of all grains was 0.83 μm. The standard deviation was 17%, the average thickness was 0.14 μm, and the average aspect ratio was 6.1. In FB-3 and 4, 90% of the total projected area of all particles is composed of particles having an aspect ratio of 3 or more, the average projected area diameter of all particles is 0.80 μm standard deviation 14%, and the average thickness is Is 0.14
μm, the average aspect ratio is 6.1, and FB
-9 and 10 were tabular grains having an aspect ratio of 3 or more in a projected area of 60% or more, but mixed with many fine particles. The stirring was performed in the same manner as in the preparation of F-A-1 to 10.

[0019]

[Table 1]

(Preparation of Dye Dispersion L) Compound F-6, dicyclohexyl phthalate, and 2.5 g of 2,4-diamylphenol each dissolved in 50 cc of ethyl acetate were dissolved in 1.5 g of sodium dodecylbenzenesulfonate and p- 90 g of an 8% gelatin aqueous solution containing 0.18 g of methyl hydroxybenzoate was mixed at 60 ° C., and the mixture was stirred at high speed with a homogenizer. After completion of high-speed stirring, a reduced pressure treatment was performed at 60 ° C. using an evaporator to remove 92 wt% of ethyl acetate. This gives a dye dispersion L having an average particle size of 0.18 μm.
Got

[0021]

[Chemical 4]

(Preparation of first layer emulsion coating solution) Emulsion F- above
The following chemicals were added to a mixture of 500 g each of A-1 and FB-1 and water was added to make 2368 cc to obtain a coating liquid 1. Coating solutions 2 to 10 were prepared in the same manner using the emulsions F-A-2 to 10 and F-B-2 to 10. Gelatin 78 g Dye dispersion L 37 g Potassium iodide 175 mg Compound F-7 4 mg Compound F-8 34 mg Compound F-9 105 mg Compound F-5 73 mg Dextran 12 g Hydroquinone monosulfonic acid 14 g Sodium polystyrene sulfonate sodium 1.6 g

[0023]

[Chemical 5]

(Preparation of Second Layer Emulsion Coating Solution) To 1 kg of the above emulsions F-A-1 to 10 were added the following chemicals, and water was added to add 2
The coating liquid was 1 to 10 with 368 cc. Gelatin 77 g Compound F-7 4 mg Compound F-8 17 mg Compound F-9 105 mg Compound F-5 36 mg Dextran 12 g Hydroquinone monosulfonic acid 14 g Sodium polystyrene sulfonate 1.6 g 1,2-bis (vinylsulfonylacetamide) ethane 1.6 g

(Preparation of Coating Solution for Surface Protective Layer) The following chemicals were added to 100 g of gelatin and water was added to 1245 cc to prepare a coating solution. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 7.2 g Compound F-10 51 mg Compound F-11 126 mg Compound F-5 256 mg Compound F-12 3.7 g Compound F-7 190 mg Compound F-13 2.5 g Compound F-14 0.2 g Sodium polystyrene sulfonate 0.6 g Caustic soda 0.3 g Sodium acetate 4 g Sodium ascorbate 0.2 g

[0026]

[Chemical 6]

(Preparation of coating sample) JP-A-62-1150
Prepared by have been prepared method described in No. 35, subjected to a primer coat in advance emulsion coating side, compound on the back surface side F-15 60mg / m ² Diacetyl cellulose 143 mg / m ² of silicon oxide 5 mg / m ²

[0028]

[Chemical 7]

The emulsion layer coating solutions 1 to 10 and the surface protective layer coating solution were combined and coated on a blue triacetyl cellulose support coated with. At this time, the coating amount of each layer was as follows. First emulsion layer coating liquid 16 cc / m ² Second emulsion layer coating liquid 46 cc / m ² Surface protective layer coating liquid 19 cc / m ² Thus, coating samples 1 to 10 were prepared, and 25 ° C. 60
After storing at% RH for 1 month, the following evaluation was performed.

(Sensitometry) Visible light used in the measurement of a sensitive material has a maximum transmittance of 60% and a λma of a tungsten light source.
The light centered at 545 nm was passed through a filter having characteristics of x545 nm and a transmitted light half value width of 13 nm. Through an optical wedge, expose for 1/20 seconds, and use a CEPROS-30 automatic developing machine manufactured by Fuji Photo Film Co., Ltd. to develop solution C.
Washing water temperature 20 using E-D30 and fixer CE-F30
SP treatment was performed at ° C. With respect to the sensitivity, the sample 1 was used as a reference (100), and the ratio of the exposure amount giving a density of 1.0 in addition to the fog was shown by the reciprocal. The results are shown in Table 2. High sense in the area of the present invention
It can be seen that the cover is low and the Dmax is high. The high Dmax is due to the disappearance of silver halide grains that escape with bubbles in the washing step.

[0031]

[Table 2]

Example 2 (Preparation of emulsion) 40 liters of water, 280 g of potassium bromide, average molecular weight 1 in a container having an inner diameter of 60 cm and a circular cross section and a depth of 80 cm.
320 g of low molecular weight gelatin of 55,000 and 10 mg of anti-aggregation agent mixture were added, and while stirring, 1440 cc of silver nitrate aqueous solution 1440 cc (silver nitrate 160 g) and potassium bromide 236 g aqueous solution 1520 cc were mixed in a container kept at 55 ° C. For 37 seconds. Next, gelatin 744
After adding an aqueous solution containing 3 g, a silver nitrate aqueous solution of 3560 cc
(Silver nitrate 392g) is added over a period of 22 minutes at 68 ° C.
The temperature was raised to. Here, 280cc of 25% aqueous ammonia solution
Was added and physically aged for 10 minutes at the same temperature,
260 cc of 100% nitric acid solution was added. Subsequently, an aqueous solution of 6120 g of silver nitrate and an aqueous solution of potassium bromide were added to p
While maintaining Ag of 8.5, the mixture was added over 35 minutes by the control double jet method. The flow rate at this time was accelerated so that the flow rate at the end of addition was 14 times the flow rate at the start of addition. After the addition was completed, add 2N potassium thiocyanate solution to 2
100 cc was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the average projected area diameter is 1.10 μm and the thickness is 0.170 μm.
8.5% monodisperse pure silver bromide tabular grains were obtained. After this,
As shown in Table 3, each compound was methanol / water (1/1)
It was added as a solvent solution, and soluble salts were removed by a coagulation sedimentation method in a container having an inner diameter of 80 cm. The temperature was raised to 40 ° C. again, and 1400 g of gelatin, 94 g of phenoxyethanol and 32 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 5.90 and pAg 8.00 with caustic soda, potassium bromide and an aqueous silver nitrate solution. This emulsion was chemically sensitized by adding the following chemicals per 1 mol of Ag while maintaining the temperature at 54 ° C. with stirring. First, sodium ethylthiosulfonate 1 × 10 ^-5 mol was added, followed by addition 1.5 mmol AgI fine diameter 0.07 .mu.m, further added thiourea dioxide 0.043 mg, as it is held for 22 minutes Then, reduction sensitization was performed. Next, 4-hydroxy-6-methyl-1,3,3a, 7-
20 mg of tetraazaindene and 400 mg and 4.0 mg of compounds A-1 and 2 were added, respectively. Further, 0.83 g of calcium chloride was added. Then sodium thiosulfate 1.
3 mg and compound A-3 2.1 mg, chloroauric acid 2.5 mg, and potassium thiocyanate 0.9 mg were added, and 40 minutes later, it cooled to 35 degreeC. Thus, the preparation of Emulsions 11 to 14 was completed. The stirring method was the same as in Example 1.

[0033]

[Chemical 8]

(Preparation of Emulsion Coating Layer) Emulsion coating solutions 11 to 1 were prepared by adding the following chemicals to 1 mole of silver halide to chemically sensitized emulsions 11 to 14 .
It was set to 4 .

[0035]

[Chemical 9]

Dye emulsion a was added to the above coating solution such that compound A-9 was 10 mg / m ² per side.

[0037]

[Chemical 10]

(Preparation of Dye Emulsion a) Compound A-9
Of 60 g and 2,4-diamylphenol of 62.8
g, 62.8 g of dicyclohexyl phthalate and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecylbenzene sulfonate, 94 g of gelatin, 581 cc of water and 28 mg of a flocculation inhibitor mixture were added and emulsified and dispersed at 60 ° C. for 30 minutes by a dissolver. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of methyl p-hydroxybenzoate was added to give a dye emulsion a. (Preparation of Surface Protective Layer Coating Solution) The surface protective layer coating solution was prepared so that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.025 ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 0.0012 ・ Polymethyl methacrylate (average particle size 3.7 μm) 072-Compound A-10 0.018-Compound A-11 0.037-Compound A-12 0.0068-Compound A-13 0.0032-Compound A-14 0.0012-Compound A-15 0.0022- Proxel 0.0010 (pH adjusted to 6.8 with NaOH)

[0039]

[Chemical 11]

(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer Compound A-17 shown below was ball milled by the method described in JP-A-63-197943.

[0041]

[Chemical 12]

Water 434 cc and Triton X200
(Registered trademark) surfactant (TX-200 (registered trademark))
And 791 cc of a 6.7% aqueous solution of the above were placed in a 2 liter ball mill. 20 g of dye were added to this solution. 400 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter) were added and the contents were milled for 4 days. After this, 160 g of 12.5% gelatin and 1.5 g of anti-agglomeration mixture were added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the crushed dye had a wide range of particle diameters from 0.05 to 1.15 μm, and the average particle diameter was 0.37 μm. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion d was obtained.

(2) Preparation of support Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the first undercoating liquid having the following composition was applied at an amount of 4.9 cc / m ^2. Thus, it was applied by a wire converter and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the compound A-9.
・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158cc ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc ・ Distilled water 801cc * in latex solution Contains 0.4 wt% of A-18 as an emulsifying dispersant with respect to the latex solid content.

[0044]

[Chemical 13]

(3) Coating of undercoat layer On each of the above-mentioned first undercoat layers, a second undercoat layer having the following composition is applied on each side so that the coating amount is as described below. 155 ℃ by wire bar coder method
It was applied and dried. -Gelatin 80 mg / m ² -Dye dispersion B (as dye solid content) 8 -Compound A-19 1.8 -Compound A-16 0.27 -Mat agent Polymethylmethacrylate 2.5 with an average particle size of 2.5 μm

[0046]

[Chemical 14]

(Preparation of photographic material) The above emulsion layers 11 to 14 were formed on the support prepared as described above.
And a surface protective layer were combined and coated on both sides by the simultaneous extrusion method to obtain samples 11 to 14 . The coated silver amount per one side was 1.75 g / m ² .

(Evaluation of Photographic Performance) The photographic material was exposed for 0.05 seconds from both sides using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. After exposure,
Sensitivity was evaluated by TP processing using a developing solution CE-D30 and a fixing solution CE-F30 with CEPROS-30 manufactured by Fuji Photo Film Co., Ltd. The sensitivity was represented by the reciprocal of the ratio of the exposure dose that gives a density of 1.0 in addition to the fog, based on Sample 1. The results are shown in Table 3. It can be seen that high feeling, low fog, and high Dmax are obtained in the region of the present invention.

[0049]

[Table 3]

Front page continuation (56) Reference JP 62-235937 (JP, A) JP 62-231246 (JP, A) JP 60-201333 (JP, A) JP 5-173268 (JP , A) Ryohei Oda, Kazuhiro Teranuma, Synthesis of surfactants and their applications, Japan, Maki Shoten, March 20, 1957, 494 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/015 G03C 1/035 G03C 1/043 G03C 1/06

Claims (2)

(57) [Claims] 1. A container having an inner diameter of 40 cm or more is used to measure the average asperity.
To produce tabular grain silver halide emulsions with a cut ratio of 3 or more .
On the other hand , a halogen characterized in that polyalkylene oxides having an HLB value of 1 to 7 are added from the time when 50% of the total amount of silver nitrate added in the grain forming step is added to the time when the desalting step is completed. Method for producing silver halide emulsion. 2. The method for producing a silver halide emulsion according to claim 1, wherein the polyalkylene oxide is a compound represented by formula (I). [Chemical 1] In the formula, X and Y represent the average degree of polymerization, and the average molecular weight is 12
00 or more, ethylene oxide content of 5 wt% or more 25
It is a combination of values that are less than or equal to wt%.