JPS62106451A - Production of photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To produce uniformly a photographic silver halide emulsion having high sensitivity and superior shelf stability, causing little fog and undergoing little reduction in the sensitivity at a low cost by producing a photographic silver halide emulsion contg. silver iodide in a vessel having >=500l capacity with a stirrer having a flow controlling plate for ejecting flows in the vertical direction. CONSTITUTION:A flow controlling plate 2 is a plate extending radially from a shaft 5 as the center over the propeller 3 of a stirrer and generates axial flows 4 in the vertical direction. The capacity of a reaction tank 1 is preferably made as large as possible because a uniform product is produced at a reduced cost by increasing production per one batch. The lower limit of the capacity of the reaction tank 1 is 500l. In case of <500l capacity, the cost of production increases and the uniformity of a product deteriorates. The preferred capacity is 800-5,000l.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing a silver halide photographic emulsion.

[Background of the invention]

Currently, in order to obtain a silver halide photographic emulsion with high sensitivity, it is necessary to contain silver iodide. Silver iodide [;t! W
Compared to silver bromide and silver chloride, it has a lower solubility, a larger ionic radius, and a different crystal system, so it is difficult to create a mixed crystal with silver bromide and silver chloride as intended. There is. In particular, performance often deviates between the small scale design stage in the laboratory and the mass-produced scale V. In the process of industrially manufacturing silver halide photographic emulsions, the process is carried out in a human-sized reaction tank (and exactly as designed).
It is necessary to obtain a silver halogenide emulsion, and for this purpose efficient stirring is required.

When producing silver halide photographic emulsions in large quantities using a conventional simple propeller-type stirrer, the silver iodide It was found that this method is not suitable as a method for producing a silver halide photographic emulsion containing.

On the other hand, in order to industrially produce silver halide photographic emulsions, reduction of production costs and uniformity of products are required.
Increasing the capacity of the reaction tank and increasing the manufacturing cost per patch (the capacity of the reaction tank used for one reaction used in the patch system).

Therefore, it is desirable to use a large-capacity reaction tank to simultaneously satisfy the contradictory requirements of (17) improving stirring efficiency.

When the tank volume V of one hatch increases, the rotation speed of the stirrer increases to increase the stirring efficiency. With a stirrer, the circular motion component only increases significantly, but the stirring efficiency is low.

For this reason, if the production quantity per hatch increases, problems such as a decrease in 8J sensitivity occur with silver iodobromide emulsions containing silver iodide, for example. In other words, good emulsion sensitivity that can be obtained on a small scale such as in a laboratory may not be as good when mass-produced industrially. Furthermore, even if one attempts to obtain a monodisperse emulsion, there is a problem in that it becomes difficult to obtain an emulsion with good monodispersity.

In particular, with conventional stirrers, the capacity of the reaction tank per hatch is 5007! Sensitivity decreases and fit
Since the deterioration of dispersibility and fog (including fog over time) becomes more noticeable, it is necessary to industrially mass-produce a 1'l denatured photographic emulsion with a thickness exceeding 500p, and to reduce the deterioration of the repositioning performance. A manufacturing method that keeps the amount as low as possible is desired.

As a stirring technique, the technique disclosed in US Pat. No. 3,415,650 is known.

These techniques are a system in which the additive liquid is mixed by a stirring blade in a small Wl and combining chamber provided in the reaction tank, and is discharged into the reaction tank. However, the problems with these techniques are: 0) The concentration of added ions (ili! ions or halide ions, especially iodide ions) is unevenly distributed in the mixing chamber.

■Since the discharge from the mixing chamber is a swirling component, the flow within the tank becomes uneven.

These problems lead to deterioration of photographic performance, similar to the above.

In this way, in the conventional method for producing sofuzone described in 1-1, when producing a silver halide emulsion containing silver iodide in a large scale industrially, an emulsion with a weight of 11 has a volcanic dispersion property. There are problems in that the sensitivity is poor, fog increases, and the sensitivity decreases as the capacity increases.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems by making it possible to uniformly produce a silver halide photographic emulsion at a low cost, with high sensitivity, low fog, excellent storage stability, and little loss of sensitivity; An object of the present invention is to provide a method for producing a silver halide photographic emulsion having excellent monodispersity.

[Structure and operation of the invention]

The present invention adopts the following configuration in order to achieve the object described in -.

That is, in the method for producing a silver halide photographic emulsion of the present invention, a silver halide photographic emulsion containing silver iodide is stirred using a stirrer having a flow control plate that discharges a liquid stream in the vertical direction.
Manufactured in a container with a capacity of 500p or more.

The silver halide photographic emulsion of ijt C7 contains silver iodide and has high sensitivity. The silver halides present in this emulsion include AgBr1, ^gBrc j! T, etc. can be used. Silver iodide content is 0.5 mol% to 4
0 mol%, especially 1 mol% to 30 mol% is preferred.

The shapes of silver halide grains include irregular shapes such as disk-like and potato-like shapes, cubic, octahedral, dodecahedral, 14-hedral, etc.
Although there are regular shapes such as a spherical shape, the shape is not particularly important in the present invention. It is also possible to add heavy metal ions such as iridium ions, bismuth ions, talion ions, and rhodium ions to silver halide photographic emulsions.

Further, the silver halide photographic emulsion is preferably a monodisperse emulsion. Here, the monodisperse emulsion is one in which ----<0.20, where the average grain size of silver halide grains is 7 and the standard deviation value is σ. This average particle size -t can be measured directly from an electronic surface mirror photograph, by a -1 Luther counter, or by centrifugal particle size distribution measurement 7H using liquid phase sedimentation as a dead tree principle.

High sensitivity can be achieved by adding silver iodide to a silver halide photographic emulsion, but the silver iodide is An example of an aspect is the CC sea lion aspect.

When C,'distribution'4 is uniform throughout the silver halide grains, or within 0.79 times the rj diameter of the silver halide grains, the L contained in the entire grain (%1soI of silver If there is a special LL20 mol% I>), 1 station 7I is ``
In the case of silver 1genide photographic emulsions, the effects of the present invention, such as increased sensitivity, are noticeable.

Furthermore, in carrying out the present invention, silver iodide is added to the silver iodide photographic emulsion by a method of adding 2@ or more of the iodide ions to be used until the V2 foot of the silver ions to be used is added. If the mode of containing -u is adopted,
The effects of the present invention, such as increased sensitivity, can be further enhanced.

Next, the inventors produced the above-mentioned silver halide photographic emulsion using a stirrer (7) by enlarging the size of a conventional propeller-type stirrer or increasing the rotation speed. We investigated the improvement of efficiency, but found that the stirring efficiency did not improve as much in G1 as the circular motion component became larger.As a result of actually trying various types of stirrers with 1.17 shots, we found the following. We have found that the stirring efficiency is good when an axial flow is generated by a stirrer having the configuration described in .

The present invention employs a method of producing a silver halide photographic emulsion containing l-silver fertilization in a container having a capacity of 500 p or more using a stirrer having a ttNl tl plate that discharges a liquid stream in the vertical direction. Surprisingly, a silver halide emulsion with less low sensitivity and excellent storage fog can be obtained, and an extremely monodisperse part 11 emulsion can be obtained.

The present invention is based on a manufacturing method using such an apparatus, and the apparatus will be explained below with reference to the drawings.

1M is a cross-sectional view of the stirrer, and FIG. 2 is an enlarged cross-sectional view of the stirrer portion. In this specification, the liquid flow in the vertical direction is referred to as an axial flow, and is indicated by the reference numeral 4 in FIG. The flow control plate 2 that creates this axial flow 4 is, for example, as shown in FIGS.
This refers to a plate 2 that spreads out radially and generates an axial flow 4 as shown in FIG. If the axial flow 4 flows from top to bottom contrary to FIG. 1, the flow control plate 2 may be installed at the bottom. FIG. 3 is a view of the agitator of FIG. 2 viewed from above. The flow control plate 2 shown in FIG. 3 may be a flat plate or may be twisted.

Further, the flow control plate 2 is not limited to the structure described in -1-, but may be simply made by drilling a hole in the disk and attaching it to a part or bottom of the propeller.

Therefore, the flow control plate referred to herein may be anything that changes the swirling flow component in the vertical direction and generates the axial flow 4, and its shape and position are not particularly limited.

The shape of the reaction tank or mixing pot 1 may be a hemispherical bottom, a disc bottom, a conical bottom, etc., but there is no particular shape. Also, the material may be stainless steel, Teflon-coated glass lining, etc., but other materials may also be used.

It is desirable that the capacity of the reaction tank 1 be as large as possible because increasing the production amount per batch reduces production costs and makes the products uniform.

The lower limit of the reaction tank capacity is 500e, which is 5007! Below this, the production cost increases, the uniformity of the product deteriorates, and the effect of the present invention is also reduced. The preferred reaction tank capacity range in the present invention is 800p to 5000#.

Further, in this case, the discharge amount of the stirrer is preferably 500//min/yield-1-. The discharge amount is determined as follows.

Dynamic pressure P. was measured using a pressure transducer, manometer, etc.

As a result, the discharge amount (Q) is determined by the following formula: Q=S·[J (S: cross-sectional area, IJ: average flow velocity).

It is difficult to achieve the purpose of the present invention if the discharge rate of the stirrer is 500/min, but the upper limit is determined by the device itself based on the foamability, liquid splash, strip shape, gelatin concentration, etc.

Next, when a silver halide photographic emulsion is liquid-added, a so-called Con-1-roll double jet method using nuclei or seed crystals can be used.

Further, the internal structure of the silver halide grains used in the present invention can have a layered structure of two or more layers.

The silver halide photographic emulsion of the present invention produced by the method described above can be used, for example, in color photographs, X-ray films, motion picture films, and the like.

The silver halide photographic emulsion of the present invention can be chemically sensitized by a combination of reduction sensitization, sulfur sensitization, gold sensitization, etc., and can also be dye sensitized with a sensitizing dye.

It is also possible to use a mixture of several emulsions of the present invention.

The light-sensitive material using the emulsion of the present invention can be automatically developed by roller conveyance using a developer containing a hardening agent.

[Embodiments of the invention]

Example-1 The following solutions were prepared.

The reaction vessels are 50i, 3001, and 50 as shown in Figure 1.
0 β and 8001 were respectively produced. Solution A was placed in a pot and kept at 65°C, and the other solutions were added at 64°C.

At this time, liquids D and D were added by a controlled double jet method, and liquids C and R were successively added by a 1-control double jet method.

The relative size of the stirrer to the pot was as shown in FIG. 1, and was increased in proportion to the size of the pot. The stirrers include the stirrer used in the present invention shown in Figure 4 (stirrer-1), the stirrer shown in Figure 4 with the flow control plate 2 removed (stirrer-2), and the diameter of the propeller. is the fifth
A stirrer (stirrer-3) using the same conventional ship-type propeller as shown in the figure was prepared.

When adding silver ion liquid and halide ion liquid, p
Ag was adjusted to 8.3±0.05 using potassium bromide solution,
The pH was adjusted to pH=2.0+0.1 using sulfuric acid.

Using the solutions prepared as described above, silver halide photographic emulsions were produced using respective stirrers. The results are shown in Table-1.

As is clear from Table 1, when the capacity of the reaction vessel is 500β or less, the types of stirrer 1 (the present invention), stirrer 2 (without flow control plate), and stirrer 3 (conventional example) are used. , regardless of the size of the discharge amount, no significant difference in good overlap was found. In other words, if the reaction vessel is small, the materials can be sufficiently stirred, so the type of stirrer does not matter much.

However, as shown in Table 1, in large pots with a capacity exceeding 5,001 kg, it becomes difficult to stir the ingredients sufficiently, so the stirring efficiency depends on the type of stirrer (stirrer 1, 2.3). It can be seen that the difference in and the magnitude of the discharge amount have a large effect on the photographic performance (monodispersity in Example 1).

Therefore, the reaction pot capacity is 50n, 300#, 500ff.
, 8001, the stirrer of the present invention (stirrer 1
), a stirrer without a flow control plate (stirrer 2), and a conventional propeller type stirrer (stirrer 3) were used, and data were collected for each stirrer with three different discharge amounts. (Data was collected in the same manner for Example 2.3).

As a result, in the case of Example I, good monodispersity was exhibited even when the pot capacity exceeded 500 ff.
And the discharge amount is 5007! This is the case when the manufacturing method of the present invention is used in which the sample size exceeds 20.2 L/min (29.30 liters).

In addition, when the stirrer does not have a flow control plate (stirrer 2), even if the discharge rate exceeds 500 N/min, the monodispersity does not improve much (Sample N [L22-24, 31-33). This shows that the presence or absence of a flow restriction plate is one of the important factors that influences monodispersity.

As described above, the method for producing a silver halide photographic emulsion of the present invention can maintain good monodispersity even if a large amount of silver halide photographic emulsion is produced at one time, as in the case of small production. It can be made suitable for industrial production, which requires low cost and product uniformity.

Example-2 The following solutions were prepared.

In the case of Example=2, the strength of the solution is 11 in accordance with claim 2. For winter wear, first put liquid F in a pot, keep it warm at 60°C, and then add liquid G for 1 minute. 1
Add 1L down the throat, and after 1 minute add G solution and H solution simultaneously at a constant flow rate. Solution G was added over 15 minutes and solution H was added over 30 minutes. H
? 1 minute after the addition of & is complete, add 1+t+L for 15 seconds or 33 minutes after adding LC and then jail A.
,, Adjust the pH to 6 and move on to the next step. Add one drop of gelatin flocculant, decant, and add one drop of water seranaso.
111, pAg8.5 pHfi, (l emulsion to t
If.

As shown in Table-2) "Agitator and 111-manufactured 1jl
λ5 for J (forming chemical y1 at 1℃, each I [, cut the most I"I !I completed v1 for the time it took to i'g degree.

Stabilizers, antifoggants, chelating agents, and spreading agents were added to the resulting chemically ripened emulsion to give a silver content of 7 g/r+ (11
I applied Megumi. On the soil surface of the emulsion layer, apply a spreading agent, Mano 1 ~ Rule,
An antistatic agent was added to provide a protective layer.

The obtained sample was exposed to light using an optical wedge at 3.2 CMS, and was coated with Ne
w Using Xrl-90 (product name), the same company's 11X-4
Development processing was performed using a 00 automatic developing machine. Table 2 shows the relative sensitivity assuming that the sample sensitivity of test rice field 1 is 100.

In addition, the obtained sample was heated at a relative humidity of 50% and a temperature of 55°C for 3 hours.
The fogging temperature was measured after being left to stand between eyes and is shown in Table 2.

Table 2 As is clear from Table 2, regarding the sensitivity, fog 7 degree, and fog after heat treatment, the capacity of the reaction pot was 5007, similar to the grass dispersibility in Example 1! Below, there is not much difference depending on the type of stirrer and the size of the discharge amount, but when it exceeds 500e, the sensitivity decreases by 1
1-1, it can be seen that the fog density and the fog after heat treatment have increased. In addition, the presence or absence of a flow control plate also affects sensitivity and fog, as in the case of Example 1.

Therefore, by using the production method of the invention, even if silver halide photographic emulsions are produced in large quantities with a reaction pot capacity of 500e or more, the 111 dispersibility is good, there is little deterioration in sensitivity, and the storage stability is resistant to fog. Be able to do two things that are excellent.

Example-3 A solution of F was prepared.

．． 1 type H ice 11□ B l Ze ■+! deceased to M A.

(divide M) The details for the 5001 pot are shown here.

Add water and gelatin to the Na30 emulsion of Example-1 and make 2
40e, use the emulsion as a seed crystal at 9.7'
I used it. Liquid J and liquid M-1 containing the seed crystals are placed in a pot and kept at 40°C. Then, liquid and M-2, and subsequently liquid L and liquid M-3 were added by double jet method. At this time, when adding liquid M-2 and
=9.90. With an atmosphere of pAg = 7.35.

10 minutes after the addition of these two liquids was completed, the inside of the pot was adjusted to pH=9.0 using acetic acid and potassium bromide solution. pAg=
After setting the temperature to 8.9, add M-3 liquid and 14 liquid. At this time, pAg was kept constant and p)l was decreased to pl+=8.0 using acetic acid in proportion to the addition time. M-3
After the addition of liquid and liquid 7, N liquid was added, and 15 minutes later, acetic acid was added to adjust the pH to 6.0.

Then, add gelatin flocculant, decant, add gelatin solution, pH=6.0゜pAg-[,
56 silver halide photographic emulsions were obtained.

Table 3 was created based on these.

As shown in Table 3, various silver halide emulsion grains were obtained by changing the pot capacity and stirrer in the same manner as in Example 1.

Chemical sensitization was performed in the same manner as in Example 2, and a coated sample was also obtained. Then, a similar test was conducted.

Regarding Example 3, as in Examples 1 and 2, the capacity of the reaction vessel was 500! By using the manufacturing method of the present invention, even when the storage temperature exceeds 41jO'), it is possible to produce a silver halide photographic emulsion with good 0 dispersion + f+, less low sensitivity, less fog, and excellent storage 41jO').

〔Effect of the invention〕

As described above, according to the production method of the present invention, a silver halide photographic emulsion with high sensitivity, low fog, excellent storage stability, and little loss of sensitivity can be produced at low cost, and a halogenated emulsion with excellent monodispersity can be produced. It can be a silver photographic emulsion.

[Brief explanation of drawings]

1 is a cross-sectional view of the stirring device, FIG. 2 is an enlarged cross-sectional view of the stirrer portion, and FIG. 3 is a plane M in FIG. 2. 1... Reaction tank (or mixing pot), 2... Board, 3...
・Propeller, 4...axial flow. Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative patent attorney: Toru Takatsuki - 3 and Jt Neichi
〒F-TXF (voluntary) Showa fi January 9, 2019
F1 11I, i'1 Director General Li,', )II Akira
Ml (Shown 1, Width ('1 indication Showa 6041 Special Revision No. 246704 2, Title of the invention) Silver Genide copy 131, Emulsion manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent details, [Column Ei of Detailed Description of the Invention-1,) di
Contents of '+F' As shown in the attached sheet (1) 1 shot (1 foam 1 INl and 11 foam [゛・
J Ro. (2) Ibid No. 13 Tei No. 1! Ni l' 1111-2.
0 10.1” [pH-2.0 above 0. I, -1a
: + City 1E-J Ru. (3) I'llX-400- on page 19, line 17 of the same book
Correct as 1+1-shi×-400-1. (4) Manufacture stirrers and drawers for use in the same book, No. 2411, line 19 and 2 (Nj. Hypo of I, F, A clasp M,
! : Add the liquid of cyanoacetic acid anseniuno, 56°
[゛-e version? ;J ripening, and the maximum sensitivity of each emulsion is C
J Otsu time only matured 1 again. Stabilizer, anti-cazoli II was added to the resulting emulsion after chemically adjusting to pH 7.
- Add punishment, chelating agent, spreading agent, 71! A silver star was applied to both sides of the polyethylene lid in an amount of 7 H/m. A spreading agent, a matting agent, and an antistatic agent were added to the first side of the emulsion Y to provide a protective layer. The obtained sample was 3.2 CMS and optically heated.
Using New XD-90 (trade name) manufactured by Nijo Co., Ltd., which was exposed and contained a hardening agent, VX-
Development processing was performed using a 400 automatic processor. Table 2 shows the relative sensitivity with the sample sensitivity of sample floor 1 set as 100. Further, after the obtained sample was left at a relative humidity of 50% and a temperature of 55° C. for 3 days, the fog density was measured and shown in Table 2. "I" ni

Claims (1)

[Claims] 1. A silver halide photographic emulsion containing silver iodide is produced using a stirrer having a flow control plate that discharges a liquid stream in the vertical direction;
A method for producing a silver halide photographic emulsion, characterized in that it is produced in a container having a capacity of 0.00 liters or more. 2. 1/1 of the silver ion used in silver halide photographic emulsion
Silver halide according to claim 1, characterized in that silver iodide is contained by a method of adding 1/2 or more of the amount of iodide ion used until 2 amounts are added. Method for producing photographic emulsion.