JPS62138844A - Device for producing silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To fabricate a device for producing a photographic emulsion with high reproducibility by providing feeding or adding pots contg. silver ion solns. having different concns. to form a silver ion soln. feeding or adding system and by connecting the pots to flow rate detectors so that only one of the solns. passes through one of the detectors. CONSTITUTION:Feeding or adding pots 3, 4 contg. silver ion solns. having different concns. are provided to form a silver ion soln. feeding or adding system and the pots 3, 4 are connected to flow rate detectors 10, 11 so that only one of the solns. passes through one of the detectors. Aqueous silver salt solns. may be used as the solns. in the pots without any special restriction but aqueous silver nitrate solns. or ammoniacal silver nitrate solns. are generally used. The span of the amount of each of the solns. added is large, addition accuracy and stability are satisfactory and a high degree of freedom is ensured when a photographic emulsion is produced.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an apparatus for producing a silver halide photographic emulsion, and more specifically, it relates to a production apparatus for a silver halide photographic emulsion with a large addition amount span and high addition precision. It is related to the device.

[Background of the Invention] Photographic silver halide emulsions (hereinafter referred to as photographic emulsions) are
It is produced by mixing a silver ion salt solution and a silver ion solution in the presence of gelatin.

The silver halide contained as a result of mixing the above solutions is determined by the type and concentration of the halide salt to be mixed, the concentration of the silver ion solution, the presence or absence of ammonia and its addition, the mixing method, the mixing speed, the coexisting substances, It is greatly affected by reaction temperature, time series, etc.
This will ultimately affect the photographic properties.

In recent years, particularly monodisperse emulsions, which have a narrow particle size molecule n (n), have been produced, and stricter conditions in the emulsion production process are required.

By the way, when functional addition is carried out in the production of photographic emulsions, the amount of reactants added must be increased as silver halide grains grow. Roughly speaking, the addition W span (ratio of minimum addition R to maximum addition amount) is required to be large in order to grow from small particles to large particles.

The amount added is expressed by the following relationship.

Addition amount [moi/min] - Solution concentration [mo, 2/
42]×solution addition flow rate [ffi/min] Therefore, in order to increase the addition amount, either increase the solution concentration, increase the solution addition flow, or increase both the solution concentration and the solution addition flow 0. There are three ways to do this.

An example of the conventional solution C thinning method is disclosed in Japanese Patent Application Laid-Open No. 55-15812.
It is disclosed in No. 4. Although this is an excellent technique as it allows for a wide addition amount span, it has the following problems.

First, in order to change the concentration, if the diluent is added after the inside of the dilution pot is in a completely mixed state, a delay in control will occur. To avoid this, if the ingredients are added without complete mixing, the accuracy of addition will deteriorate. Furthermore, if the dilution pot is made smaller in order to achieve both control delay and addition accuracy, the addition amount span becomes smaller.

Second, the amount added cannot be reduced arbitrarily.

In other words, when changing the growth environment of silver halide crystals (for example, the ammonia concentration in the reaction pot, the concentration of ions, the composition of halogen ions in α, etc.), the rate of crystal formation changes; Depending on the situation, it may be necessary to reduce the amount added. However, this method reduces the added G only at the end. Therefore, when attempting to obtain silver halide crystals with arbitrary structures or crystal habits, there is a difficulty in the degree of freedom.

In addition, U.S. Patent No. 4,242,445 discloses a method to increase the degree of freedom by controlling the amount of addition by adding a flow meter, but this method does not solve the second problem mentioned above. However, the first problem remains unresolved.

[Object of the Invention] In view of the above-mentioned conventional problems, the present invention has a large addition amount span, good addition accuracy and addition stability, and has a large degree of freedom in producing photographic emulsions, and improves reproducibility. It is an object of the present invention to provide an apparatus for producing a high-quality photographic emulsion.

[Structure of the Invention] In order to achieve the above object, the present invention provides a supply and addition system for a silver ion solution and a halide ion solution, each of which includes at least a supply and addition tank for each of the ion solutions, a flow rate detector, and an addition line that connects these. In an apparatus for producing a silver halide photographic emulsion in which the silver ion solution and the halide ion solution are simultaneously added while maintaining a predetermined silver ion concentration, at least the silver ion solution supply addition system has a concentration of the addition solution, respectively. having at least two different feed addition vessels, and one flow rate detector having one of said addition solutions;
Each feed addition tank is connected to a flow detector so that only the type of flow passes through.

In the present invention, the addition solution in the silver ion solution supply addition pot is not particularly limited as long as it is an aqueous solution of silver salt, but generally an aqueous silver nitrate solution, an ammoniacal aqueous silver nitrate solution, or the like is used.

As the flow rate detector used in the present invention, a highly accurate electromagnetic flow meter is particularly preferable. The electrodes of this electromagnetic flowmeter may be made of platinum-iridium, tantalum, zirconium, stainless steel, or the like.

Silver halide photography according to the present invention? The apparatus for producing the L agent is particularly effective in producing monodisperse emulsions. The present invention is also effective in producing silver halide photographic emulsions containing silver halide grains whose crystal habits are controlled, such as octahedral grains, tetradecahedral grains, and cubic lattice grains. Further, the present invention can be used to produce a silver halide photographic emulsion containing silver halide grains such as silver chloride, silver bromide, silver iodide, and mixed crystals thereof, but in particular, in the production of mixed crystals, the ratio of the It can be freely controlled within the range that allows production of mixed crystals. Furthermore, the present invention provides an emulsion (
For example, emulsions doped with rhodium, iridium, etc.)
It can also be used in the production of

[Examples] Specific examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

Iil! An aqueous solution of silver I acid solution was assembled as shown in FIG. In the figure, reference numerals 1 to 8 are supply and addition vessels filled with an aqueous silver nitrate solution, 9 to 17 are electromagnetic flowmeters, and 18 to 26 are needle valves, which are used to adjust the flow M.

27 to 34 are on/off valves for the supply addition tank, 35 to 44 are three-way valves used for flow path switching, 45 to 48 are addition lines connecting the above, and 49 to 52 are for reacting silver ions and halide ions. It is a reaction vessel.

Each of the feed addition pots 1 to 8 is a glass-lined 2001 pot made by Nippon Glass. Of these, pot 1.3 is a 0.2N silver nitrate aqueous solution, pots 2.4 and 6.8 are 1, ON, pot 5.7
A 0.04 N silver nitrate aqueous solution was added.

9 to 17 are Yamatake Honeywell electromagnetic current C meters NNM-110
It is a type. A platinum-iridium alloy was used as the material for each flowmeter electrode and ground ring. 9 of these
．． 10.11.12.14゜16 electromagnetic flowmeter has a diameter of 6
mm, 13.15°17 electromagnetic flowmeter has a diameter of 10mm
It was used.

An electromagnetic flowmeter with a diameter of 6n+m has a flow rate of 1.6 at a flow rate of 1m/sec.
9 Q/min, 1Qm/see 16.9
The flow rate is p/min. Electromagnetic current fHf with a diameter of 10 mm
is 4.721/min at a flow rate of 1 m/sec, 1
0n+/sec is 47.2 (17 min flow rate).

In this example, the electric currents of 6 mm in diameter are 11
It is used at a flow rate of 852/min to 852/min, and the electromagnetic flowmeter with a diameter of 1Q mm is used at a flow rate of 8.5 m/min to 42.5 m/min.
．． (Used at a flow rate of /min.

Flow control valves 18 to 26 used Fujikin zirconium needle valves. 27-34 on-off valves, 35-44
The three-way valve is 4 to 3F Teflon I, IJ, and 45.
The addition line No. 8 was made of 4.6-fluoride Teflon lining.

Figure 1 (a) shows how the 0.2N silver nitrate solution in pot 1 is heated to fJ.
J m': A total of 9, 1.7.2/m1n-8
, 5ffi/1n. The corresponding molar addition rate of silver ions is 0.34 moi/min ~+,
70 mob/min.

1.7 (For addition rates exceeding 1+o/min, add 1.ON silver nitrate solution in pot 2 to 30,000 valve 35,
If led to electric ln flowmeter 9, 171/min ~ 8.5
．． As the molar addition rate corresponding to a metering of 9/1n, 1
．． 70moffi/iin ~8.5mo, g/m
in is (q). The addition span corresponding to this case is 0.34 moffi/min ~ 8, 5mo fl /
min, 1:25.

Next, the figure (b) corresponding to the present invention shows that when 0.2N silver nitrate in the pot 3 is introduced into the electromagnetic flowmeter 10, the molar addition rate is 0.34.
mop/min to 1.70 moi/min was obtained, and 1.70 moi/min of pot 4 was obtained. When ON silver nitrate is led to the electromagnetic current R meter 11, the flow rate is 1.70 moffi/min ~ 8.5 moj
! /min is obtained, and the addition span 1:2 is the same as in (a).
It becomes 5. .

Next, in the same figure (C), the 0.04N silver nitrate solution in pot 5 is
leading to the electromagnetic flowmeter 12, 1.7. (/min~8.52
7 min to 114i1. The corresponding molar addition rate of silver ions is 0.068 moi/min ~0.
34 mop/min, and the electromagnetic flow meter 1
3 is used, 0.34 mofi/min ~1.7
moi/min If you use the electromagnetic flow meter 12 from pot 6, it will be 1.7 mo fl/min ~ 8.5 mo! l
/min, 8 if using electromagnetic flowmeter 13 from pot 6
．． 5 moi/min to 42.5 moi/min can be obtained. The addition span corresponding to this case is 0.068
mo9. /min ~42.5moi /min, 1
: 625.

Next, in the same figure (d) corresponding to the present invention, an electromagnetic flowmeter 14 is connected from the pot 7, an electromagnetic flowmeter 15 is connected to the pot 7, an electromagnetic flowmeter 16 is connected to the pot 8, and an electric current meter 17 is connected to the pot 8. By using the same addition span as (C), 0.068mo
Q/min to 42.5 moQ/min is obtained.

The flow (1) was controlled by needle valves 18 to 26, forming a feedback loop for adjusting the valve opening in response to a signal from an electromagnetic flowmeter.

Before starting the experiment, the reproducibility accuracy of each of 9 to 17 electromagnetic flowmeters was confirmed. 9.10.11゜12.14.1
In No. 6, a 1N nitrate radical aqueous solution was flowed for 10 minutes at a flow rate of 5 liters/min. The spilled liquid is in a container.

1 mountain was determined in advance, and the river was
The density measured using a direction meter MODEL-0M61 was used to convert from rice m to six boats. All experimental atmospheres are 2.
The temperature was adjusted to 5°C. Same (0 on the hill.
The experiment was also carried out using a 04N silver nitrate solution.

The flow meter on 13.15.17 was run in the same manner for 6 minutes at a flow rate of 25ffi/min. Measurements were repeated three times with different concentrations of the silver nitrate aqueous solution for each flowmeter, and the deviations from the theoretical values calculated from the density are shown in Table 1.

As is clear from Table 1, the fluctuation range is ±1 for both 1N and 0.04N silver nitrate aqueous solutions.
Within %. Therefore, when a flow n meter of No. 9 to 17 is used alone, it is considered that the reproducibility accuracy within ±1% is maintained even when measuring an aqueous silver nitrate solution.

Next, silver halide grains were actually produced using the apparatus shown in FIG.

Example 1 The apparatus shown in FIG. 1(b) is used for the silver ion addition system and the halide ion addition system to assemble the production apparatus according to the present invention as shown in FIG. was manufactured.

Solution A (in pot 50) Ossein gelatin 0.500'kg Distilled water 50.000ffi Solution B
(Inside pot 3') Ossein gelatin 0.340kg
Potassium bromide 2.018k (1 with distilled water 85.000 ffi Finishing solution C (in pot 4') Ossein gelatin 0.68k (1 potassium bromide 20.18k with Q distilled water)
170.00 i Finishing solution D (in pot 3) Silver nitrate 2.890 kg with distilled water as, oool Finishing solution E (in pot 4) li0 acid silver 28.90 k (+
With distilled water 170.00 i Finishing pot 5
While stirring the solution A in 0.0 at 60 DEG C., a Toa Denpa-Rei 1) H electrode and a silver ion electrode were immersed in the solution A according to the method described in JP-A-57-197534. Then 11H and pAg of solution A
The pAq and pH were adjusted to 3.0 and 2.0 using a silver nitrate solution and a 1N nitrification solution, respectively.

1) While controlling the flow rate of solutions B and D to maintain the pH value of
and D were added. Solution B was added from pot 3' through flow meter 10', and solution D was added from pot 3 through flow meter 10.

Solutions B and D were each heated at 2.5 i/m for 6 minutes from the start of addition.
Add at an addition rate of 0.1 l/ff1 for the next 20 minutes.
The addition was terminated at 4.5 l/...in. After 4 minutes, the valves 36 and 36' are switched and the valves 30 and 30' are opened, and solutions C and E are added at 0.00%, respectively.
Addition was started at a flow rate of 9i/min, with a final flow rate of 2.5i/min.
The speed was increased to 5i/min.

The time required for addition was 100 minutes, and a total amount of 170 ml was added.

When this emulsion was examined using an electron microscope (1°0.0
) was a monodisperse emulsion with a crystal habit of Table 2 shows the results of examining the grain size and distribution of the emulsion using a CAP A 500 grain size distribution analyzer manufactured by Horiba, Ltd.

Table 2 shows the results of repeating the above silver halide grain production five times.

The distribution (%) is expressed as standard deviation/average particle size) x 100.

Comparative Example 1 A manufacturing apparatus was assembled as shown in FIG. 3 using the apparatus shown in FIG. 1(a) for the silver ion addition system and the halogen ion addition system.

Solutions A, B, C, and D were prepared in the same manner as in Example-1.

Adjust E and hooks 49.1' and 2' respectively.

1.2, at the same temperature as in Example-1, 1) A+
J, silver halide grains were prepared with a similar addition pattern while maintaining the pH value. The particle size and distribution were examined in the same manner as in Example 1, and the results are shown in Table 2.

Table 2 From the results shown in Table 2, it can be seen that the production apparatus of the present invention has excellent dosing accuracy and stability, and therefore has excellent reproducibility of the average particle size and distribution of silver halide grains to be packaged. ing.

Example 2 Using the apparatus shown in FIG. 1(d) for the silver ion addition system and the halide ion addition system, a manufacturing apparatus according to the present invention was assembled as shown in FIG. 4, and silver halide grains were manufactured.

Solution A (in pot 52) Ossein gelatin O, 5ooka distilled water 50. OOO [Polyisopropyleneoxy-polyethyleneoxy ester sodium salt 10% ethanol solution 0.150p solution B (
(in pot 7') Ossein gelatin 0.782 kg Potassium iodide 0.5192 kg Potassium bromide 0.5583 k (] With distilled water
195.50 i Finishing solution C (in pot 8') Ossein gelatin 0.800 kg Potassium iodo 5.312 kg Potassium bromide 5.712 kg With distilled water
200.00 more (raise solution D (in pot 7) Silver nitrate 1.329 klJ with distilled water 195.50 Q Finishing solution E (in pot 8) Silver nitrate 13.6 kg with distilled water 200.002 Solution A in finishing pot 52 l) H and ρΔ as in Example-1 while stirring at 60°C.
Using q measurement, 1Nli'I at pH = 2.0 and pAa = 3.0, respectively. 1 silent solution and a silver nitrate aqueous solution. So that pAg and I)H maintain this value,
Solutions B and D were placed in the pot 52 while controlling the flow rates, and B and D were added using a double jet method. Solution B was passed through the flowmeters in pots 7' to 14', and the solution was passed through the flowmeters in pots 7 to 14 for the first 5 minutes at an addition rate of 8.5.97ml.
・Added at a constant rate. Immediately after that, add solutions B and D for 40' each.
.

42', 40. Switch the 3-way valve of 42 to flow ■Total 15'
, 15 into the pot 52 by the double jet method.

The flow rates ranged from 8.5 p/min to 0.0 p/min, respectively.
71 i and added for 12 minutes.

The total amount added was 195.5.9 for both B and D.

Then, 4 minutes later, solutions C and E were added. Solutions C, E
were added in the same manner using the double jet method, but the flow rate was increased from 1.7 i/min to a final 3.3 ffi/min. The time required for the addition was 80 minutes. The addition series numbers were 2002 for both C and E. The flow meter is 16
', 16 was used. When the emulsion was examined using an electron microscope, it was found to be a monodisperse emulsion with a crystal habit of (1,1,1).

The above process of producing silver halide grains was repeated five times to produce an example
Table 3 shows the results of examining the average particle size and distribution using the same method as in 1.
Shown below.

Comparative Example 2 A manufacturing apparatus was assembled as shown in FIG. 5 using the apparatus shown in FIG. 1(C) for the silver ion addition system and the halogen ion addition system. Solutions A, B, C, D, E were prepared in the same manner as in Example-2.
were prepared, respectively, and the pots 51.5', 6', and 5.
It was introduced in '6.

pl-1 and pAg were adjusted in the same manner as in Example-2, and solutions B and D were added by the double jet method while maintaining them.

Solution B was led from the pot 5' to the flow meter 12' and added into the pot 51. For the melt aD, a flow meter 12 was used from the pot 5. The flow rate and time are the same as in Example-2. Immediately after that, solution B
1D each 38'.

39', 38. Switch the 3-way valve of 39 to flow total 13.
', 13 into the pot 51 by the double jet method. The flow rate was increased at a rate of 0.71 i/min from 8.5 i/min, and the flow rate was 1/min as in Example-2.
Added for 2 minutes.

Then, after 4 minutes, add 37' of solutions C and E, respectively.

The three-way valves 38', 39', and 37, 38, and 39 were cut open, and addition was made in the same manner as in Example 2 using flowmeters 12 and 12'.

The above production of silver halide grains was repeated five times, and the average grain size and distribution were examined in the same manner as in Example-1. The results are shown in Table-3.

From the results shown in Table 3, the production apparatus of the present invention can produce silver halide grains with excellent average grain size and distribution reproducibility.

[Brief explanation of drawings]

"II(a), (C), FIG. 3, and FIG. 5 are block diagrams showing comparative examples, and FIG. 1(b), (d), FIG. 2, and FIG. It is a configuration diagram showing an example. 1.2.3, 4.5.6.7.8... Supply addition pot, 9
．． 10.11.12.13, 14.15゜16.17・
...Electromagnetic flowmeter, 18.19.20.21, 22, 23.24°25.2
6... Needle valve, 27.28.29.30.31, 32.33°34...
・Opening/closing valve, 35.36.37.38.39.40,41°42.4
3.44...3-way valve,

Claims (1)

[Claims] Each of the supply and addition systems for the silver ion solution and the halide ion solution has at least a supply and addition tank for each of the ion solutions, a flow rate detector, and an addition line that connects these, and the silver ion solution is supplied to the silver ion solution while maintaining a predetermined silver ion concentration. In an apparatus for producing a silver halide photographic emulsion in which a solution and the halide ion solution are simultaneously added, at least the silver ion solution supply addition system includes at least two additive solutions each having a different concentration.
The silver halide silver halide is characterized in that the silver halide has two supply addition vessels, and each supply addition vessel and the flow rate detector are connected so that only one type of the additive solution passes through one flow rate detector. Photographic emulsion manufacturing equipment.