JP2002355541A - Stirring apparatus and method of preparing silver halide photographic emulsion using this stirring apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stirring apparatus with which a high-speed rotation of stirrer blades is made possible, the processing speed for mixing is easily improved and further, the wear of the stirrer blades and vessel walls and heat generation are prevented to improve the quality of mixing, and a method of preparing a silver halide photographic emulsion by using the stirring apparatus. SOLUTION: In the stirring apparatus and the method of preparing the silver halide photographic emulsion by using the stirring apparatus, since a pair of built-in magnet type stirrer blades which are freely rotatably held around supporting shafts implanted into the inside surfaces of the respective vessel walls hermetically sealing the top and bottom ends of the stirring vessels by means of magnetical couplings with external magnets rotationally driven by means of motors disposed on the outside of the vessels and are disposed to face each other separately within the stirring vessel are driven to rotate reverse from each other while the solutions to be mixed are admitted into the stirring vessels from respective inflow ports and the mixed solutions are discharged from discharge ports, thereby the respective solutions in the stirring vessels are mixed, even if the respective stirrer blades are rotated at a high speed, the axial centers of rotation of the respective stirrer blades are not biased and the attachment and detachment of the magnetical couplings can be prevented.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、溶液の攪拌、混合
の連続処理に適した攪拌装置及び攪拌方法に関するもの
で、詳しくは高速反応系における処理速度を向上させる
急速均一混合及び急速排出により処理品質を向上させる
ための改良に関するものである。更に、、本発明は前記
攪拌装置を用いたハロゲン化銀写真乳剤の製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stirrer and a stirrer method suitable for continuous processing of solution stirring and mixing. More specifically, the present invention relates to rapid uniform mixing and rapid discharge for improving the processing speed in a high-speed reaction system. It relates to improvements for improving quality. Furthermore, the present invention relates to a method for producing a silver halide photographic emulsion using the above-mentioned stirring device.

【０００２】[0002]

【従来の技術】図３は、溶液を槽内に流入させながら連
続的に攪拌、混合が可能な従来の攪拌装置の要部を示す
縦断面図である。ここに示した攪拌装置は、特開平１０
−４３５７０号公報に開示された略円筒状の攪拌槽１８
と該攪拌槽１８内で磁気的カップリングで回転駆動され
る一対の攪拌翼２１，２２とそれらを槽外から駆動する
外部モーター２８，２９とを具備して成っていた。前記
攪拌槽１８は、混合すべき溶液を槽内に流入させる流入
口１１，１２，１３が胴部１９の下方側面に配設される
と共に、混合処理済みの混合液を槽外に排出させる排出
口１６が胴部上方側面に配設された 略密閉型の槽であ
る。2. Description of the Related Art FIG. 3 is a longitudinal sectional view showing a main part of a conventional stirring device capable of continuously stirring and mixing while flowing a solution into a tank. The stirrer shown here is disclosed in
-Catalyst Stirring Tank 18 disclosed in JP-A-43570
And a pair of stirring blades 21 and 22 that are driven to rotate by magnetic coupling in the stirring tank 18 and external motors 28 and 29 that drive them from outside the tank. The agitation tank 18 has inflow ports 11, 12, 13 through which a solution to be mixed flows into the tank, and is disposed on a lower side surface of the body portion 19, and discharges the mixed liquid after the mixing to the outside of the tank. The outlet 16 is a substantially closed type tank provided on the upper side surface of the body.

【０００３】また、前記一対の攪拌翼２１，２２は、密
閉された前記攪拌槽内で離間して対向し且つ互いに同一
方向に回転するように、前記攪拌槽１８外に配設された
前記外部モーター２８，２９で回転駆動される外部磁石
２６と磁気的にカップリングされている。このような構
成によって、前記各流入口１１，１２，１３から前記攪
拌槽１８内に流入した前記各溶液は、前記各攪拌翼２
１，２２の回転により攪拌作用を受けた後、前記排出口
１６から槽外に排出されるので連続処理が可能であっ
た。[0003] The pair of stirring blades 21 and 22 are arranged outside the stirring tank 18 so as to be opposed to each other in the closed stirring tank and rotate in the same direction as each other. It is magnetically coupled to an external magnet 26 that is rotationally driven by motors 28 and 29. With such a configuration, the respective solutions flowing into the stirring tank 18 from the respective inlets 11, 12, and 13 are separated from the respective stirring blades 2.
After being subjected to the stirring action by the rotation of the rotations 1 and 22, the mixture is discharged from the discharge port 16 to the outside of the tank, so that continuous processing was possible.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、前記従
来装置は、急速攪拌のために駆動モーターの回転速度を
高めると、前記各攪拌翼２１，２２の回転軸芯が偏倚し
て偏心振動を起こし、磁気的なカップリングの離脱を誘
発し、攪拌不能となり易かった。その結果、陽暦の混合
処理品質の低下を招き、混合処理速度の向上が困難にな
る難点があった。また、攪拌槽器壁２０と前記各攪拌翼
２１，２２が摺接するため、前記器壁２０と前記各攪拌
翼２１，２２との接触面が磨耗すると共に、大きな摩擦
熱も発生して混合処理品質の低下させていた。However, in the conventional apparatus, when the rotation speed of the drive motor is increased for rapid stirring, the rotation axes of the stirring blades 21 and 22 are deviated to cause eccentric vibration. The magnetic coupling was detached, and it was easy to stir. As a result, there is a problem that the mixing process quality in the Chinese calendar is deteriorated, and it is difficult to improve the mixing process speed. Further, since the agitating vessel wall 20 and the agitating blades 21 and 22 are in sliding contact with each other, the contact surfaces between the agitating vessel wall 20 and the agitating blades 21 and 22 are worn, and a large amount of frictional heat is generated, thereby causing a mixing process. The quality had been reduced.

【０００５】本発明は、上述した従来技術の問題点を解
消し、攪拌翼の高速回転を可能にし、混合処理速度を容
易に向上させ、更に攪拌翼と器壁との磨耗、発熱を防止
して混合品質の向上を図ることが可能な攪拌装置及び前
記攪拌装置を用いたハロゲン化銀写真乳剤の製造方法を
提供することを目的とするものである。The present invention solves the above-mentioned problems of the prior art, enables high-speed rotation of the stirring blade, easily improves the mixing processing speed, and prevents wear and heat generation between the stirring blade and the vessel wall. It is an object of the present invention to provide a stirrer capable of improving the mixing quality by using a stirrer and a method for producing a silver halide photographic emulsion using the stirrer.

【０００６】[0006]

【課題を解決するための手段】本発明のかかる目的は、
攪拌対象の液体を流入させる所定の液供給口と瞬時攪拌
処理を終えた混合液体を瞬時に排出する液排出口とを備
えた攪拌槽と、該攪拌槽内で回転駆動されることで該攪
拌槽内の液体を瞬時混合する手段とを備えて成る攪拌装
置であって、前記攪拌手段として、密閉された攪拌槽内
に相対向する二個所に離間して配置されて互いに逆向き
に回転駆動される一対の攪拌翼を装備したことを特徴と
した攪拌装置において、各攪拌翼は、磁石を内蔵し、回
転軸を備えたプレートの回転軸にボールベアリングを介
して結合され、槽壁の外側に配置された外部磁石と磁気
カップリングを構成し、それぞれの外部磁石を槽外に配
備されたモータで回転駆動することで各攪拌翼が回転操
作されることを特徴とする攪拌装置によって達成され
る。SUMMARY OF THE INVENTION The object of the present invention is as follows.
A stirring tank having a predetermined liquid supply port through which a liquid to be stirred is introduced, and a liquid discharge port that instantaneously discharges the mixed liquid that has been subjected to the instant stirring process; and the stirring is performed by being rotationally driven in the stirring tank. And a means for instantly mixing the liquid in the tank, wherein the stirring means is disposed at two opposing locations in a closed stirring tank and is rotationally driven in opposite directions. The stirring device is equipped with a pair of stirring blades, each stirring blade has a built-in magnet, is coupled to the rotation axis of a plate having a rotation axis via a ball bearing, outside the tank wall. This is achieved by a stirrer characterized by comprising a magnetic coupling with an external magnet arranged in the apparatus, and each stirring blade is rotated by rotating each external magnet with a motor arranged outside the tank. You.

【０００７】更に、本発明のかかる目的は、攪拌対象の
液体の平均滞留時間ｔが、０．０５〜５．００秒である
ことを特徴とする攪拌装置によって達成される。ここ
で、ｔは次式で定義される。 ｔ＝Ｖｍ／(ΣＱｉ) Ｖｍ ；攪拌有効容量 [ｃｃ] ΣＱｉ；流入溶液の総流量 [ｃｃ／ｓｅｃ]。Further, the above object of the present invention is achieved by a stirring apparatus characterized in that the average residence time t of the liquid to be stirred is 0.05 to 5.00 seconds. Here, t is defined by the following equation. t = Vm / (ΣQi) Vm; effective stirring capacity [cc] ΣQi; total flow rate of inflow solution [cc / sec].

【０００８】更に、本発明のかかる目的は、攪拌対象の
液体の流入口通過時の平均流速ｕが、２０〜２００ｃｍ
／ｓｅｃであることを特徴とする攪拌装置によって達成
される。ここで、ｕは次式で定義される。 ｕ＝４Ｑ／πφ² Ｑ；溶液の流量 [ｃｃ／ｓｅｃ] φ；流入口の口径 [ｃｍ]Further, the object of the present invention is that the average flow velocity u of the liquid to be stirred when passing through the inlet is 20 to 200 cm.
/ Sec. Here, u is defined by the following equation. u = 4Q / πφ ² Q; flow rate of solution [cc / sec] φ; diameter of inlet [cm]

【０００９】更に、本発明のかかる目的は、攪拌翼径と
攪拌槽内径の比ｄ／Ｄが０．７０〜０．９０であること
を特徴とする攪拌装置によって達成される。 ｄ；攪拌翼径 [ｃｍ] Ｄ；攪拌槽内径 [ｃｍ]Further, the above object of the present invention is achieved by a stirring apparatus characterized in that the ratio d / D of the diameter of the stirring blade to the inside diameter of the stirring tank is 0.70 to 0.90. d: stirring blade diameter [cm] D: stirring tank inner diameter [cm]

【００１０】更に、本発明のかかる目的は、攪拌翼の回
転によって攪拌槽内壁との間に生じる剪断力τが１００
０ｓｅｃ^-1以上であることを特徴とする攪拌装置によっ
て達成される。ここで、τは次式で定義される。 τ＝πｄＮ／σ ｄ；攪拌翼径 [ｃｍ] Ｎ；攪拌回転数 [ｒｐｓ] σ＝（Ｄ−ｄ）／２ [ｃｍ][0010] Further, the object of the present invention is that the rotation of the stirring blade causes a shearing force τ generated between the stirring tank and the inner wall of the stirring tank to be 100%.
This is achieved by a stirring device characterized by being at least 0 sec ^-1 . Here, τ is defined by the following equation. τ = πdN / σ d; stirring blade diameter [cm] N; stirring rotation speed [rps] σ = (D−d) / 2 [cm]

【００１１】更に、本発明のかかる目的は、前記攪拌装
置を用いたハロゲン化銀写真乳剤の製造方法によって達
成される。Further, the object of the present invention is achieved by a method for producing a silver halide photographic emulsion using the above-mentioned stirring device.

【００１２】[0012]

【作用】本発明の攪拌装置及び前記攪拌装置を用いたハ
ロゲン化銀写真乳剤の製造方法は、混合すべき溶液を各
流入口から攪拌槽内に流入しながら排出口から混合溶液
を排出する間に、槽外に配設されたモータを介して回転
駆動される外部磁石との磁気的なカップリングによっ
て、前記攪拌槽の上下端部を密封する各器壁内面に植設
された支軸を中心に回転自在に保持され且つ前記攪拌槽
内で離間して対設した一対の磁石内蔵型攪拌翼を互いに
逆向きに回転するように駆動させて前記攪拌槽内の各溶
液を混合した後、該混合液を排出口から前記攪拌槽外に
排出する場合、前記混合すべき溶液の前記各流入口通過
時の平均流速ｕを２０〜２００ｃｍ／ｓｅｃ、前記攪拌
翼径と前記攪拌槽内径の比ｄ／Ｄを０．７０〜０．９
０、前記攪拌翼の回転によって前記攪拌槽内壁との間に
生じる剪断力τを１０００ｓｅｃ ^-1以上、前記混合すべ
き溶液の平均滞留時間ｔを０．０５〜５．００秒として
混合処理するので、前記各攪拌翼を高速回転させても前
記支軸によって前記各攪拌翼の回転軸芯が偏倚せず、磁
気的なカップリングの離脱が阻止される。The stirrer according to the present invention and the c using the stirrer
The method for producing a silver halide photographic emulsion is as follows.
While flowing into the stirring tank from the inlet, the mixed solution from the outlet
While discharging, is rotated via a motor arranged outside the tank.
Magnetic coupling with an external magnet driven
And planted on the inner surface of each vessel wall to seal the upper and lower ends of the stirring tank
The stirring tank is held rotatably about a supported spindle.
A pair of built-in magnet type stirring blades that are spaced apart from each other
Driving in the opposite direction to rotate each solution in the stirring tank
After mixing the liquid, the mixed liquid was discharged from the outlet through the stirring tank.
When discharging, the solution to be mixed passes through each of the inlets
When the average flow velocity u is 20 to 200 cm / sec, the stirring is performed.
The ratio d / D of the blade diameter to the inner diameter of the stirring tank is 0.70 to 0.9.
0, between the inner wall of the stirring tank and the rotation of the stirring blade
Generated shear force τ is 1000 seconds ^-1All of the above
The average residence time t of the solution is 0.05 to 5.00 seconds.
Since the mixing process is performed, even if each of the stirring blades is rotated at a high speed,
The rotation axis of each stirring blade is not deviated by the support shaft,
Disengagement of the coupling is prevented.

【００１３】更に、本発明の拌装置及び前記攪拌装置を
用いたハロゲン化銀写真乳剤の製造方法は、槽内に対設
された前記一対の攪拌翼がそれぞれ向きの異なる高速攪
拌流を形成するので、槽内に高速乱流を発生させて急速
混合を可能にする。Further, in the stirring apparatus of the present invention and the method for producing a silver halide photographic emulsion using the stirring apparatus, the pair of stirring blades provided in the tank form high-speed stirring flows having different directions. Therefore, high-speed turbulence is generated in the tank to enable rapid mixing.

【００１４】また、急速混合性能を向上させるために
は、本発明の攪拌装置及び前記攪拌装置を用いたハロゲ
ン化銀写真乳剤の製造方法において、前記溶液の前記各
流入口通過時の前記平均流速ｕ、前記攪拌翼径と前記攪
拌槽内径の比ｄ／Ｄ、前記攪拌翼の回転によって前記攪
拌槽内壁との間に生じる前記剪断力τのような各因子を
最適に選定、組み合わせることが好ましい。特に、前記
平均流速ｕが小さいと、前記各攪拌翼の回転によって発
生する遠心力のために前記攪拌槽内の溶液が前記各流入
口側に逆流することがあり好ましくない。前記平均流速
ｕは２０〜２００ｃｍ／ｓｅｃがこの好ましく、３０〜
１５０ｃｍ／ｓｅｃであることが更に好ましい。In order to improve the rapid mixing performance, in the stirring apparatus of the present invention and the method for producing a silver halide photographic emulsion using the stirring apparatus, the average flow rate of the solution when passing through each of the inlets is described. u, a ratio d / D of the diameter of the stirring blade to the inner diameter of the stirring tank, and various factors such as the shear force τ generated between the stirring blade and the inner wall of the stirring tank due to the rotation of the stirring blade are preferably selected and combined optimally. . In particular, if the average flow velocity u is small, the solution in the stirring tank may flow backward to the respective inlets due to the centrifugal force generated by the rotation of the stirring blades. The average flow velocity u is preferably 20 to 200 cm / sec, more preferably 30 to 200 cm / sec.
More preferably, it is 150 cm / sec.

【００１５】前記攪拌翼径と前記攪拌槽内径の比ｄ／Ｄ
が小さいと、攪拌効率の低下を招き易くなり好ましくな
い。一方、大き過ぎると、前記溶液の各流入口からの流
入の妨げとなる。前記攪拌翼径と前記攪拌槽内径の比ｄ
／Ｄは０．７０〜０．９０が好ましい。前記攪拌翼の回
転によって前記攪拌槽内壁との間に生じる前記剪断力τ
は攪拌翼回転数に比例して増大する。前記剪断力τを高
くすることで急速混合性能の向上が可能となる。前記剪
断力τは１０００ｓｅｃ^-1以上が好ましく、１５００ｓ
ｅｃ^-1以上であることが更に好ましい。The ratio d / D of the diameter of the stirring blade to the diameter of the stirring tank.
Is small, the stirring efficiency tends to decrease, which is not preferable. On the other hand, if it is too large, it will hinder the inflow of the solution from each inlet. Ratio d of the stirring blade diameter and the stirring tank inner diameter
/ D is preferably from 0.70 to 0.90. The shearing force τ generated between the stirring tank and the inner wall of the stirring tank by the rotation of the stirring blade.
Increases in proportion to the rotation speed of the stirring blade. The rapid mixing performance can be improved by increasing the shearing force τ. The shearing force τ is preferably at least 1000 sec ⁻¹ ,
It is more preferably at least ec ⁻¹ .

【００１６】[0016]

【発明の実施の形態】本発明の攪拌装置及び前記攪拌装
置を用いたハロゲン化銀写真乳剤の製造方法の一実施態
様について添付した図面に基づいて以下に詳述する。図
２は本発明に基づく攪拌装置の要部を示す縦断面図であ
り、図3は本発明に基づく攪拌装置の攪拌翼を拡大して
示した縦断面図である。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the stirring apparatus of the present invention and a method for producing a silver halide photographic emulsion using the stirring apparatus will be described in detail below with reference to the accompanying drawings. FIG. 2 is a longitudinal sectional view showing a main part of the stirring device according to the present invention, and FIG. 3 is an enlarged longitudinal sectional view showing a stirring blade of the stirring device according to the present invention.

【００１７】本発明に基づく攪拌装置３０は、反応液の
急速稀釈、急速混合反応、急速排出を実現することが出
来、好適な攪拌装置である。具体的には図２に示すよう
に、混合すべき溶液を流入させる二つの流入口３１，３
２と、混合処理を終えた混合液を排出する排出口３３と
を備えた円筒状の攪拌槽３４と、該攪拌槽３４内で互い
に逆向きに回転するように駆動される一対の攪拌翼３
５，３６を具備して成る。前記攪拌槽３４は、上下方向
に沿って中心軸を設定した円筒状の槽本体３０と、該攪
拌槽本体３０の上下の開口端を密閉する器壁となり、且
つ支軸４６を植設したシールプレート３７を具備する。The stirrer 30 according to the present invention is a suitable stirrer capable of realizing rapid dilution, rapid mixing reaction and rapid discharge of the reaction solution. Specifically, as shown in FIG. 2, two inflow ports 31 and 3 through which a solution to be mixed flows in.
2, a cylindrical stirring tank 34 having a discharge port 33 for discharging the mixed liquid after the mixing process, and a pair of stirring blades 3 driven to rotate in opposite directions in the stirring tank 34.
5, 36. The stirring tank 34 serves as a cylindrical tank body 30 having a central axis set along the vertical direction, a container wall for sealing the upper and lower open ends of the stirring tank body 30, and a seal in which a support shaft 46 is implanted. A plate 37 is provided.

【００１８】また、前記攪拌槽３４は少なくとも前記各
シールプレート３７が透磁性に優れた非磁性材料で形成
される。前記二つの流入口３１，３２は前記槽本体３０
の下方端の前記攪拌翼３６近傍の槽胴部に対設され、例
えば、一方の流入口３１から混合すべき主成分の溶液
を、他方の流入口３２から主成分の溶液に添加して主成
分の溶液を均質に攪拌混合させる添加液をの流入させ
る。なお、前記排出口３３は、前記槽本体３０の上方端
の前記攪拌翼３５近傍の槽胴部に、且つ気泡が溜り難い
位置に配設される。In the stirring tank 34, at least each of the seal plates 37 is formed of a non-magnetic material having excellent magnetic permeability. The two inlets 31, 32 are connected to the tank body 30.
For example, a solution of the main component to be mixed from one inlet 31 is added to the solution of the main component from the other inlet 32 so as to be opposed to the tank body near the stirring blade 36 at the lower end of the main body. An additive liquid for causing the solution of the components to be homogeneously stirred and mixed is introduced. In addition, the discharge port 33 is provided in a tank body near the stirring blade 35 at an upper end of the tank body 30 and at a position where bubbles hardly accumulate.

【００１９】前記各攪拌翼３５，３６は、各磁石３８,
３９を内蔵し、その回転軸芯に沿って例えば、セラミッ
クボールベアリングのような耐食性玉軸受４５を嵌着さ
せて前記各シールプレート３７の前記支軸４６に前記玉
軸受４５を介して回転自在に保持される。一方、前記各
シールプレート３７の外側に前記各攪拌翼３５，３６に
近接して対設される各外部磁石４０,４１によって、前
記各攪拌翼３５，３６との磁気的なカップリングが構成
され、各モーター４２，４３に機械的に連結された前記
各外部磁石４０，４１を互いに逆回転させる。Each of the stirring blades 35, 36 has a magnet 38,
For example, a corrosion-resistant ball bearing 45 such as a ceramic ball bearing is fitted along the rotation axis of the shaft 39 so as to be rotatable on the support shaft 46 of each seal plate 37 via the ball bearing 45. Will be retained. On the other hand, magnetic couplings with the stirring blades 35 and 36 are formed by the external magnets 40 and 41 provided outside the sealing plates 37 and adjacent to the stirring blades 35 and 36, respectively. The external magnets 40, 41 mechanically connected to the motors 42, 43 are rotated in opposite directions.

【００２０】以上記述したように構成される前記各攪拌
翼３５，３６及び前記各シールプレート３７によって高
速回転時における磁気的なカップリングの離脱現象の発
生を効果的に阻止する。その結果、前記各攪拌翼３５,
３６の高速回転に伴って混合処理速度を容易に向上させ
ることが可能になり、前記攪拌槽３４内の各溶液の滞留
させることなく急速に混合及び排出が可能となり、混合
処理品質の低下を防止することが出来る。The agitating blades 35 and 36 and the seal plates 37 configured as described above effectively prevent the magnetic coupling detachment phenomenon during high-speed rotation. As a result, each of the stirring blades 35,
The high-speed rotation of 36 makes it possible to easily improve the mixing processing speed, and enables the mixing and discharging of each solution in the stirring tank 34 without stagnation, thereby preventing the deterioration of the mixing processing quality. You can do it.

【００２１】なお、本発明の攪拌装置は、各種溶液の混
合が必要となる様々な工業分野で広く利用できるもので
ある。また、混合すべき各溶液も、純粋な溶液に限定す
るものではなく、固形成分を含有する溶液の混合にも適
用可能である。更に、本発明の攪拌装置は、ハロゲン化
銀写真乳剤の調製にも適用可能であり、外ハロゲン化銀
写真乳剤に含まれるハロゲン化銀粒子は、銀塩水溶液と
ハロゲン化物塩水溶液の高速反応プロセスを経て得られ
るため、前記攪拌装置を使用する利点が大きい。以下、
前記ハロゲン化銀写真乳剤の調製に関する本発明攪拌装
置の適用例を記述する。The agitator of the present invention can be widely used in various industrial fields that require mixing of various solutions. Further, each solution to be mixed is not limited to a pure solution, but can be applied to mixing of a solution containing a solid component. Further, the stirring apparatus of the present invention is also applicable to the preparation of a silver halide photographic emulsion, and the silver halide grains contained in the outer silver halide photographic emulsion are subjected to a high-speed reaction process of an aqueous silver salt solution and an aqueous halide salt solution. Thus, the advantage of using the stirring device is great. Less than,
An application example of the stirring apparatus of the present invention for preparing the silver halide photographic emulsion will be described.

【００２２】前記ハロゲン化銀写真乳剤に含まれる前記
ハロゲン化銀粒子の形成は、一般的に結晶核形成工程と
該核を用いた結晶成長工程に分けられる。また、多くの
場合、前記写真乳剤に用いられる前記ハロゲン化銀粒子
は、写真感度向上を目的として粒子内に転位線を有し、
該転位線を発生させる工程も含まれる。本発明の攪拌装
置を用いて形成される前記ハロゲン化銀微粒子は、前記
核として用いることができる。また、極めてサイズの小
さい前記ハロゲン化銀微粒子を用いれば、結晶成長工程
に用いることもできる。この場合、予め存在する前記核
より小さいサイズの前記ハロゲン化銀微粒子を用いるこ
とで、オストワルド熟成により前記核の結晶成長が生じ
る。また、前記転位線を発生させる工程では、例えば特
開２０００−６８７９６に開示されているようにヨウ化
銀微粒子を用いることが出来るが、本発明の攪拌装置を
用いて該微粒子を形成しても良い。The formation of the silver halide grains contained in the silver halide photographic emulsion is generally divided into a crystal nucleus forming step and a crystal growing step using the nucleus. In many cases, the silver halide grains used in the photographic emulsion have dislocation lines in the grains for the purpose of improving photographic sensitivity,
The step of generating the dislocation lines is also included. The silver halide fine particles formed using the stirring device of the present invention can be used as the nuclei. If the silver halide fine particles having an extremely small size are used, they can be used in a crystal growth step. In this case, the crystal growth of the nucleus occurs by Ostwald ripening by using the silver halide fine particles having a smaller size than the nucleus existing beforehand. In the step of generating dislocation lines, for example, silver iodide fine particles can be used as disclosed in JP-A-2000-68796, but the fine particles can be formed using the stirring device of the present invention. good.

【００２３】前記銀塩水溶液は通常硝酸銀水溶液が用い
られる。本発明の方法で得られる前記ハロゲン化銀粒子
を前記核として用いる場合、前記銀塩水溶液の濃度は
４．０ｍｏｌ／ｌ以下が好ましく、１．０ｍｏｌ／ｌ以
下がさらに好ましく、０．２ｍｏｌ／ｌL以下が最も好
ましい。結晶成長に用いる場合は、生産性の観点から高
濃度の前記銀塩水溶液を用いることが好ましい。０．５
ｍｏｌ／ｌ以上４ｍｏｌ／ｌ以下が好ましく、１．０ｍ
ｏｌ／ｌ以上が更に好ましい。前記銀塩水溶液の温度は
５℃以上７５℃以下が好ましい。The silver salt aqueous solution is usually a silver nitrate aqueous solution. When the silver halide grains obtained by the method of the present invention are used as the nucleus, the concentration of the silver salt aqueous solution is preferably 4.0 mol / l or less, more preferably 1.0 mol / l or less, and 0.2 mol / lL. The following are most preferred. When used for crystal growth, it is preferable to use the silver salt aqueous solution having a high concentration from the viewpoint of productivity. 0.5
mol / l or more and 4 mol / l or less, preferably 1.0 m
ol / l or more is more preferable. The temperature of the silver salt aqueous solution is preferably from 5 ° C to 75 ° C.

【００２４】前記ハロゲン化物塩水溶液は、通常、臭化
カリウム、臭化ナトリウム、塩化カリウム、塩化ナトリ
ウム、沃化カリウム、沃化ナトリウム及びそれらの混合
物の水溶液が用いられる。本発明の方法で得られる前記
ハロゲン化銀粒子を前記核として用いる場合、前記ハロ
ゲン化物水溶液の濃度は４．０ｍｏｌ／ｌ以下が好まし
く、１．０ｍｏｌ／ｌ以下がさらに好ましく、０．２ｍ
ｏｌ／ｌ以下が最も好ましい。結晶成長に用いる場合
は、生産性の観点から高濃度の水溶液を用いることが好
ましい。Ｏ．５ｍｏｌ／ｌ以上４．０ｍｏｌ／ｌ以下が
好ましく、１．０ｍｏｌ／ｌ以上が更に好ましい。前記
ハロゲン化物塩水溶液の温度は５℃以上７５℃以下が好
ましい。As the aqueous halide salt solution, an aqueous solution of potassium bromide, sodium bromide, potassium chloride, sodium chloride, potassium iodide, sodium iodide or a mixture thereof is usually used. When the silver halide grains obtained by the method of the present invention are used as the core, the concentration of the aqueous halide solution is preferably 4.0 mol / l or less, more preferably 1.0 mol / l or less, and 0.2 m / l or less.
ol / l or less is most preferred. When used for crystal growth, it is preferable to use a high-concentration aqueous solution from the viewpoint of productivity. O. It is preferably from 5 mol / l to 4.0 mol / l, more preferably from 1.0 mol / l. The temperature of the aqueous halide salt solution is preferably from 5 ° C to 75 ° C.

【００２５】前記銀塩水溶液と前記ハロゲン化物塩水溶
液の少なくとも一方には保護コロイドとしてゼラチンが
含まれることが好ましい。前記ゼラチンは生成する前記
ハロゲン化銀粒子中の双晶発生確率に大きな影響を与え
るため、好ましいゼラチン水溶液濃度は、生成する前記
微粒子ハロゲン化銀粒子の使用目的によって異なる。It is preferable that at least one of the aqueous silver salt solution and the aqueous halide salt solution contains gelatin as a protective colloid. Since the gelatin greatly affects the probability of twinning in the silver halide grains to be formed, the preferred concentration of the aqueous gelatin solution varies depending on the intended use of the fine silver halide grains to be formed.

【００２６】平板状ハロゲン化銀粒子調製を行う際の前
記核として連続生成された前記ハロゲン化銀粒子を利用
する場合、平行二重双晶核が必要なため、所望する前記
双晶発生確率が達成されるように前記ゼラチン水溶液濃
度を調節することが必要である。前記銀塩水溶液と前記
ハロゲン化物塩水溶液が混合されたときに前記硝酸銀１
ｇあたりのゼラチン量が０．０３ｇ以上０．４ｇ以下と
なるように前記ゼラチン水溶液濃度を選ぶことが好まし
く、０．３ｇ以下にすることが更に好ましい。When the silver halide grains continuously produced are used as the nuclei in preparing the tabular silver halide grains, parallel double twin nuclei are required. It is necessary to adjust the concentration of the aqueous gelatin solution to achieve it. When the silver salt aqueous solution and the halide salt aqueous solution are mixed, the silver nitrate 1
The concentration of the gelatin aqueous solution is preferably selected so that the amount of gelatin per g is 0.03 g or more and 0.4 g or less, and more preferably 0.3 g or less.

【００２７】前記結晶成長に利用する場合には、添加し
た前記ハロゲン化銀粒子が速やかに溶解することが好ま
しい。そのため、前記双晶核が少ない方が好ましく、前
記ゼラチン水溶液濃度は高い方が好ましい。前記ゼラチ
ン水溶液濃度は添加される前記硝酸銀１ｇに対して０．
２ｇ以上、１ｇ以下、前記ゼラチンが添加される濃度に
することが好ましく、０．３ｇ以上にすることが更に好
ましく、０．４ｇ以上にすることが最も好ましい。前記
ゼラチン水溶液濃度を高くした場合、前記ゼラチン水溶
液の粘度が増加し添加が困難になる。前記ゼラチンを酵
素分解などの手法で低分子量化することにより、粘度を
低下させることができる。前記ゼラチンの分子量は５０
００以上、１０万以下であることが好ましく、５万以下
であることが更に好ましく、３万以下であることが最も
好ましい。When used for the crystal growth, it is preferable that the added silver halide grains be rapidly dissolved. Therefore, it is preferable that the twin nuclei be small, and that the concentration of the gelatin aqueous solution be high. The concentration of the aqueous gelatin solution was 0.1 to 1 g of the added silver nitrate.
The concentration is preferably 2 g or more and 1 g or less, to which the above-mentioned gelatin is added, more preferably 0.3 g or more, and most preferably 0.4 g or more. When the concentration of the aqueous gelatin solution is increased, the viscosity of the aqueous gelatin solution increases, making it difficult to add. The viscosity can be reduced by reducing the molecular weight of the gelatin by a technique such as enzymatic decomposition. The molecular weight of the gelatin is 50
It is preferably at least 00 and at most 100,000, more preferably at most 50,000 and most preferably at most 30,000.

【００２８】前記結晶成長に利用する場合、前記ハロゲ
ン化銀粒子と共に添加される前記ゼラチンが前記平板状
ハロゲン化銀粒子の厚さに影響を及ぼす。厚さへの影響
は前記ゼラチンの化学修飾によって様々に変化させるこ
とができる。薄い前記平板状ハロゲン化銀粒子を得るた
めに、酸化処理、コハク化処理、トリメリット化処理を
好ましく用いることができる。以下、従来の攪拌装置と
本発明の攪拌装置をハロゲン化銀写真乳剤調整に適用し
た実施例と比較例によって本発明の攪拌装置の新規な効
果を説明する。When used for the crystal growth, the gelatin added together with the silver halide grains affects the thickness of the tabular silver halide grains. The effect on thickness can be varied in various ways by chemical modification of the gelatin. In order to obtain the thin tabular silver halide grains, an oxidation treatment, a succination treatment, and a trimellitization treatment can be preferably used. Hereinafter, the novel effects of the stirrer of the present invention will be described with reference to Examples and Comparative Examples in which the conventional stirrer and the stirrer of the present invention are applied to the preparation of a silver halide photographic emulsion.

【００２９】「比較例１」特開平１０−４３５７０号公
報に記載の攪拌装置に、硝酸銀水溶液とゼラチンを含む
臭化銀水溶液を添加して、臭化銀微粒子を生成させた。
その濃度が０．０８２６ｍｏｌ／ｌの硝酸銀水溶液硝酸
銀水溶液とその濃度が０．３５０％の低分子量ゼラチン
(分子量２万)を含む濃度が０．０８３６ｍｏｌ／ｌの臭
化カリウム水溶液をそれぞれ２００ｃｃ／ｍｉｎの流量
でセル内に添加した。攪拌回転数は二つの攪拌翼ともに
３０００ｒｐｍであった。このとき、ｔ＝２．３秒、ｕ
＝２５ｃｍ／ｓｅｃ、ｄ／Ｄ＝０．６０、τ＝８００ｓ
ｅｃ^-1であった。生成したハロゲン化銀微粒子を透過型
電子顕微鏡で観察した。ハロゲン化銀微粒子の電子線に
よる損傷を防ぐために、サンプルは溶液窒素を用いて−
１２０℃まで冷却した。観察されたハロゲン化銀微粒子
は略球形であり、３００個の粒子についてサイズを測定
した結果、その平均直径は１６．２ｎｍ、変動係数は３
３％であった。Comparative Example 1 An aqueous silver nitrate solution and an aqueous silver bromide solution containing gelatin were added to a stirring device described in JP-A-10-43570 to produce silver bromide fine particles.
An aqueous silver nitrate solution having a concentration of 0.0826 mol / l An aqueous silver nitrate solution and a low molecular weight gelatin having a concentration of 0.350%
An aqueous potassium bromide solution having a concentration of 0.0836 mol / l containing (molecular weight: 20,000) was added into the cell at a flow rate of 200 cc / min. The number of rotations for stirring was 3000 rpm for both of the stirring blades. At this time, t = 2.3 seconds, u
= 25 cm / sec, d / D = 0.60, τ = 800 s
ec ^-1 . The generated fine silver halide particles were observed with a transmission electron microscope. In order to prevent the silver halide fine particles from being damaged by the electron beam, the sample was prepared using solution nitrogen.
Cooled to 120 ° C. The observed silver halide fine particles were substantially spherical, and as a result of measuring the size of 300 grains, the average diameter was 16.2 nm and the variation coefficient was 3
3%.

【００３０】「実施例１」図２の攪拌装置を用いて、
「比較例１」と同様の条件で臭化銀微粒子を生成させ
た。各攪拌翼は１０．０００ｒｐｍの高速回転駆動が可
能であった。また、Ｖｍ、φ、ｄ、Ｄ、の選択により、
ｔ＝０．６秒、ｕ＝１０５ｃｍ／ｓｅｃ、ｄ／Ｄ＝０．
８５、τ＝２５００ｓｅｃ^-1とした。得られたハロゲン
化銀微粒子の平均直径は１３．０ｎｍであり、変動係数
は２５%であった。本発明の攪拌装置を用いることによ
り、小サイズかつ単分散性に優れたハロゲン化銀微粒子
の生成が可能であることが分る。この微粒子を核として
用いることで単分散性に優れたハロゲン化銀写真乳剤の
調製が可能となる。Example 1 Using the stirring device of FIG. 2,
Silver bromide fine particles were produced under the same conditions as in “Comparative Example 1”. Each stirring blade was capable of driving at a high speed of 10.000 rpm. Also, by selecting Vm, φ, d, and D,
t = 0.6 second, u = 105 cm / sec, d / D = 0.
85, τ = 2500 sec ⁻¹ . The average diameter of the obtained silver halide fine particles was 13.0 nm, and the coefficient of variation was 25%. It can be seen that the use of the stirrer of the present invention enables the production of silver halide fine particles having a small size and excellent monodispersibility. By using these fine particles as a nucleus, a silver halide photographic emulsion having excellent monodispersibility can be prepared.

【００３１】「比較例２」先ず、ＫＢｒを２６．４ｇ、
低分子量酸化処理ゼラチン(メチオニン基を酸化処理し
酵素により低分子量化したアルカリ処理オセインゼラチ
ンで、メチオニン基含有率４μｍｏｌ／ｇ、平均分子量
１５０００)を６５．９ｇ含む水溶液３４．３ｌを３５
℃に保ち、撹拌した。（１ｓｔ液調製） 次に、Ａｇ−１水溶液（１００ｍｌ中にＡｇＮＯ_３を
４．９ｇ含有する）２００５ｍｌと、Ｘ−１水溶液（１
００ｍｌ中にＫＢｒを５．２ｇ含有する）１５３０ｍ
ｌ、及びゼラチン水溶液（１００ｍｌ中に前記の低分子
量酸化処理ゼラチンを８．０ｇ含有する）４４８ｍｌを
トリプルジェット法で、一定の流量で３０秒間にわたり
添加した（添加１）。Comparative Example 2 First, 26.4 g of KBr was added.
35% of an aqueous solution containing 65.9 g of low-molecular-weight oxidized gelatin (an alkali-treated ossein gelatin obtained by oxidizing a methionine group and reducing the molecular weight by an enzyme and having a methionine group content of 4 μmol / g and an average molecular weight of 15000) is 35
C. and stirred. (1st solution preparation) then, (containing 4.9g of AgNO ₃ in 100 ml) Ag-1 aqueous solution 2005ml and, X-1 aqueous solution (1
(Containing 5.2 g of KBr in 00 ml) 1530 m
1 and 448 ml of an aqueous gelatin solution (containing 8.0 g of the low molecular weight oxidized gelatin in 100 ml) were added at a constant flow rate over 30 seconds by a triple jet method (addition 1).

【００３２】その後、ＫＢｒ１７１ｇを添加し、温度を
７５℃に昇温した。昇温後１２分間の熟成工程を経た
後、ゼラチン水溶液（１００ｍｌ中にメチオニン基を酸
化処理したアルカリ処理オセインゼラチンを１２．７ｇ
含有する）７９００ｍｌを添加し、次いで、４，５−ジ
ヒドロキシ−１，３−ジスルホン酸ジナトリウム一水和
物を５５．３ｇ、二酸化チオ尿素を０．０５ｇを１分間
づつ間隔をあけて順次添加した。次に、Ａｇ−２水溶液
(１００ｍｌ中にＡｇＮＯ_３を３２ｇ含有する)１３３５
８ｍｌとＸ−２水溶液（１００ｍｌ中に、ＫＢｒを２
２．０ｇ及びＫＩを１．１ｇ含有する）をダブルジェッ
ト法で４６分間にわたり添加した。この時、Ａｇ−２の
添加は一定の流量で行い、Ｘ−２水溶液の添加は反応容
器内のバルク乳剤溶液のｐＡｇが７．８６を保つように
行った。（添加３）Thereafter, 171 g of KBr was added, and the temperature was raised to 75 ° C. After a ripening step for 12 minutes after the temperature was raised, an aqueous gelatin solution (12.7 g of an alkali-treated ossein gelatin having a methionine group oxidized in 100 ml) was used.
7900 ml), followed by 55.3 g of disodium 4,5-dihydroxy-1,3-disulfonate monohydrate and 0.05 g of thiourea dioxide at intervals of 1 minute. did. Next, Ag-2 aqueous solution
(Contains 32 g of AgNO ₃ in 100 ml) 1335
8 ml and X-2 aqueous solution (KBr is 2
2.0 g and 1.1 g KI) were added by the double jet method over 46 minutes. At this time, the addition of Ag-2 was performed at a constant flow rate, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel maintained 7.86. (Addition 3)

【００３３】更に、Ａｇ−４水溶液（１００ｍｌ中にＡ
ｇＮＯ３を３２．０ｇ含有する）４１１４ｍｌと、Ｘ−
４水溶液（１００ｍｌ中にＫＢｒを２２．４ｇ含有す
る）をダブルジェット法で１７分間にわたり添加した。
この時、Ａｇ−４水溶液の添加は一定の流量で行い、Ｘ
−３水溶液の添加は反応容器内のバルク乳剤溶液のｐＡ
ｇが７．５２を保つように行った。（添加４） その後、ベンゼンチオスルホン酸ナトリウムを１．８
ｇ、オセインゼラチン水溶液（１００ｍｌ中にアルカリ
処理オセインゼラチンを１２．０ｇ含有する）３２９７
ｍｌを、１分間づつ間隔をあけて順次添加した。次いで
ＫＢｒをバルク乳剤溶液のｐＡｇを９．００になるよう
に添加してから、ＡｇＩ微粒子乳剤（１００ｇ中に平均
粒径０．０４７μｍのＡｇＩ微粒子を１３．０ｇ含有す
る）１９５０ｇを添加し、その２分後から、Ａｇ−４水
溶液６５６７ｍｌと、Ｘ−４水溶液をダブルジェット法
で添加した。この時Ａｇ−４水溶液は一定の流量で９分
間にわたって添加し、Ｘ−４水溶液は最初の３．３分間
だけ反応容器内のバルク乳剤溶液のｐＡｇを９．００に
保つように添加し、残りの５．７分間は添加をせず、反
応容器内のバルク乳剤溶液のｐＡｇが最終的に８．４に
なるようにした。（添加５）その後、フロキュレーショ
ン法により脱塩を行い、次いで、攪拌しながら水、Ｎａ
ＯＨ、前記のゼラチン−１を添加し、５６℃でｐＨ６．
４、ｐＡｇ８．６になるように調整した（乳剤Ａ）。Further, an aqueous solution of Ag-4 (A in 100 ml)
4114 ml containing 32.0 g of gNO3) and X-
Four aqueous solutions (containing 22.4 g of KBr in 100 ml) were added by the double jet method over 17 minutes.
At this time, the Ag-4 aqueous solution was added at a constant flow rate, and X
-3 aqueous solution was added to the pA of the bulk emulsion solution in the reaction vessel.
g was maintained at 7.52. (Addition 4) Thereafter, 1.8 g of sodium benzenethiosulfonate was added.
g, aqueous solution of ossein gelatin (containing 12.0 g of alkali-treated ossein gelatin in 100 ml) 3297
ml were added sequentially at one minute intervals. Next, KBr was added so that the pAg of the bulk emulsion solution became 9.00, and 1950 g of an AgI fine grain emulsion (containing 13.0 g of AgI fine grains having an average particle size of 0.047 μm in 100 g) was added. Two minutes later, 6567 ml of an Ag-4 aqueous solution and an X-4 aqueous solution were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added only for the first 3.3 minutes so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.00, and the remaining was added. Was added for 5.7 minutes, so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4. (Addition 5) Thereafter, desalting is performed by the flocculation method, and then water and Na
OH and the above-mentioned gelatin-1 were added, and the pH was adjusted to 56.degree.
4, pAg was adjusted to 8.6 (emulsion A).

【００３４】得られた粒子は、（１１１）面を主平面と
する平板状ハロゲン化銀粒子であり、平均円相当径１．
４６μｍ、平均厚さ０．１５μｍであった。これらの粒
子を透過型電子顕微鏡で観察したところ、粒子のフリン
ジ(縁)部分に１粒子辺り平均３０本以上の転位線が観察
された。The obtained grains are tabular silver halide grains having a (111) plane as a main plane, and have an average equivalent circle diameter of 1.
The average thickness was 46 μm and the average thickness was 0.15 μm. When these particles were observed with a transmission electron microscope, an average of 30 or more dislocation lines per particle were observed at the fringe (edge) of the particles.

【００３５】「比較例３」添加２のＡｇ−２水溶液とＸ
−２水溶液を、特開平１０−４３５７０号公報に記載の
攪拌装置を用いて混合し、形成される平均サイズ０．０
３３μｍの沃臭化銀超微粒子を含むハロゲン化銀乳剤を
吐出後直ちに添加するように変更した。この時、Ｘ−２
水溶液は添加量１３５５８ｍｌとなるように一定流量で
添加し、バルク液のｐＡｇは、Ｘ−１を添加しながら
７．８６になるように保った。上記以外は、比較例１と
同様にした。なお、攪拌機の回転数は３．０００ｒｐ
ｍ、ｔ＝１．５秒、ｕ＝２８ｃｍ／ｓｅｃ、ｄ／Ｄ＝
０．６０、τ＝８００ｓｅｃ^-1であった（乳剤Ｂ）。得
られた粒子は、（１１１）面を主平面とする平板状ハロ
ゲン化銀粒子と０．０６μｍ程度の正常晶微粒子の混合
物であった。添加２で加えたハロゲン化銀微粒子の一部
が溶解せずに残存する結果となった。平板状粒子は、平
均円相当径１．６９μｍ、平均厚さ０．０８μｍであっ
た。[Comparative Example 3] Ag-2 aqueous solution of addition 2 and X
-2 aqueous solution was mixed using a stirrer described in JP-A-10-43570, and the average size formed was 0.0
The silver halide emulsion containing ultrafine silver iodobromide particles of 33 μm was changed to be added immediately after ejection. At this time, X-2
The aqueous solution was added at a constant flow rate to make the addition amount 13558 ml, and the pAg of the bulk liquid was kept at 7.86 while adding X-1. Except for the above, the procedure was the same as in Comparative Example 1. The rotation speed of the stirrer was 3000 rpm
m, t = 1.5 seconds, u = 28 cm / sec, d / D =
0.60, τ = 800 sec ⁻¹ (emulsion B). The obtained grains were a mixture of tabular silver halide grains having a (111) plane as a main plane and normal crystal grains of about 0.06 μm. The result was that some of the silver halide fine particles added in Addition 2 remained without being dissolved. The tabular grains had an average equivalent circle diameter of 1.69 μm and an average thickness of 0.08 μm.

【００３６】「実施例２」比較例２において、特開平１
０−４３５０号公報に記載の攪拌機の代わりに、図２の
攪拌装置を用いる以外は、比較例２と同様にした。生成
するハロゲン化銀微粒子の平均サイズは０．０１５μｍ
であった。なお、攪拌回転数は１０．０００ｒｐｍ、ｔ
＝０．４ｓｅｃ、ｕ＝１４０ｃｍ／ｓｅｃ、ｄ／Ｄ＝
０．８５、τ＝２５００ｓｅｃ^-1であった（乳剤Ｃ）。
得られた粒子は、（１１１）面を主平面とする平板状ハ
ロゲン化銀粒子であり正常晶微粒子は殆ど観察されなか
った。平板状粒子は、平均円相当径１．９１μｍ、平均
厚さ０．０８μｍであった。これらの粒子を透過型電子
顕微鏡で観察したところ、粒子のフリンジ(縁)部分に１
粒子辺り平均３０本以上の転位線が観察された。本発明
の攪拌装置を用いることにより、厚さが薄くなおかつ微
粒子の残存が少ない平板状粒子の形成が可能となった。
乳剤Ａ、Ｂ及びＣそれぞれに対し、式ＥｘＳ−１、Ｅｘ
Ｓ−２及びＥｘＳ−３の各増感色素を用いた分光増感を
行い、更にチオ硫酸ナトリウム、塩化金酸、チオシアン
酸カリウム、Ｎ，Ｎ−ジメチルセレノウレアを用いて金
−イオウ−セレン増感を施し、写真性能を比較した。乳
剤Ａに対して乳剤Ｃは、増感色素を多量に吸収できるた
め、より高い写真感度が得られた。乳剤Ｂでは、微粒子
が多く残存しており、高い写真感度は得られなかった。"Example 2" In Comparative Example 2,
Comparative Example 2 was performed except that the stirrer shown in FIG. 2 was used instead of the stirrer described in JP-A No. 0-4350. The average size of the resulting silver halide fine particles is 0.015 μm.
Met. The stirring rotation speed is 10.000 rpm, t
= 0.4 sec, u = 140 cm / sec, d / D =
0.85, τ = 2500 sec ⁻¹ (emulsion C).
The obtained grains were tabular silver halide grains having a (111) plane as a main plane, and almost no normal crystal grains were observed. The tabular grains had an average equivalent circle diameter of 1.91 μm and an average thickness of 0.08 μm. Observation of these particles with a transmission electron microscope revealed that one fringe (edge) of the particles was observed.
An average of 30 or more dislocation lines per grain was observed. By using the stirring device of the present invention, it is possible to form tabular grains having a small thickness and little residual fine particles.
For each of emulsions A, B and C, the formulas ExS-1, Ex
Spectral sensitization was performed using each of the sensitizing dyes S-2 and ExS-3, and gold-sulfur-selenium was further sensitized using sodium thiosulfate, chloroauric acid, potassium thiocyanate, and N, N-dimethylselenourea. The photographic performance was compared. Emulsion C was able to absorb a larger amount of sensitizing dye than Emulsion A, and thus higher photographic sensitivity was obtained. In Emulsion B, many fine particles remained, and high photographic sensitivity was not obtained.

【００３７】[0037]

【化１】 Embedded image

【００３８】[0038]

【発明の効果】以上、記述した本発明の攪拌装置及び前
記攪拌装置を用いたハロゲン化銀写真乳剤の製造方法は
次に記すような新規な効果を奏するものである。即ち、
本発明の攪拌装置及び前記攪拌装置を用いたハロゲン化
銀写真乳剤の製造方法は、混合すべき溶液を各流入口か
ら攪拌槽内に流入しながら排出口から混合溶液を排出す
る間に、槽外に配設されたモータを介して回転駆動され
る外部磁石との磁気的なカップリングによって、前記攪
拌槽の上下端部を密封する各器壁内面に植設された支軸
を中心に回転自在に保持され且つ前記攪拌槽内で離間し
て対設した一対の磁石内蔵型攪拌翼を互いに逆向きに回
転するように駆動させて前記攪拌槽内の各溶液を混合し
た後、該混合液を排出口から前記攪拌槽外に排出する場
合、前記混合すべき溶液の前記各流入口通過時の平均流
速ｕを２０〜２００ｃｍ／ｓｅｃ、前記攪拌翼径と前記
攪拌槽内径の比ｄ／Ｄを０．７０〜０．９０、前記攪拌
翼の回転によって前記攪拌槽内壁との間に生じる剪断力
τを１０００ｓｅｃ^-1以上、前記混合すべき溶液の平均
滞留時間ｔを０．０５〜５．００秒として混合処理する
ので、前記各攪拌翼を高速回転させても前記支軸によっ
て前記各攪拌翼の回転軸芯が偏倚せず、磁気的なカップ
リングの離脱を防止することが可能になった。The stirrer according to the present invention described above and the method for producing a silver halide photographic emulsion using the stirrer have the following novel effects. That is,
The stirrer of the present invention and the method for producing a silver halide photographic emulsion using the stirrer include a step of discharging a mixed solution from an outlet while flowing a solution to be mixed into each stirrer from each inlet. By means of a magnetic coupling with an external magnet which is rotationally driven via a motor disposed outside, the shaft is rotated about a spindle planted on the inner surface of each vessel wall which seals the upper and lower ends of the stirring tank. A pair of magnet built-in stirring blades, which are freely held and spaced apart in the stirring tank, are driven to rotate in opposite directions to mix each solution in the stirring tank, and then the mixed solution Is discharged from the outlet through the outlet, the average flow velocity u of the solution to be mixed when passing through each of the inlets is 20 to 200 cm / sec, and the ratio d / D of the diameter of the stirring blade to the inner diameter of the stirring tank. 0.70 to 0.90, by the rotation of the stirring blade Serial shearing force generated between the stirring vessel inner wall τ a of 1,000 sec ^-1 or more, since the mixing process the mean residence time t of the solution to be the mixture as 0.05 to 5.00 seconds, high-speed rotation of the respective stirring blades Even if it does, the rotation axis of each of the stirring blades is not deviated by the support shaft, and it is possible to prevent the magnetic coupling from being detached.

【００３９】更に、本発明の攪拌装置及び前記攪拌装置
を用いたハロゲン化銀写真乳剤の製造方法は、槽内に対
設された前記一対の攪拌翼がそれぞれ向きの異なる高速
攪拌流を形成するので、槽内に高速乱流を発生させて急
速混合を行うことが可能になった。その結果、より安定
な高速回転を可能にし瞬間混合の品質向上ができた。ま
た、該攪拌装置をハロゲン化銀写真乳剤の調製に用いる
ことで、小サイズかつ単分散性に優れたハロゲン化銀粒
子の形成が可能となる。それを核形成や結晶成長に用い
ることで、単分散ハロゲン化銀写真乳剤や、厚さの薄い
平板状ハロゲン化銀写真乳剤の調製を行うことが可能に
なった。Further, in the stirring apparatus of the present invention and the method for producing a silver halide photographic emulsion using the stirring apparatus, the pair of stirring blades provided in the tank form a high-speed stirring flow having different directions. Therefore, it has become possible to generate a high-speed turbulent flow in the tank to perform rapid mixing. As a result, more stable high-speed rotation was enabled and the quality of instantaneous mixing was improved. In addition, by using the stirring apparatus for preparing a silver halide photographic emulsion, it is possible to form silver halide grains having a small size and excellent monodispersity. By using it for nucleation and crystal growth, it has become possible to prepare monodispersed silver halide photographic emulsions and thin tabular silver halide photographic emulsions.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明に基づく攪拌装置の要部を示す縦断面図
である。FIG. 1 is a longitudinal sectional view showing a main part of a stirring device according to the present invention.

【図２】本発明に基づく攪拌装置の攪拌翼を拡大して示
した縦断面図である。FIG. 2 is an enlarged longitudinal sectional view of a stirring blade of a stirring device according to the present invention.

【図３】従来の攪拌装置の要部を示す縦断面図である。FIG. 3 is a longitudinal sectional view showing a main part of a conventional stirring device.

【符号の説明】[Explanation of symbols]

１０ 従来の攪拌装置 １１ 流入口 １２ 流入口 １３ 流入口 １６ 排出口 １８ 攪拌槽 １９ 槽本体 ２０ 攪拌槽器壁 ２１ 攪拌翼 ２２ 攪拌翼 ２６ 外部磁石 ２８ モータ ２９ モータ ３０ 本発明に基づく攪拌装置 ３１ 流入口 ３２ 流入口 ３３ 排出口 ３４ 攪拌槽 ３５ 攪拌翼 ３６ 攪拌翼 ３７ シールプレート ３８ 磁石 ３９ 磁石 ４０ 外部磁石 ４１ 外部磁石 ４２ モータ ４３ モータ ４５ 玉軸受 ４６ 支軸 DESCRIPTION OF SYMBOLS 10 Conventional stirring apparatus 11 Inflow port 12 Inflow port 13 Inflow port 16 Outlet 18 Stirring tank 19 Tank body 20 Stirring vessel wall 21 Stirring blade 22 Stirring blade 26 External magnet 28 Motor 29 Motor 30 Stirring device 31 according to the present invention Inlet 32 Inlet 33 Outlet 34 Stirring tank 35 Stirrer blade 36 Stirrer blade 37 Seal plate 38 Magnet 39 Magnet 40 External magnet 41 External magnet 42 Motor 43 Motor 45 Ball bearing 46 Support shaft

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 攪拌対象の液体を流入させる所定の液供
給口と瞬時攪拌処理を終えた混合液体を瞬時に排出する
液排出口とを備えた攪拌槽と、該攪拌槽内で回転駆動さ
れることで該攪拌槽内の液体を瞬時混合する手段とを備
えて成る攪拌装置であって、 前記攪拌手段として、密閉された攪拌槽内に相対向する
二個所に離間して配置されて互いに逆向きに回転駆動さ
れる一対の攪拌翼を装備したことを特徴とした攪拌装置
において、 各攪拌翼は、磁石を内蔵し、回転軸を備えたプレートの
回転軸にボールベアリングを介して結合され、槽壁の外
側に配置された外部磁石と磁気カップリングを構成し、
それぞれの外部磁石を槽外に配備されたモータで回転駆
動することで各攪拌翼が回転操作されることを特徴とす
る攪拌装置。1. A stirring tank having a predetermined liquid supply port through which a liquid to be stirred flows in and a liquid discharge port through which a mixed liquid that has been subjected to instantaneous stirring processing is instantaneously discharged, and is rotationally driven in the stirring tank. A means for instantaneously mixing the liquid in the stirring tank, wherein the stirring means is disposed apart from each other at two opposing locations in a closed stirring tank and is mutually separated. A stirring device comprising a pair of stirring blades driven to rotate in opposite directions, wherein each stirring blade has a built-in magnet and is coupled to a rotation shaft of a plate having a rotation shaft via a ball bearing. Constituting a magnetic coupling with an external magnet arranged outside the tank wall,
A stirring device, wherein each stirring blade is rotated by driving each of the external magnets by a motor provided outside the tank. 【請求項２】 攪拌対象の液体の平均滞留時間ｔが、
０．０５〜５．００秒であることを特徴とする請求項1
に記載の攪拌装置。ここで、ｔは次式で定義される。 ｔ＝Ｖｍ／(ΣＱｉ) Ｖｍ ；攪拌有効容量 [ｃｃ] ΣＱｉ；流入溶液の総流量 [ｃｃ／ｓｅｃ]。2. An average residence time t of the liquid to be stirred is:
2. The method according to claim 1, wherein the time is 0.05 to 5.00 seconds.
The stirrer according to item 1. Here, t is defined by the following equation. t = Vm / (ΣQi) Vm; effective stirring capacity [cc] ΣQi; total flow rate of inflow solution [cc / sec]. 【請求項３】 攪拌対象の液体の流入口通過時の平均流
速ｕが、２０〜２００ｃｍ／ｓｅｃであることを特徴と
する請求項２に載の攪拌装置。ここで、ｕは次式で定義
される。 ｕ＝４Ｑ／πφ² Ｑ；溶液の流量 [ｃｃ／ｓｅｃ] φ；流入口の口径 [ｃｍ]3. The stirrer according to claim 2, wherein an average flow velocity u of the liquid to be stirred when passing through the inlet is 20 to 200 cm / sec. Here, u is defined by the following equation. u = 4Q / πφ ² Q; flow rate of solution [cc / sec] φ; diameter of inlet [cm] 【請求項４】 攪拌翼径と攪拌槽内径の比ｄ／Ｄが０．
７０〜０．９０であることを特徴とする請求項３に載の
攪拌装置。 ｄ；攪拌翼径 [ｃｍ] Ｄ；攪拌槽内径 [ｃｍ]4. The ratio d / D of the diameter of the stirring blade to the inner diameter of the stirring tank is set at 0.1.
The stirrer according to claim 3, wherein the ratio is 70 to 0.90. d: stirring blade diameter [cm] D: stirring tank inner diameter [cm] 【請求項５】 攪拌翼の回転によって攪拌槽内壁との間
に生じる剪断力τが１０００ｓｅｃ^-1以上であることを
特徴とする請求項４に記載の攪拌装置。ここで、τは次
式で定義される。 τ＝πｄＮ／σ ｄ；攪拌翼径 [ｃｍ] Ｎ；攪拌回転数 [ｒｐｓ] σ＝（Ｄ−ｄ）／２ [ｃｍ]5. The stirrer according to claim 4, wherein a shearing force τ generated between the inner wall of the stirrer and the inner wall of the stirrer by rotation of the stirrer is 1000 sec ⁻¹ or more. Here, τ is defined by the following equation. τ = πdN / σ d; stirring blade diameter [cm] N; stirring rotation speed [rps] σ = (D−d) / 2 [cm] 【請求項６】 請求項1に記載の攪拌装置を用いたハロ
ゲン化銀写真乳剤の製造方法。6. A method for producing a silver halide photographic emulsion using the stirring device according to claim 1.