JP2000338620A - Method for manufacturing silver halide photographic emulsion - Google Patents
Method for manufacturing silver halide photographic emulsionInfo
- Publication number
- JP2000338620A JP2000338620A JP2000082482A JP2000082482A JP2000338620A JP 2000338620 A JP2000338620 A JP 2000338620A JP 2000082482 A JP2000082482 A JP 2000082482A JP 2000082482 A JP2000082482 A JP 2000082482A JP 2000338620 A JP2000338620 A JP 2000338620A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- silver
- aqueous solution
- solution
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は写真用感光材料のハ
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 method for producing a silver halide photographic emulsion of a photographic light-sensitive material.
【０００２】[0002]
【従来の技術】ハロゲン化銀写真乳剤の製造は、通常の
場合、攪拌機を備えた反応容器内に銀イオンとハロゲン
化物イオンを添加して行われる。初期の添加によって核
形成が起こり、その後の添加によって結晶成長が行われ
る。攪拌方法には、例えば特開平７−２１９０９２号、
特開平８−１７１１５６号、特開平４−２８３７４１
号、特公平８−２２７３９号各公報、米国特許第３，７
８２，９５４号等に記載されているような様々な方法が
ある。しかし、このような方法で核形成を行う場合、い
ずれの攪拌方法を用いても、反応容器内を液が循環する
ために核形成と核成長が並行して起こり、単分散な核を
生成することが困難である。2. Description of the Related Art A silver halide photographic emulsion is usually produced by adding silver ions and halide ions into a reaction vessel equipped with a stirrer. Nucleation occurs with the initial addition, and crystal growth occurs with subsequent additions. As the stirring method, for example, JP-A-7-219092,
JP-A-8-171156, JP-A-4-283741
And Japanese Patent Publication No. 8-22739, U.S. Pat.
There are various methods as described in U.S. Pat. However, when nucleation is performed by such a method, nucleation and nucleus growth occur in parallel because the liquid circulates in the reaction vessel, and a monodisperse nucleus is generated regardless of the stirring method. It is difficult.
【０００３】ハロゲン化銀写真分野では感光素子として
受光面積の大きい平板状ハロゲン化銀粒子が広く用いら
れている。受光効率を上げるために、厚さの薄い平板状
ハロゲン化銀粒子が好ましい。しかし、上述ような方法
では、循環のために、成長途中の平板状ハロゲン化銀粒
子が銀イオンまたはハロゲン化物イオン添加口近傍の高
過飽和領域を通過し、平板状粒子の厚さが増加する弊害
が生じる。In the field of silver halide photography, tabular silver halide grains having a large light receiving area are widely used as photosensitive elements. In order to increase the light receiving efficiency, tabular silver halide grains having a small thickness are preferred. However, in the method described above, the tabular silver halide grains during growth pass through the high supersaturated region near the silver ion or halide ion addition port due to circulation, and the thickness of the tabular grains increases. Occurs.
【０００４】これらの問題を解決するために、前記反応
容器の他に外部混合器を設け、該外部混合器でハロゲン
化銀微粒子を形成し、それを核形成工程や成長工程等に
用いる方法がある。この方法では、外部混合器に銀塩水
溶液とハロゲン化物塩水溶液と分散媒水溶液を添加し、
連続的に微粒子を形成する。微粒子は核形成かつ/また
は成長に用いることが出来る。このような方法では外部
混合器はできるだけ短時間で添加液を完全に混合できる
ことが望まれる。混合に長時間を要したり、添加液が外
部混合器内部を循環することは好ましくない。In order to solve these problems, there is a method in which an external mixer is provided in addition to the above-mentioned reaction vessel, and silver halide fine particles are formed by the external mixer, and are used in a nucleation step, a growth step and the like. is there. In this method, an aqueous silver salt solution, an aqueous halide salt solution and an aqueous dispersion medium are added to an external mixer,
Fine particles are continuously formed. Fine particles can be used for nucleation and / or growth. In such a method, it is desired that the external mixer can completely mix the additive liquid in as short a time as possible. It is not preferable that the mixing takes a long time or that the additive liquid circulates inside the external mixer.
【０００５】前述の反応容器として様々な形式のものを
用いることが出来る。例えば、米国特許第５，２５０，
４０３号や特開平１０−４３５７０号では、小容量の混
合器の中で攪拌羽根によって混合を行う。しかし、この
ような方法は容器内で添加液が混合器内部を循環する。
特開平４−１３９４４０号や特表平６−５０７２５５号
では、機械的攪拌を伴わずに混合を行うため、添加液の
循環は存在しない。しかし、これらの方法では攪拌が存
在しないために混合力が不十分である。機械的攪拌を伴
わずに十分な混合力を保つために、添加液を噴流として
その運動エネルギーによって混合を行う方法がある。特
開平８−３３４８４８にはそのような噴流の運動エネル
ギーを利用するハロゲン化銀写真乳剤の製造方法が開示
されている。しかし、前記特許はシングルジェット法に
よるハロゲン化銀写真乳剤の製造方法に関するものであ
り、外部混合器とは全く異なるものである。さらにここ
で用いられている運動エネルギーは反応容器全体の混合
を行うには不十分なため、機械的攪拌が併用されてい
る。[0005] Various types of reaction vessels can be used as the above-mentioned reaction vessel. For example, US Pat. No. 5,250,
In 403 and JP-A-10-43570, mixing is performed by a stirring blade in a small-capacity mixer. However, in such a method, the additive liquid circulates inside the mixer in the container.
In JP-A-4-139440 and JP-A-6-507255, since mixing is performed without mechanical stirring, there is no circulation of the additive liquid. However, these methods have insufficient mixing power due to the absence of stirring. In order to maintain sufficient mixing power without mechanical stirring, there is a method in which mixing is performed by kinetic energy using an additive liquid as a jet. JP-A-8-334848 discloses a method for producing a silver halide photographic emulsion utilizing the kinetic energy of such a jet. However, the patent relates to a method for producing a silver halide photographic emulsion by a single jet method, which is completely different from an external mixer. Further, since the kinetic energy used here is insufficient to mix the entire reaction vessel, mechanical stirring is also used.
【０００６】[0006]
【発明が解決しようとする課題】本発明により、小サイ
ズかつ単分散なハロゲン化銀粒子を連続的に生成するこ
とが可能となる。これを核として用いることで、単分散
ハロゲン化銀粒子が得られる。また、これを結晶成長に
用いることで、厚さの薄い平板状ハロゲン化銀粒子の形
成が可能になる。According to the present invention, it is possible to continuously produce small-sized and monodispersed silver halide grains. By using this as a nucleus, monodispersed silver halide grains can be obtained. By using this for crystal growth, tabular silver halide grains having a small thickness can be formed.
【０００７】[0007]
【課題を解決するための手段】本発明の目的は以下の方
法によって達成される。The object of the present invention is achieved by the following method.
【０００８】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、前記
二種類の溶液を短時間内に混合してハロゲン化銀粒子を
連続的に生成するハロゲン化銀写真乳剤の製造方法。[0008] At least one of the aqueous silver salt solution and the aqueous halide salt solution is a linear jet having a high flow rate, and the two types of solutions are mixed within a short time to continuously produce silver halide grains. Production method of silver photographic emulsion.
【０００９】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、前記
二種類の溶液を循環させずに混合してハロゲン化銀粒子
を連続的に生成するハロゲン化銀写真乳剤の製造方法。At least one of an aqueous solution of a silver salt and an aqueous solution of a halide salt is formed into a linear jet having a high flow rate, and the two types of solutions are mixed without being circulated to continuously produce silver halide grains. Production method of silver photographic emulsion.
【００１０】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、前記
二種類の溶液を機械的攪拌を伴わずに混合してハロゲン
化銀粒子を連続的に生成するハロゲン化銀写真乳剤の製
造方法。At least one of the aqueous silver salt solution and the aqueous halide salt solution is formed into a linear jet having a high flow rate, and the two types of solutions are mixed without mechanical stirring to continuously produce silver halide grains. Of producing a silver halide photographic emulsion.
【００１１】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、該噴
流に平行でかつ内部に窪みを有する細管に前記二種類の
溶液を通過させて、短時間内に混合してハロゲン化銀粒
子を連続的に生成するハロゲン化銀写真乳剤の製造方
法。At least one of the silver salt aqueous solution and the halide salt aqueous solution is a linear jet having a high flow rate, and the two kinds of solutions are passed through a narrow tube parallel to the jet and having a recess therein, for a short time. A method for producing a silver halide photographic emulsion in which silver halide grains are continuously produced by mixing silver halide grains.
【００１２】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、該噴
流に平行でかつ内部に窪みを有する細管に前記二種類の
溶液を通過させて、循環させずに混合してハロゲン化銀
粒子を連続的に生成するハロゲン化銀写真乳剤の製造方
法。At least one of the silver salt aqueous solution and the halide salt aqueous solution is formed into a linear jet having a high flow rate, and the two solutions are passed through a narrow tube parallel to the jet and having a recess therein, and circulated. Of producing a silver halide photographic emulsion in which silver halide grains are continuously produced by mixing the emulsions without mixing.
【００１３】銀塩水溶液とハロゲン化物塩水溶液の少
なくとも一方を高い流速を持つ直線状の噴流とし、該噴
流に平行でかつ内部に窪みを有する細管に前記二種類の
溶液を通過させて、機械的攪拌を伴わずに混合してハロ
ゲン化銀粒子を連続的に生成するハロゲン化銀写真乳剤
の製造方法。At least one of the aqueous silver salt solution and the aqueous halide salt solution is a linear jet having a high flow rate, and the two solutions are passed through a narrow tube parallel to the jet and having a recess therein. A method for producing a silver halide photographic emulsion in which silver halide grains are continuously produced by mixing without stirring.
【００１４】[0014]
【発明の実施の形態】本発明の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ハロゲン
化銀粒子を核として用いる場合、水溶液の濃度は4mol/
リットル以下が好ましく、1mol/リットル以下がさらに
好ましく、0.2mol/リットル以下が最も好ましい。結晶
成長に用いる場合には、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く、0.5mol/リットル以上4mol/
リットル以下が好ましく、1.0mol/ リットル以上がさら
に好ましい。水溶液の温度は5℃以上75℃以下が好まし
い。本発明の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、沃化ナトリウムおよびそれらの混合
物の水溶液が用いられる。本発明の方法で得られるハロ
ゲン化銀粒子を核として用いる場合、水溶液の濃度は4m
ol/リットル以下が好ましく、1mol/リットル以下がさら
に好ましく、0.2mol/リットル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く、その濃度は0.5mol/リット
ル以上4mol/リットル以下が好ましく、1.0mol/リットル
以上がさらに好ましい。水溶液の温度は5℃以上75℃以
下が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The aqueous silver salt solution of the present invention is usually an aqueous silver nitrate solution. When the silver halide grains obtained by the method of the present invention are used as nuclei, the concentration of the aqueous solution is 4 mol / mol.
Liter or less, more preferably 1 mol / liter or less, most preferably 0.2 mol / liter or less. When used for crystal growth, it is preferable to use a high concentration aqueous solution from the viewpoint of productivity, 0.5 mol / liter or more 4 mol /
Liter or less, more preferably 1.0 mol / liter or more. The temperature of the aqueous solution is preferably from 5 ° C to 75 ° C. As the aqueous halide salt solution of the present invention, an aqueous solution of potassium bromide, sodium bromide, potassium chloride, sodium chloride, potassium iodide, sodium iodide or a mixture thereof is usually used. When using silver halide grains obtained by the method of the present invention as nuclei, the concentration of the aqueous solution is 4 m
ol / liter or less is preferable, 1 mol / liter or less is more preferable, and 0.2 mol / liter or less is most preferable. When used for crystal growth, it is preferable to use a high-concentration aqueous solution from the viewpoint of productivity, and the concentration is preferably 0.5 mol / L or more and 4 mol / L or less, more preferably 1.0 mol / L or more. The temperature of the aqueous solution is preferably from 5 ° C to 75 ° C.
【００１５】本発明の銀塩水溶液とハロゲン化物塩水溶
液の少なくとも一方に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。ゼラチンは生成するハロゲン化
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、生成する微粒子ハロゲン
化銀粒子の使用目的によって異なる。平板状ハロゲン化
銀粒子調製を行う際の核として連続生成されたハロゲン
化銀粒子を利用する場合、平行二重双晶核が必要なた
め、所望の双晶発生確率が達成されるようにゼラチン水
溶液濃度を調節することが必要である。銀塩水溶液とハ
ロゲン化物塩水溶液が混合されたときに銀１ｇあたりの
ゼラチン量が０．０３ｇ以上０．４ｇ以下となるように
ゼラチン濃度を選ぶことが好ましく、０．３ｇ以下にす
ることがさらに好ましい。It is preferable that at least one of the aqueous silver salt solution and the aqueous halide salt solution of the present invention contains gelatin as a protective colloid. Since gelatin greatly affects the probability of twinning in silver halide grains to be formed, a preferable concentration of an aqueous gelatin solution varies depending on the intended use of the fine silver halide grains to be formed. When using continuously generated silver halide grains as nuclei for preparing tabular silver halide grains, parallel double twin nuclei are required, so that gelatin is required to achieve a desired twin generation probability. It is necessary to adjust the concentration of the aqueous solution. It is preferable to select the gelatin concentration such that the amount of gelatin per gram of silver is 0.03 g or more and 0.4 g or less when the silver salt aqueous solution and the halide salt aqueous solution are mixed, and more preferably 0.3 g or less. preferable.
【００１６】本発明によって得られた微粒子ハロゲン化
銀乳剤はハロゲン化銀粒子の結晶成長時に核として用い
ることができる。結晶成長に利用する場合には、添加し
た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、双晶核が少ない方が好ましく、ゼラチン
水溶液濃度は高い方が好ましい。ゼラチン水溶液濃度は
添加される硝酸銀１ｇに対して０．２g以上、１ｇ以
下、ゼラチンが添加される濃度にすることが好ましく、
０．３g以上にすることがさらに好ましく、０．４g以上
にすることが最も好ましい。The fine grain silver halide emulsion obtained by the present invention can be used as a nucleus during crystal growth of silver halide grains. When used for crystal growth, it is preferable that the added silver halide grains be rapidly dissolved. Therefore, it is preferable that the number of twin nuclei is small, and that the concentration of the aqueous gelatin solution is high. The concentration of the aqueous gelatin solution is preferably 0.2 g or more and 1 g or less per 1 g of added silver nitrate, and the concentration is preferably such that gelatin is added.
More preferably, it is 0.3 g or more, most preferably, 0.4 g or more.
【００１７】ゼラチン水溶液濃度を高くした場合、ゼラ
チン水溶液の粘度が増加し添加が困難になる。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。ゼラチンの分子量は5000
以上、10万以下であることが好ましく、5万以下である
ことがさらに好ましく、3万以下であることが最も好ま
しい。結晶成長に利用する場合、ハロゲン化銀粒子と共
に添加されるゼラチンが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。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 gelatin by a method such as enzymatic decomposition. The molecular weight of gelatin is 5000
As described above, it is preferably 100,000 or less, more preferably 50,000 or less, and most preferably 30,000 or less. When used for crystal growth, gelatin added together with silver halide grains affects the thickness of tabular silver halide grains. The effect on thickness can be varied in various ways by chemical modification of the gelatin. In order to obtain thin tabular silver halide grains, an oxidation treatment, a succination treatment,
Trimeritization treatment can be preferably used.
【００１８】噴流として添加される水溶液の流速は、１
００ｍ／ｓｅｃ以上であることが好ましく、２５０ｍ／
ｓｅｃ以上であることがさらに好ましく、５００ｍ／ｓ
ｅｃ以上であることが最も好ましい。The flow rate of the aqueous solution added as a jet is 1
00 m / sec or more, preferably 250 m / sec.
sec or more, more preferably 500 m / s
It is most preferable that it is ec or more.
【００１９】溶液を混合する細管の直径は、直線状噴流
添加口の直径の２０倍以下であることが好ましく、１０
倍以下であることがさらに好ましく、７倍以下であるこ
とが最も好ましい。溶液を混合する細管の長さは、その
直径の１０倍以上であることが好ましく、５０倍以上で
あることがさらに好ましく、１００倍以上であることが
最も好ましい。細管は内部に窪みを有することができ
る。添加された溶液が細管内を流れる際にこの窪みによ
って流れはより細かな乱流となり、混合をより均一化す
る。高い流速を持つ噴流による混合を行う場合、混合液
の温度が上昇するため、該装置には冷却器を付属するこ
とが好ましい。The diameter of the narrow tube into which the solution is mixed is preferably 20 times or less the diameter of the straight jet addition port.
It is more preferably at most 7 times, most preferably at most 7 times. The length of the capillary for mixing the solution is preferably at least 10 times the diameter, more preferably at least 50 times, and most preferably at least 100 times the diameter. The capillaries can have depressions inside. As the added solution flows through the capillaries, the depressions result in finer turbulence and more uniform mixing. When mixing is performed by a jet having a high flow velocity, the temperature of the mixed solution increases. Therefore, it is preferable that a cooler is attached to the apparatus.
【００２０】銀塩水溶液とハロゲン化物塩水溶液の混合
は短時間に行うことが好ましい。混合時間は０．５秒以
下であることが好ましく、０．１秒以下であることが好
ましく、０．０５秒以下であることが最も好ましい。銀
塩水溶液とハロゲン化物塩水溶液の混合の際に外部混合
器内で添加液の循環が起こらないことが好ましい。添加
溶液が外部混合器内部を循環すると、生成したハロゲン
化銀微粒子の成長が生じ易いため好ましくない。The mixing of the aqueous silver salt solution and the aqueous halide salt solution is preferably performed in a short time. The mixing time is preferably 0.5 seconds or less, more preferably 0.1 seconds or less, and most preferably 0.05 seconds or less. It is preferable that the addition liquid does not circulate in the external mixer when the silver salt aqueous solution and the halide salt aqueous solution are mixed. It is not preferable that the added solution circulates inside the external mixer because the generated silver halide fine particles are likely to grow.
【００２１】銀塩水溶液とハロゲン化物塩水溶液の混合
は機械的攪拌を伴わないことが好ましい。機械的攪拌を
伴うと、循環が起こらない混合が困難である。また、
０．１秒以下のような短い混合時間の場合、機械的攪拌
では十分な混合を行うことが困難である。The mixing of the aqueous silver salt solution and the aqueous halide salt solution preferably does not involve mechanical stirring. With mechanical stirring, mixing without circulation is difficult. Also,
In the case of a short mixing time such as 0.1 second or less, it is difficult to perform sufficient mixing by mechanical stirring.
【００２２】本発明の要件を満たす混合方法として、Ｂ
ＥＥ ＩＮＴＥＲＮＡＴＩＯＮＡＬ社製の高圧ホモジェ
ナイザー(ＤｅＢＥＥ２０００)を応用して用いることが
できる。該装置のデュアルフィード法を用いて、銀塩水
溶液またはハロゲン化物塩水溶液の一方を高速噴流と
し、もう一方の液と混合することができる。噴流とする
水溶液に高圧をかけることで高い運動エネルギーを持た
せ、二つの液を極めて短時間に混合することが可能であ
る。また、この方法では添加された液が再び添加口近傍
に戻るような循環が発生せず、さらに、添加液が十分な
運動エネルギーを持つために機械的攪拌も不要である。As a mixing method satisfying the requirements of the present invention, B
A high-pressure homogenizer (DeBEE2000) manufactured by EE International can be used. Using the dual feed method of the apparatus, one of the silver salt aqueous solution and the halide salt aqueous solution can be made into a high-speed jet and mixed with the other liquid. By applying high pressure to the aqueous solution to be jetted, high kinetic energy can be imparted, and the two liquids can be mixed in an extremely short time. Further, in this method, no circulation occurs in which the added liquid returns to the vicinity of the addition port again. Further, since the added liquid has a sufficient kinetic energy, no mechanical stirring is required.
【００２３】[0023]
【実施例】以下、本発明を実施例によって説明する。The present invention will be described below with reference to examples.
【００２４】＜実施例１＞ （比較例）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。該攪拌装置は機
械的攪拌によって混合を行う。濃度0.0826mol/リットル
硝酸銀水溶液硝酸銀水溶液と濃度0.350%の低分子量ゼラ
チン(分子量2万)を含む濃度0.0836mol/リットルの臭化
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。添加液の混合容器内滞留時間は2.3 秒であっ
た。<Example 1> (Comparative Example) An aqueous silver nitrate solution and an aqueous silver bromide solution containing gelatin were added to a stirrer described in JP-A-10-43570 to produce silver bromide fine particles. The stirrer performs mixing by mechanical stirring. A silver nitrate aqueous solution having a concentration of 0.0826 mol / l and a potassium bromide aqueous solution having a concentration of 0.0836 mol / l containing a low molecular weight gelatin (molecular weight: 20,000) having a concentration of 0.350% were added into the cell at a flow rate of 200 cc / min. The residence time of the additive liquid in the mixing vessel was 2.3 seconds.
【００２５】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、サンプルは液体窒素を用いて−120
℃まで冷却した。観察されたハロゲン化銀微粒子はほぼ
球形であり、３００粒子についてサイズ測定を行った結
果、平均直径16.2nm、変動係数は33%であった。The produced fine silver halide particles were observed with a transmission electron microscope. To prevent silver halide fine particles from being damaged by the electron beam, the sample was
Cooled to ° C. The observed fine particles of silver halide were almost spherical, and as a result of measuring the size of 300 particles, the average diameter was 16.2 nm and the coefficient of variation was 33%.
【００２６】（本発明）ＢＥＥ ＩＮＴＥＲＮＡＴＩＯ
ＮＡＬ社製の高圧ホモジェナイザーＤｅＢＥＥ２０００
を混合器として応用することによって、硝酸銀水溶液と
ゼラチンを含む臭化銀水溶液を混合して臭化銀微粒子を
生成させた。該装置のデュアルフィード法を用い、濃度
0.0826mol/リットル硝酸銀水溶液を直線状噴流とした。
噴流は吐出圧9.8×107Paの圧力下で直径0.1mmの細孔を
通過させることによって生成した。硝酸銀水溶液の添加
速度は280cc/min、流速は600m/secであった。もう一方
の添加口から、ピストンによって流量制御を行いながら
ゼラチンを含む臭化カリウム水溶液を添加した。臭化カ
リウム濃度は0.0836mol/リットルであり、ゼラチン水溶
液濃度は0.350%であった。ゼラチンは分子量約20000の
低分子量ゼラチンを用いた。添加速度は280cc/minであ
った。この方法により、硝酸銀水溶液とハロゲン化物塩
水溶液を、0.012秒の混合時間で、循環なく、機械的攪
拌を伴わずに混合した。得られたハロゲン化銀微粒子の
平均直径は13.8nmであり変動係数は24%であった。(Invention) BEE INTERNATIO
High pressure homogenizer DeBEE2000 manufactured by NAL
Was applied as a mixer to mix silver nitrate aqueous solution and silver bromide aqueous solution containing gelatin to produce silver bromide fine particles. Using the dual feed method of the device, the concentration
A 0.0826 mol / liter silver nitrate aqueous solution was used as a linear jet.
The jet was generated by passing through a 0.1 mm diameter pore under a discharge pressure of 9.8 × 10 7 Pa. The addition rate of the aqueous silver nitrate solution was 280 cc / min, and the flow rate was 600 m / sec. An aqueous potassium bromide solution containing gelatin was added from the other addition port while controlling the flow rate with a piston. The potassium bromide concentration was 0.0836 mol / liter, and the gelatin aqueous solution concentration was 0.350%. As the gelatin, a low molecular weight gelatin having a molecular weight of about 20,000 was used. The addition rate was 280 cc / min. According to this method, the aqueous silver nitrate solution and the aqueous halide salt solution were mixed for 0.012 seconds with no circulation and without mechanical stirring. The average diameter of the obtained silver halide fine particles was 13.8 nm, and the coefficient of variation was 24%.
【００２７】上記より、本発明により、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。From the above, it can be seen that the present invention makes it possible to produce silver halide fine particles having a small size and excellent monodispersity. By using these fine particles as a nucleus, a silver halide photographic emulsion having excellent monodispersibility can be prepared.
【００２８】＜実施例２＞ （乳剤Ａ／比較例１）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１５００
０)を６５．９ｇ含む水溶液３４．３Lを３５℃に保ち、
撹拌した。（１st 液調製）<Example 2> (Emulsion A / Comparative Example 1) 26.4 g of KBr, low molecular weight oxidized gelatin (alkali-treated ossein gelatin whose methionine group was oxidized to lower the molecular weight with an enzyme and contained a methionine group Rate 4 μmol / g, average molecular weight 1500
3) 3L of an aqueous solution containing 65.9 g of
Stirred. (Preparation of 1st liquid)
【００２９】Ａｇ−１水溶液（１００ｍｌ中にＡｇＮＯ
３を４．９ｇ含有する）２００５ｍｌと、Ｘ−１水溶液
（１００ｍｌ中にＫＢｒを５．２ｇ含有する）１５３０
ｍｌ、およびゼラチン水溶液（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）４４８ｍ
ｌ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）。Ag-1 aqueous solution (AgNO in 100 ml)
3, 4.9 g) and an aqueous X-1 solution (containing 5.2 g of KBr in 100 ml) 1530
and an aqueous gelatin solution (containing 8.0 g of the low molecular weight oxidized gelatin in 100 ml) 448 m
1 was added by a triple jet method at a constant flow rate over 30 seconds (addition 1).
【００３０】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。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.
【００３１】次に、Ａｇ−２水溶液(１００ｍｌ中にＡ
ｇＮＯ３を３２ｇ含有する)１３３５８ｍｌとＸ−２水
溶液（１００ｍｌ中に、ＫＢｒを２２．０ｇおよび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）Next, an aqueous solution of Ag-2 (A in 100 ml)
13358 ml of XNO aqueous solution (containing 22.0 g of KBr and KI in 100 ml)
1.1 g) was added over 46 minutes by the double jet method. 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)
【００３２】さらに、Ａｇ−４水溶液（１００ｍｌ中に
ＡｇＮＯ３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）Further, 4114 ml of an Ag-4 aqueous solution (containing 32.0 g of AgNO3 in 100 ml) and X
-4 aqueous solution (containing 22.4 g of KBr in 100 ml) was 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)
【００３３】その後、ベンゼンチオスルホン酸ナトリウ
ムを１．８ｇ、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）３２９７ｍｌ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９．０
０になるように添加してから、ＡｇＩ微粒子乳剤（１０
０ｇ中に平均粒径０．０４７μｍのＡｇＩ微粒子を１
３．０ｇ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ｐＡ
ｇ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、ＮａＯＨ、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。Thereafter, 1.8 g of sodium benzenethiosulfonate and 3297 ml of an aqueous ossein gelatin solution (containing 12.0 g of alkali-treated ossein gelatin in 100 ml) were successively added at intervals of 1 minute. Then, KBr was added to the pAg of the bulk emulsion solution at 9.0.
0, and then AgI fine grain emulsion (10
0 g of AgI fine particles having an average particle size of 0.047 μm in 1 g
1950 g (containing 3.0 g) was added, and 2 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 to the pA of the bulk emulsion solution in the reaction vessel.
g was added to keep it at 9.00, and no addition was made for the remaining 5.7 minutes, so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4. (Addition 5). afterwards,
Desalting is performed by a flocculation method, and then water, NaOH and the above-mentioned gelatin-1 are added with stirring.
It adjusted so that it might become pH6.4 and pAg8.6 at 56 degreeC.
【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】（乳剤Ｂ／比較例２）添加２のＡｇ−２水
溶液とＸ−２水溶液を、特開平１０−４３５７０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．
０３３μｍ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水溶液は添加量が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。(Emulsion B / Comparative Example 2) The Ag-2 aqueous solution and the X-2 aqueous solution of Addition 2 were mixed by using a stirrer described in JP-A-10-43570, and the average size of the resulting emulsion was 0.2.
The silver halide emulsion containing ultrafine silver iodobromide particles of 033 μm was changed to be added immediately after ejection. At this time, X-
The 2 aqueous solutions were added at a constant flow rate so that the addition amount became 13558 mL, and the pAg of the bulk liquid was kept at 7.86 while adding X-1. Other than the above, Comparative Example 1
Same as.
【００３６】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。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 have an average equivalent circle diameter of 1.69 μm and an average thickness of 0.
08 μm.
【００３７】（乳剤Ｃ／本発明）比較例２において、特
開平１０−４３５０号公報に記載の攪拌機の代わりに、
ＤｅＢＥＥ２０００を混合器として用いる以外は、比較
例２と同様にした。ＤｅＢＥＥ２０００から生成する微
粒子の平均サイズは０．０１６μｍであった。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。(Emulsion C / Invention) In Comparative Example 2, instead of the stirrer described in JP-A-10-4350,
The procedure was the same as Comparative Example 2, except that DeBEE2000 was used as the mixer. The average size of the fine particles generated from DeBEE2000 was 0.016 μm. 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 have an average equivalent circle diameter of 1.91 μm and an average thickness of 0.
08 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. According to the present invention, tabular grains having a small thickness and a small amount of fine particles remaining can be formed.
【００３８】＜実施例３＞特開平５−３４６６３１号公
報の実施例１と同様にして、化学増感および分光増感を
を行い、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着できるため、より高い写真感
度がえられた。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 3> Chemical sensitization and spectral sensitization were performed in the same manner as in Example 1 of JP-A-5-346631, and photographic performance was compared. Emulsion C to Emulsion A
Has a higher photographic sensitivity because it can adsorb a large amount of the sensitizing dye. In Emulsion B, many fine particles remained, and high photographic sensitivity was not obtained.
【００３９】[0039]
【発明の効果】本発明により、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
製が可能となる。According to the present invention, silver halide grains having a small size and excellent monodispersity can be formed. By using it for nucleation and crystal growth, it becomes possible to prepare a monodispersed silver halide photographic emulsion or a thin tabular silver halide photographic emulsion.
Claims (6)
くとも一方を高い流速を持つ直線状の噴流とし、前記二
種類の溶液を短時間内に混合してハロゲン化銀粒子を連
続的に生成することを特徴とするハロゲン化銀写真乳剤
の製造方法。At least one of an aqueous silver salt solution and an aqueous halide salt solution is a linear jet having a high flow rate, and the two solutions are mixed within a short time to continuously produce silver halide grains. A method for producing a silver halide photographic emulsion.
くとも一方を高い流速を持つ直線状の噴流とし、前記二
種類の溶液を循環させずに混合してハロゲン化銀粒子を
連続的に生成することを特徴とするハロゲン化銀写真乳
剤の製造方法。2. A silver halide grain is continuously produced by mixing at least one of an aqueous solution of a silver salt and an aqueous solution of a halide salt as a linear jet having a high flow rate and mixing the two kinds of solutions without circulation. A method for producing a silver halide photographic emulsion.
くとも一方を高い流速を持つ直線状の噴流とし、前記二
種類の溶液を機械的攪拌を伴わずに混合してハロゲン化
銀粒子を連続的に生成することを特徴とするハロゲン化
銀写真乳剤の製造方法。3. A method according to claim 1, wherein at least one of the aqueous silver salt solution and the aqueous halide salt solution is a linear jet having a high flow rate, and the two types of solutions are mixed without mechanical stirring to continuously form silver halide grains. And a method for producing a silver halide photographic emulsion.
くとも一方を高い流速を持つ直線状の噴流とし、該噴流
に平行でかつ内部に窪みを有する細管に前記二種類の溶
液を通過させて、短時間内に混合してハロゲン化銀粒子
を連続的に生成することを特徴とするハロゲン化銀写真
乳剤の製造方法。4. A method according to claim 1, wherein at least one of the silver salt aqueous solution and the halide salt aqueous solution is a linear jet having a high flow rate, and the two types of solutions are passed through a thin tube parallel to the jet and having a recess therein. A method for producing a silver halide photographic emulsion, comprising mixing silver halide grains continuously within a short time.
くとも一方を高い流速を持つ直線状の噴流とし、該噴流
に平行でかつ内部に窪みを有する細管に前記二種類の溶
液を通過させて、循環させずに混合してハロゲン化銀粒
子を連続的に生成することを特徴とするハロゲン化銀写
真乳剤の製造方法。5. A method according to claim 1, wherein at least one of the silver salt aqueous solution and the halide salt aqueous solution is a linear jet having a high flow rate, and the two types of solutions are passed through a thin tube parallel to the jet and having a recess therein. A method for producing a silver halide photographic emulsion, characterized in that silver halide grains are continuously produced by mixing without circulation.
くとも一方を高い流速を持つ直線状の噴流とし、該噴流
に平行でかつ内部に窪みを有する細管に前記二種類の溶
液を通過させて、機械的攪拌を伴わずに混合してハロゲ
ン化銀粒子を連続的に生成することを特徴とするハロゲ
ン化銀写真乳剤の製造方法。6. A method according to claim 1, wherein at least one of the silver salt aqueous solution and the halide salt aqueous solution is a linear jet having a high flow rate, and the two types of solutions are passed through a thin tube parallel to the jet and having a recess therein. A method for producing a silver halide photographic emulsion, characterized by continuously producing silver halide grains by mixing without mechanical stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000082482A JP2000338620A (en) | 1999-03-25 | 2000-03-23 | Method for manufacturing silver halide photographic emulsion |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-82332 | 1999-03-25 | ||
| JP8233299 | 1999-03-25 | ||
| JP2000082482A JP2000338620A (en) | 1999-03-25 | 2000-03-23 | Method for manufacturing silver halide photographic emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000338620A true JP2000338620A (en) | 2000-12-08 |
Family
ID=26423360
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000082482A Pending JP2000338620A (en) | 1999-03-25 | 2000-03-23 | Method for manufacturing silver halide photographic emulsion |
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| JP (1) | JP2000338620A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6878511B2 (en) | 2002-04-26 | 2005-04-12 | Fuji Photo Film Co., Ltd. | Process of producing silver halide photographic emulsions |
| US7297179B2 (en) | 2002-09-30 | 2007-11-20 | Fujifilm Corporation | Method of producing metal particles, and metal oxide obtained from the particles |
-
2000
- 2000-03-23 JP JP2000082482A patent/JP2000338620A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6878511B2 (en) | 2002-04-26 | 2005-04-12 | Fuji Photo Film Co., Ltd. | Process of producing silver halide photographic emulsions |
| US7297179B2 (en) | 2002-09-30 | 2007-11-20 | Fujifilm Corporation | Method of producing metal particles, and metal oxide obtained from the particles |
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