EP0600543B1 - Verfahren zur Herstellung von Silberhalogenidkörnern - Google Patents

Verfahren zur Herstellung von Silberhalogenidkörnern Download PDF

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Publication number
EP0600543B1
EP0600543B1 EP19930203293 EP93203293A EP0600543B1 EP 0600543 B1 EP0600543 B1 EP 0600543B1 EP 19930203293 EP19930203293 EP 19930203293 EP 93203293 A EP93203293 A EP 93203293A EP 0600543 B1 EP0600543 B1 EP 0600543B1
Authority
EP
European Patent Office
Prior art keywords
gelatin
range
process according
reactor
chloride
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.)
Expired - Lifetime
Application number
EP19930203293
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English (en)
French (fr)
Other versions
EP0600543A1 (de
Inventor
John Arthur Kodak Limited Bee
Andrew Kodak Limited Hartman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
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Publication date
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Publication of EP0600543A1 publication Critical patent/EP0600543A1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins

Definitions

  • This invention relates to a process for producing silver halide grains and to a process for the formation of a photographic emulsion.
  • nucleus formation is a step in which new crystals are formed and a sharp increase in the number of crystals takes place.
  • Crystal growth is a step in which new layers are added to existing crystals. Nucleus formation is rapid, generally taking less than a minute. Crystal growth is slower, generally taking 20 to 60 minutes.
  • silver halide grains are precipitated in the presence of a protective colloid i.e. gelatin.
  • a protective colloid i.e. gelatin.
  • Conventional gelatin solutions display a sol-gel property and this generally constrains precipitation of silver halide emulsions in which gelatin is used as a peptizing agent to temperatures above 35°C.
  • European Patent Application EP-A-374853 relates to a process of producing silver halide grains in which the inventive step is to separate nucleus formation step (a) from crystal growth step (b) by carrying out the former in a separate mixer outside the reactor in which (b) takes place.
  • the stated aim of this process is to produce silver crystal grains having a homogeneous halide composition in each crystal and having no halide distribution among the grains.
  • the nucleus formation step in this process is carried out at a reduced temperature in the presence of low molecular weight gelatin which can be obtained from ordinary gelatin.
  • the use of low molecular weight gelatin in this process is confined to step (a) in the mixer. It is not used in step (b) in the main reactor.
  • Japanese patent applications JP-A-2000838 and JP-A-1213637 disclose silver halide emulsions comprising silver halide grains, specifically tabular grains, produced by a process wherein nucleus formation and crystal growth take place in the presence of a low molecular weight gelatin, to provide grains of uniform particle size and monodispersibility.
  • JP-A-4110934 and JP-A-4110935 disclose the use of a low molecular weight gelatin in a process of nucleus formation and crystal growth of silver halide grains at a temperature of at least 40°C to overcome fog formation and low sensitivity.
  • a process for the production of silver chloride grains in which an aqueous solution comprising a water-soluble chloride, a water-soluble silver salt and a protective colloid is produced in a reactor and silver chloride grains are formed in the reactor by reaction of the chloride and the silver salt, wherein a major proportion of the protective colloid is a modified mammalian gelatin having a mean molecular weight in the range 5000 to 30000, characterised in that nucleus formation and crystal growth both take place in the reactor and that the process is carried out at a temperature in the range 5 to 35°C.
  • a process for the formation of a photographic emulsion in which an aqueous solution comprising a water-soluble chloride, a water-soluble silver salt and a protective colloid is produced in a reactor and silver chloride grains are formed in the reactor by reaction of the chloride and the silver salt, wherein a major proportion of the protective colloid is a modified mammalian gelatin having a mean molecular weight in the range 5000 to 30000, characterised in that nucleus formation and crystal growth both take place in the reactor and that the process is carried out at a temperature in the range 5 to 35°C
  • the silver chloride grains are produced by reacting an aqueous silver salt solution and an aqueous chloride solution in an aqueous colloid solution in the reactor.
  • Possible modes of operation include the single jet method and the double jet method.
  • the single jet method the aqueous solution of the colloid and the chloride are placed in the reactor and the aqueous silver salt solution is added with stirring for a suitable time.
  • the double jet method which is preferred, the aqueous colloid solution is placed in the reactor and the aqueous chloride solution and the aqueous salt solution are added to the solution in the reactor.
  • the modified mammalian gelatin has a mean molecular weight in the range 5000 to 30000, preferably in the range 10000 to 20000.
  • modified gelatin can be obtained in a variety of ways. It can be obtained by treating an aqueous solution of normal gelatin, which generally will have a mean molecular weight of approximately 100000, with a gelatin decomposing enzyme such as trypsin. Alternatively the gelatin can be hydrolised with an acid, heating it at a low pH e.g. in the range 1 to 3, or with a base, heating it at a high pH e.g. in the range 10 to 12.
  • the process is carried out at a temperature up to 35°C, a preferred range being 5 to 35°C.
  • ambient temperature i. e. the range 18 to 20°C
  • Heating of the reactor is preferably avoided.
  • the process temperature is preferably controlled within a narrow range, i.e. to within 0.5 degrees and particularly to within the range 0.25 to 0.3 degrees C.
  • Halides and silver salts are preferred which can be used to precipitate silver chloride, bromide, bromoiodide or chlorobromide.
  • the halide used is sodium chloride and the silver salt silver nitrate is preferred.
  • halide and the silver salt are supplied to the reactor in the double jet method, it is convenient for them to be supplied at the same or at similar rates, suitable rates depending partly upon the scale of operation. It is preferred that during the process the vAg of the solution is controlled to prevent significant variation.
  • the vAg of the solution is controlled to prevent significant variation.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Colloid Chemistry (AREA)

Claims (12)

  1. Verfahren zur Herstellung von Silberchloridkörnern, bei dem eine wässrige Lösung mit Wasser-löslichem Chlorid, einem Wasser-löslichen Silbersalz und einem Schutzkolloid in einem Reaktor erzeugt und Silberchloridkörner in dem Reaktor erzeugt werden durch Umsetzung des Chlorides und des Silbersalzes, wobei ein Hauptanteil des Schutzkolloides eine modifizierte Säugetier-Gelatine mit einem mittleren Molekulargewicht im Bereich von 5000 bis 30000 ist, dadurch gekennzeichnet, daß die Keimbildung und das Kristallwachstum beide in dem Reaktor stattfinden und daß das Verfahren bei einer Temperatur im Bereich von 5 bis 35°C durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Säugetier-Gelatine ein mittleres Molekulargewicht im Bereich von 10000 bis 20000 hat.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Behandlung von normaler Gelatine mit dem Gelatine zersetzenden Enzym Trypsin.
  4. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Behandlung von normaler Gelatine bei einem niedrigen pH-Wert im Bereich von 1 bis 3.
  5. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Behandlung von normaler Gelatine bei einem hohen pH-Wert im Bereich von 10 bis 12.
  6. Verfahren zur Herstellung einer photographischen Emulsion, bei dem eine wässrige Lösung mit einem Wasser-löslichen Chlorid, einem Wasser-löslichen Silbersalz und einem Schutzkolloid in einem Reaktor erzeugt und Silberchloridkörner in dem Reaktor erzeugt werden durch Umsetzung des Chlorides und des Silbersalzes, wobei ein Hauptteil des Schutzkolloides eine modifizierte Säugetier-Gelatine mit einem mittleren Molekulargewicht im Bereich von 5000 bis 30000 ist, dadurch gekennzeichnet, daß die Keimbildung und das Kristallwachstum beide in dem Reaktor erfolgen und das Verfahren bei einer Temperatur im Bereich von 5 bis 35°C durchgeführt wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die Säugetier-Gelatine ein Molekulargewicht im Bereich von 10000 bis 20000 hat.
  8. Verfahren nach Anspruch 6 oder Anspruch 7, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Behandlung von normaler Gelatine mit einem Gelatine zersetzenden Enzym.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Gelatine zersetzende Enzym Trypsin ist.
  10. Verfahren nach Anspruch 6 oder Anspruch 7, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Erhitzung von normaler Gelatine bei einem niedrigen pH-Wert im Bereich von 1 bis 3.
  11. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß die Säugetier-Gelatine erhalten wurde durch Erhitzung von normaler Gelatine bei einem hohen pH-Wert im Bereich von 10 bis 12.
  12. Verfahren nach einem der Ansprüche 6 bis 11, dadurch gekennzeichnet, daß die Prozeß-Temperatur derart gesteuert wird, daß sie innerhalb des Bereiches von 0,25 bis 0,3°C liegt.
EP19930203293 1992-11-28 1993-11-25 Verfahren zur Herstellung von Silberhalogenidkörnern Expired - Lifetime EP0600543B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9224967 1992-11-28
GB929224967A GB9224967D0 (en) 1992-11-28 1992-11-28 Process for producing silver halide grains

Publications (2)

Publication Number Publication Date
EP0600543A1 EP0600543A1 (de) 1994-06-08
EP0600543B1 true EP0600543B1 (de) 1999-03-03

Family

ID=10725837

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19930203293 Expired - Lifetime EP0600543B1 (de) 1992-11-28 1993-11-25 Verfahren zur Herstellung von Silberhalogenidkörnern

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EP (1) EP0600543B1 (de)
JP (1) JPH06214329A (de)
DE (1) DE69323697T2 (de)
GB (1) GB9224967D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6344312B1 (en) 1999-02-10 2002-02-05 Fuji Photo Film Co., Ltd. Heat developable photosensitive material

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1501821A (fr) * 1966-09-20 1967-11-18 Kodak Pathe Nouvelle émulsion photographique à grand pouvoir couvrant
GB1173196A (en) * 1967-01-24 1969-12-03 Wolfen Filmfab Veb Photographic Material Containing Silver Halide and Process for its Manufacture
JP2559264B2 (ja) * 1987-12-17 1996-12-04 富士写真フイルム株式会社 ハロゲン化銀乳剤及びその製造方法
JPH01213637A (ja) * 1988-02-22 1989-08-28 Fuji Photo Film Co Ltd ハロゲン化銀乳剤とその製造方法並びに処理方法
JP2700676B2 (ja) * 1988-12-22 1998-01-21 富士写真フイルム株式会社 ハロゲン化銀粒子の製造方法
JPH04110935A (ja) * 1990-08-31 1992-04-13 Konica Corp ハロゲン化銀写真乳剤
JP2926435B2 (ja) * 1990-08-31 1999-07-28 コニカ株式会社 ハロゲン化銀写真乳剤及びその製造方法

Also Published As

Publication number Publication date
JPH06214329A (ja) 1994-08-05
EP0600543A1 (de) 1994-06-08
GB9224967D0 (en) 1993-01-20
DE69323697T2 (de) 1999-09-30
DE69323697D1 (de) 1999-04-08

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