DE2844942A1 - METHOD OF MANUFACTURING MONODISPERSE PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONS - Google Patents
METHOD OF MANUFACTURING MONODISPERSE PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONSInfo
- Publication number
- DE2844942A1 DE2844942A1 DE19782844942 DE2844942A DE2844942A1 DE 2844942 A1 DE2844942 A1 DE 2844942A1 DE 19782844942 DE19782844942 DE 19782844942 DE 2844942 A DE2844942 A DE 2844942A DE 2844942 A1 DE2844942 A1 DE 2844942A1
- Authority
- DE
- Germany
- Prior art keywords
- silver halide
- salt
- solution
- crystals
- rhodium
- 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.)
- Ceased
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 45
- 239000004332 silver Substances 0.000 title claims description 45
- 239000000839 emulsion Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 3
- -1 silver halide Chemical class 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 23
- 150000003283 rhodium Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 230000006911 nucleation Effects 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- BWYMLYMBQPWYCL-UHFFFAOYSA-N [Na].[Rh] Chemical compound [Na].[Rh] BWYMLYMBQPWYCL-UHFFFAOYSA-N 0.000 claims 1
- 210000004072 lung Anatomy 0.000 claims 1
- 239000002609 medium Substances 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical class [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- 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
- G03C1/015—Apparatus or processes for the preparation of emulsions
-
- 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
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/0357—Monodisperse emulsion
-
- 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
- G03C2200/00—Details
- G03C2200/06—Additive
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Colloid Chemistry (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
DR. BERG mPL.-ING. GTAPF DIPL.-ING. 3CHWA3E DR. DR. SANDMAIRDR. BERG mPL.-ING. GTAPF DIPL.-ING. 3CHWA3E DR. DR. SANDMAIR
PATENTANWÄLTE Postfach 860245 · 8000 München 86 2 8 4 A 9 4PATENTANWÄLTE PO Box 860245 8000 Munich 86 2 8 4 A 9 4
Anwaltsakte 29 511 16, Oktober 1978Attorney File 29 511 16 October 1978
ILPORD LIMITED Basildon, Essex / GroßbritannienILPORD LIMITED Basildon, Essex / Great Britain
Verfahren zur Herstellung von monodispersen photographischen SilberhalogenidemulsionenProcess for the preparation of monodisperse photographic silver halide emulsions
90981 6/101290981 6/1012
r (OSJ) 988272 Telegramme: Bankkonten: Hypo-Bank München 4410122850r (OSJ) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850
988273 BERGSTAPFPATENT München (BLZ 70020011) Swift Code: HYPO DE MM988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM
9SJ274 TELEX: Bayec Vereinsbank München 453100 (BLZ 70020270) 9SJ274 TELEX: Bayec Vereinsbank Munich 453100 (BLZ 70020270)
583310 0524560BERGd Postscheck München 65343-808 (BLZ 70010080)583310 0524560BERGd Postscheck Munich 65343-808 (BLZ 70010080)
Case 8-11388/lLF 1158/+
DeutschlandCase 8-11388 / lLF 1158 / +
Germany
Verfahren zur Herstellung von monodispersen photographischen SilberhalogenidemulsionenProcess for the preparation of monodisperse photographic silver halide emulsions
Die vorliegende Erfindung betrifft die Herstellung photographischer Silberhalogenidemulsionen und deren Verwendung in photographischen Materialien.The present invention relates to the preparation of photographic silver halide emulsions and their use in photographic materials.
In der deutschen Offenlegungsschrift 22 21 082 ist ein Verfahren zur Herstellung einer Silberhalogenidemulsion vom monodispersen Typus beschrieben, bei welchem man die wässrige Lösung eines Silbersalzes und die wässrige Lösung eines Alkali- oder Ammoniumhalogenids einem wässrigen Dispergiermedium zusetzt, das ein Schutzkolloid in solcher Konzentration enthält, dass sich Silberhalogenidkristallkeime bilden, und durch Zugabe wässriger Silbersalzlösung und wässriger Alkali- oder Ammoniumhalogenidlösung zum wässrigen Dispergiermedium die Silberhalogenidkristalle in ihrer Grosse zunehmen lässt, wobei man durch Kontrolle der Bedingungen im wässrigen Dispergiermedium dafür sorgt, dass der Uebersättigungsgrad an Silberhalogenid in Lösung in der flüssigen Phase des Dispergiermediums zu weitgehend jedem Zeitpunkt während der Wachstumsstufe grosser ist als X-mal der Uebersättigungsgrad an Silberhalogenid in Lösung, bei dem unter den gleichen Löslichkeitsverhältnissen Keimbildung eintreten würde, wobei zum jeweiligen Zeitpunkt während der Kristallwachstumsstufe giltIn the German Offenlegungsschrift 22 21 082 discloses a method for preparing a monodisperse type silver halide emulsion in which one the aqueous solution of a silver salt and the aqueous solution of an alkali or ammonium halide one added aqueous dispersing medium, which contains a protective colloid in such a concentration that silver halide crystal nuclei form, and by adding aqueous silver salt solution and aqueous alkali or ammonium halide solution to the aqueous dispersing medium, the silver halide crystals are allowed to increase in size, whereby one by controlling the conditions in the aqueous dispersion medium ensures that the degree of supersaturation increases Silver halide in solution in the liquid phase of the dispersing medium at substantially every point in time during the growth stage is greater than X times the degree of supersaturation of silver halide in solution, at which below the same solubility ratios nucleation would occur at each point in time during the Crystal growth stage applies
X = Cr1)2 / (r2)2 ,X = Cr 1 ) 2 / (r 2 ) 2 ,
worin r, die mittlere lineare Grosse der Kristalle unmittelbar nach Beendigung der Keimbildung war und r2 die mittlere lineare Grosse der Kristalle zum jeweiligen Zeitpunkt ist.where r, was the mean linear size of the crystals immediately after the end of the nucleation and r 2 is the mean linear size of the crystals at the respective point in time.
909816/101 2909816/101 2
28U94228U942
Der Uebersättigungsgrad sei definiert als die Konzentration an Silberhalogenid in Lösung in der flüssigen Phase des Dispergiermediums minus der Gleichgewichtskonzentration an Silberhalogenid in Lösung in der flüssigen Phase des Silberhalogenidkristalle der gleichen Grosse enthaltenden Mediums. Der Uebersättigungsgrad stellt somit ein Mass für die zum Kristallwachstum verfügbare Menge Silberhalogenid in Lösung dar.The degree of supersaturation is defined as the concentration of silver halide in solution in the liquid Phase of the dispersing medium minus the equilibrium concentration of silver halide in solution in the liquid Phase of the medium containing silver halide crystals of the same size. The degree of oversaturation represents thus a measure of the amount of silver halide available for crystal growth in solution.
Der Uebersättigungsgrad an Silberhalogenid in Lösung in der flüssigen Phase des Dispergiermediums soll für den grössten Teil der Kristallwachstumsstufe oder sogar für deren Gesamtdauer grosser als X-mal der Uebersättigungsgrad an Silberhalogenid in Lösung sein, bei dem Keimbildung eintritt. Kurzzeitig darf der Uebersättigungsgrad jedoch unter diesen Wert sinken.The degree of supersaturation of silver halide in solution in the liquid phase of the dispersing medium should be for most of the crystal growth stage or even for its total duration greater than X times the degree of supersaturation be of silver halide in solution at which nucleation occurs. The degree of oversaturation is allowed for a short time however fall below this value.
Auf einen Phototräger gegossene, bildweise belichtete und entwickelte monodisperse Silberhalogenidemulsionen neigen dazu, eine photographische Abbildung von höherem Kontrast zu liefern als ähnliche Silberhalogenidemulsionen, die nicht monodispers sind. Für gewisse Zwecke ist es jedoch wünschenswert, ein Silberbild von höherem Kontrast zu erzeugen, als unter "Verwendung monodisperser Silberhalogenidemulsion erhältlich ist.Monodisperse silver halide emulsions cast on a photo carrier, imagewise exposed and developed tend to give a photographic image of higher contrast than similar silver halide emulsions, which are not monodisperse. However, for certain purposes it is desirable to have a higher contrast silver image than can be obtained using "monodisperse silver halide emulsion."
Eine Aufgabe der vorliegenden Erfindung besteht nun darin, ein Verfahren zur Erzeugung von Silberhalogenidemulsionen nach der aus der deutschen Offenlegungsschrift 22 21 082 bekannten Methode vorzuschlagen ,welche jedoch bei der Belichtung und Entwicklung einen höheren Kontrast aufweisen.It is an object of the present invention to provide a method for producing silver halide emulsions to propose according to the method known from German Offenlegungsschrift 22 21 082, which, however have higher contrast during exposure and development.
Gegenstand vorliegender Erfindung ist ein Verfahren zur Herstellung einer Silberhalogenidemulsion vom monodispersen Typus nach der Methode der deutschen Offenlegungsschrift 22 21 082, welches dadurch gekennzeichnet ist, dass man die Silberhalogenidkristallkeimbildung in Gegenwart eines wasserlöslichen Rhodiumsalzes vornimmt und/oder die Silberhalogenidkristalle in Gegenwart eines wasserlöslichen Rhodiumsalzes wachsen lässt.The present invention relates to a process for preparing a monodisperse silver halide emulsion Type according to the method of the German Offenlegungsschrift 22 21 082, which is characterized by that the silver halide crystal nucleation is carried out in the presence of a water-soluble rhodium salt and / or growing the silver halide crystals in the presence of a water-soluble rhodium salt.
909816/1012909816/1012
Als Rhodiumsalze eignen sich wasserlösliche Rhodium-III-salze, wie die Halogenide (Chloride) oder Sulfate, einschliesslich komplexer Rhodium-III-salze wie Natrium- oder Kaliumrhodiumhalogenide oder -sulfate.Suitable rhodium salts are water-soluble rhodium (III) salts, such as the halides (chlorides) or Sulphates, including complex rhodium III salts such as sodium or potassium rhodium halides or sulphates.
Bei Anwendung des erfindungsgemässen Verfahrens erhält man die grösste Kontrastzunahme, wenn man die Silberhalogenidkristalle in Gegenwart eines wasserlöslichen Rhodiumsalzes wachsen lässt. Wird das Rhodiumsalz der Emulsion zugesetzt, nachdem das Wachstum der Silberhalogenidkristalle aufgehört hat, so erhält man praktisch keine Zunahme im Kontrast.When using the method according to the invention, the greatest increase in contrast is obtained when the Silver halide crystals can grow in the presence of a water-soluble rhodium salt. It will Rhodium salt added to the emulsion after the growth of the silver halide crystals has stopped, there is practically no increase in contrast.
Besonders bevorzugt ist es wenn man während der gesamten Zeit des Silberhalogenidwachstums laufend geringe Mengen Rhodium salz zusetzt. Somit kann man das Rhodiumsalz während des Wachstums entweder mit der Silbersalzlösung, mit der Halogenidlösung oder auch getrennt in die Emulsion einbrigenn. BesondersIt is particularly preferred if the silver halide growth is continuously low Amounts of rhodium salt added. Thus, the rhodium salt can either be mixed with the silver salt solution during growth, with the halide solution or separately in the emulsion. Particularly
bevorzugt wird es in der Halogenidlösung aufgelöst und daher mit dieser zusammen während des Wachstums zugesetzt.it is preferably dissolved in the halide solution and therefore together with it during growth added.
Besonders bevorzugt ist ein lösliches Rhodiumkomplexsalz, wie insbesondere das wasserlösliche Natiumhexachlororhodit A soluble rhodium complex salt, such as in particular the water-soluble sodium hexachlororhodite, is particularly preferred
aoRhCT,;).aoRhCT ,;).
Die der Emulsion zugesetzte Rhodiumsalzmenge kann in weiten Grenzen schwanken, aber Quantitäten über 7 · 10" Mol Rhodiumsalz pro Mol Silberhalogenid ergeben keine weitere Aenderung des Kontrasts. Eine zu verwendende Rhodiumsalzmenge im Bereich von 2 . 10 bisThe amount of rhodium salt added to the emulsion can vary within wide limits, but quantities exceed Yield 7x10 "moles of rhodium salt per mole of silver halide no further change in contrast. An amount of rhodium salt to be used in the range of 2. 10 to
_«v
2,7 · 10 ' pro Mol Silberhalogenid ist besonders geeignet._ «V
2.7x10 'per mole of silver halide is particularly suitable.
_r7_ r 7
Grossere Rhodiummengen als 2,7 · 10 neigen dazu, die photographische Empfindlichkeit des Materials auf in der Regel nicht mehr brauchbare Werte zu vermindern.Greater amounts of rhodium than 2.7 · 10 tend to be to reduce the photographic sensitivity of the material to values that are generally no longer usable.
Vorzugsweise wird das Rhodiumsalz während des Wachstums, das üblicherweise bei einer zwischen 30°C und 65°C gehaltenen Temperatur stattfindet, in den Silberhalogenidkristall eingebaut. Ebenfalls wird derThe rhodium salt is preferably used during growth, which is usually carried out at a temperature between 30 ° C and 65 ° C held temperature takes place in the silver halide crystal built-in. The
909816/1012909816/1012
pAg des Emulsionsmediums während der Rhodiumzugabe vorzugsweise zwischen 3,.4 und 9,4 gehalten.pAg of the emulsion medium during the rhodium addition is preferred held between 3.4 and 9.4.
Als Schutzkolloid wird Gelatine und als Silbersalz Silbernitrat bevorzugt.Gelatin is preferred as the protective colloid and silver nitrate as the silver salt.
Die Silberhalogenidemulsionen, "welche einen weiteren Gegenstand dieser Erfindung darstellen, werden besonders in photographischen Materialien verwendet, wo ein sehr hoher Kontrast gefordert wird, beispielsweise in gewissen Filmen für das graphische Gewerbe und in Photopapieren mit besonders hohem Kontrast.The silver halide emulsions "which are a further object of this invention become especially used in photographic materials where very high contrast is required, for example in certain films for the graphic industry and in photo papers with particularly high contrast.
Das nachfolgende Beispiel dient zur Erläuterung
der Erfindung.
BEISPIEL Herstellung der Emulsion I. The following example serves to explain the invention.
EXAMPLE Preparation of Emulsion I.
Man gibt 120 ml einer photographischen Emulsion, die kubische Silberhalogenidkristalle (Chlorobromid 70/30) von 0,12 μΐη mittlerer Würfelkantenlänge enthält, zusammen mit 600 .ml 5%iger wässriger Gelatinelösung in ein rostfreies Stahlgefäss. Die Emulsion war durch Doppeleindüsung gleicher Mengen 4,7-molarer wässriger Silbernitratlösung und 4,7-molarer wässriger Ammoniumchlorid/Ammoniumbromidlösung (Gewichtsverhältnis 70/30) in Gelatine hergestellt worden. Die dispergierte Emulsion enthält 3% Gelatine. An ein Regelgerät angeschlossene Elektroden sind in die dispergierte Emulsion eingesetzt und dienen dazu, die freie Silberionenkonzentration zu messen und konstant zu halten. Die Emulsion wird gerührt und bei einer Temperatur von 400C gehalten. Dann lässt man die Silberhalogenidkristalle durch Doppeleindüsung gleicher Mengen Silbernitratlösung und Ammoniumchlorid/Ammoniumbromid (Gewichtsverhältnis 70/30) derselben 4,7-molaren Konzentration wachsen. Die Zugabegeschwindigkeit, die zugesetzte Menge Lösung und die mittlere Kristallkantenlänge zu Beginn der Zugabe sind in der nachfolgenden Tabelle angegeben:120 ml of a photographic emulsion containing cubic silver halide crystals (chlorobromide 70/30) with an average cube edge length of 0.12 μm are added to a stainless steel vessel together with 600 ml of 5% aqueous gelatin solution. The emulsion was prepared by injecting equal amounts of 4.7 molar aqueous silver nitrate solution and 4.7 molar aqueous ammonium chloride / ammonium bromide solution (weight ratio 70/30) into gelatine. The dispersed emulsion contains 3% gelatin. Electrodes connected to a control device are inserted into the dispersed emulsion and serve to measure the free silver ion concentration and keep it constant. The emulsion is stirred and maintained at a temperature of 40 0 C. The silver halide crystals are then allowed to grow by double injection of equal amounts of silver nitrate solution and ammonium chloride / ammonium bromide (70/30 weight ratio) of the same 4.7 molar concentration. The rate of addition, the amount of solution added and the average crystal edge length at the beginning of the addition are given in the table below:
9098 16/10129098 16/1012
Zugabege- Bei der jeweiligen Mittlere Würfelkan-Addition- At the respective middle cube can-
schwindigkeit Geschwindigkeit zu- tenlänge zu Beginn speed speed tenlänge to-start
ίτηΐ/νΛ gesetzte Menge der jeweiligen Ge-ίτηΐ / νΛ set amount of the respective
Silbernitrat (ml) schwindigkeitSilver Nitrate (ml) speed
(μΐη)(μΐη)
624 24,2 0,12624 24.2 0.12
975 67,0 · 0,15975 67.0 x 0.15
1733 110,4 0,201733 110.4 0.20
2708 164,8 0,252708 164.8 0.25
3900 . 230,2 0,303900. 230.2 0.30
Die Zugabegeschwindigkeiten werden so berechnet, dass sie proportional dem Quadrat der mittleren linearen Abmessung der Kristallgrösse zunehmen. Die fertige Emulsion weist Kristalle mit einer mittleren Kantenlänge von 0,35 μπι auf.The addition rates are calculated to be proportional to the square of the mean linear Increase the size of the crystal. The finished emulsion has crystals with a medium edge length of 0.35 μπι on.
Bei diesem Beispiel,hört die Keimbildung auf, wenn die Kristalle 0,12 μπι erreichen.In this example, the nucleation stops when the crystals reach 0.12 μm.
X = (O,12)2 / (0,35)2 = 0,12X = (O, 12) 2 / (0.35) 2 = 0.12
Wenn die Kristalle 0,35 μπι mittlere Kantenlänge erreichen, liegen somit solche Verhältnisse im Dispergiermedium vor," dass der Uebersättigungsgrad an Silberhalogenid in der flüssigen Phase nicht weniger als 0,12-mal den Uebersättigungsgrad an Silberhalogenid in Lösung beträgt, bei dem unter den Versuchsbedingungen Keimbildung eingetreten wäre.When the crystals reach 0.35 μm mean edge length, if there are such conditions in the dispersing medium, " that the degree of supersaturation of silver halide in the liquid phase is not less than 0.12 times the degree of supersaturation of silver halide in solution, in which nucleation occurred under the experimental conditions were.
Aus den Werten für die Wachstumsgeschwindigkeit der im Beispiel gebildeten Kristalle berechnet sich der Uebersättigungsgrad als 0,84-mal derjenige, bei dem mit Kristallen von 0,31 μπι Keimbildung eintreten würde, bzw. 0,66-mal derjenige, bei dem mit Kristallen von 0,35 μπι Keimbildung eintreten würde.The is calculated from the values for the growth rate of the crystals formed in the example Degree of oversaturation than 0.84 times that at which nucleation would occur with crystals of 0.31 μm, or 0.66 times that in which μπι with crystals of 0.35 Nucleation would occur.
Beim erfindungsgemässen Verfahren ist es erforderlich, Uebersättigungsgrade von mehr als 0,15, wenn die Kristalle 0,31 μπι erreichen, bzw. 0,12, wenn die Kristalle 0,35 μπι erreichen,aufrechtzuerhalten. Im Beispiel sind diese Werte eingehalten.In the method according to the invention, it is necessary Degrees of supersaturation of more than 0.15 when the crystals reach 0.31 μπι, or 0.12 when the Crystals 0.35 μπι reach, maintain. These values are adhered to in the example.
9 0 9 8 16/10129 0 9 8 16/1012
Man lässt die Silberchlorobromidkristalle (0,12 μπι) durch Doppeleindüsung auf 0,35 μπι wachsen, wobei man die Uebersättigungsgrade wie beider.Herstellung der Emulsion I aufrechterhält. Jedoch setzt man dabei während des gesamten Wachstums 0,03 ml O,l%ige Natriumhexachlororhoditlösung in lOn-Lithiumchlorid pro I^ Gramm-mol Silber über die 4,7-molare wässrige Ammoniumchlorid/ Ammoniumbromidlösung (Gewichtsverhältnis 70/30) dazu.One leaves the silver chlorobromide crystals (0.12 μm) by double injection to 0.35 μπι grow, with the Degrees of supersaturation as in both. Production of the emulsion I maintains. However, 0.03 ml of 0.1% sodium hexachlororhodite solution is used during the entire growth in lOn lithium chloride per 1 ^ gram-mol Silver over the 4.7 molar aqueous ammonium chloride / Add ammonium bromide solution (weight ratio 70/30).
Die so erhaltenen Emulsionen (I) und (II) werden dann ausgeflockt und mit Wasser gewaschen, bevor man sie in 25%iger wässriger Gelatinelösung redispergiert und mit Schwefelsensibilisator reift. Nach Zugabe satz von Netzmittel und Härter als Giesshilfsmittel werden die stabilisierten Emulsionen auf einem mit Polyäthylen beschichteten Träger vergossen. Die Güsse werden sensitometrisch belichtet und in einem üblichen Entwickler (P.Q. Universal, Warenzeichen der Firma Ilford Ltd.) verarbeitet. Man erhält die folgenden sensitometrischen Werte.The resulting emulsions (I) and (II) are then flocculated and washed with water before they are redispersed in 25% aqueous gelatin solution and matured with a sulfur sensitizer. After adding Set of wetting agents and hardeners as casting aids, the stabilized emulsions are coated with polyethylene coated carrier potted. The casts are exposed sensitometrically and in a conventional Developer (P.Q. Universal, trademark of Ilford Ltd.) processed. The following are obtained sensitometric values.
Emulsion Relative logarithmische Logarithmischer Emulsion Relative logarithmic logarithmic mixer
Empfindlichkeit bei Belichtungsbereich Schwärzung 0,7 Sensitivity at exposure range density 0.7
(D 2,67 . 1,03(D 2.67, 1.03
(II) 2,43 0,93(II) 2.43 0.93
Die durch das Rhodium erzielte Kontrastzunahme wird durch die Differenz der Zahlen für den logarithmischen Belichtungsbereich angezeigt.The increase in contrast achieved by the rhodium is indicated by the difference in the numbers for the logarithmic exposure area.
0 9516/10120 9516/1012
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB43073/77A GB1535016A (en) | 1977-10-17 | 1977-10-17 | Monodispersed emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2844942A1 true DE2844942A1 (en) | 1979-04-19 |
Family
ID=10427213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19782844942 Ceased DE2844942A1 (en) | 1977-10-17 | 1978-10-16 | METHOD OF MANUFACTURING MONODISPERSE PHOTOGRAPHIC SILVER HALOGENIDE EMULSIONS |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5465521A (en) |
| BE (1) | BE871278R (en) |
| CH (1) | CH638904A5 (en) |
| DE (1) | DE2844942A1 (en) |
| FR (1) | FR2406228A2 (en) |
| GB (1) | GB1535016A (en) |
| IT (1) | IT1157371B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58190943A (en) * | 1982-04-30 | 1983-11-08 | Fuji Photo Film Co Ltd | Silver halide photosensitive material and its developing method |
| JPS59212826A (en) * | 1983-05-18 | 1984-12-01 | Konishiroku Photo Ind Co Ltd | Preparation of silver halide photographic emulsion |
| JPS61245151A (en) | 1985-04-23 | 1986-10-31 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| JPS61250645A (en) | 1985-04-30 | 1986-11-07 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| JPS61250643A (en) | 1985-04-30 | 1986-11-07 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| EP0209118B1 (en) | 1985-07-17 | 1991-10-23 | Konica Corporation | Silver halide photographic material |
| JP2515115B2 (en) * | 1987-01-26 | 1996-07-10 | 富士写真フイルム株式会社 | Negative type silver halide photographic light-sensitive material |
| EP0476327B1 (en) | 1990-08-20 | 1999-11-17 | Fuji Photo Film Co., Ltd. | Data-retainable photographic film product and process for producing color print |
| DE69230387T2 (en) | 1991-04-22 | 2000-06-29 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and methods of processing them |
| EP0557616A1 (en) * | 1992-02-07 | 1993-09-01 | Agfa-Gevaert N.V. | A silver halide material suitable for use in a silver salt diffusion transfer process |
| JP2777949B2 (en) | 1992-04-03 | 1998-07-23 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| JP2603189B2 (en) * | 1993-10-27 | 1997-04-23 | コニカ株式会社 | Photosensitive silver halide emulsion |
| EP0782042B1 (en) | 1995-12-27 | 1999-12-01 | Fuji Photo Film Co., Ltd. | Hydrazine compound and silver halide photographic photosensitive material comprising the same |
| EP2003946A4 (en) | 2006-03-28 | 2010-11-03 | Fujifilm Corp | Conductive film, method for producing same, and light-transmitting electromagnetic shielding film |
| CN101512682B (en) | 2006-09-28 | 2012-11-28 | 富士胶片株式会社 | Spontaneous emission display, spontaneous emission display manufacturing method, transparent conductive film, electroluminescence device, solar cell transparent electrode, and electronic paper transpa |
| JP5588597B2 (en) | 2007-03-23 | 2014-09-10 | 富士フイルム株式会社 | Manufacturing method and manufacturing apparatus of conductive material |
| EP2009977A3 (en) | 2007-05-09 | 2011-04-27 | FUJIFILM Corporation | Electromagnetic shielding film and optical filter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1597560A1 (en) * | 1966-12-02 | 1970-08-13 | Eastman Kodak Co | Process for making developable silver halide photographic emulsions |
| DE2221082A1 (en) * | 1971-05-03 | 1972-11-16 | Ilford Ltd | Process for preparing a silver halide emulsion |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE309974C (en) * | 1918-09-21 | |||
| GB775197A (en) * | 1954-10-08 | 1957-05-22 | Ici Ltd | Colour photographic process |
| DE2107118A1 (en) * | 1970-02-16 | 1971-09-02 | Eastman Kodak Co | Salt process for the precipitation of metal |
| US3901713A (en) * | 1971-06-02 | 1975-08-26 | Fuji Photo Film Co Ltd | Process for the manufacture of silver halide photographic emulsion containing iridium and rhodium |
| JPS4933781A (en) * | 1972-07-31 | 1974-03-28 | ||
| JPS585419B2 (en) * | 1975-08-01 | 1983-01-31 | 富士写真フイルム株式会社 | Method for producing silver halide photographic emulsion |
-
1977
- 1977-10-17 GB GB43073/77A patent/GB1535016A/en not_active Expired
-
1978
- 1978-10-11 JP JP12422078A patent/JPS5465521A/en active Granted
- 1978-10-13 CH CH1064878A patent/CH638904A5/en not_active IP Right Cessation
- 1978-10-13 IT IT51489/78A patent/IT1157371B/en active
- 1978-10-16 BE BE191130A patent/BE871278R/en not_active IP Right Cessation
- 1978-10-16 DE DE19782844942 patent/DE2844942A1/en not_active Ceased
- 1978-10-16 FR FR7829445A patent/FR2406228A2/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1597560A1 (en) * | 1966-12-02 | 1970-08-13 | Eastman Kodak Co | Process for making developable silver halide photographic emulsions |
| DE2221082A1 (en) * | 1971-05-03 | 1972-11-16 | Ilford Ltd | Process for preparing a silver halide emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CH638904A5 (en) | 1983-10-14 |
| JPS6133177B2 (en) | 1986-07-31 |
| BE871278R (en) | 1979-04-17 |
| IT1157371B (en) | 1987-02-11 |
| JPS5465521A (en) | 1979-05-26 |
| GB1535016A (en) | 1978-12-06 |
| FR2406228A2 (en) | 1979-05-11 |
| IT7851489A0 (en) | 1978-10-13 |
| FR2406228B2 (en) | 1982-04-30 |
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