EP0584189A1 - Procede d'obtention de grains tabulaires monodisperses. - Google Patents
Procede d'obtention de grains tabulaires monodisperses.Info
- Publication number
- EP0584189A1 EP0584189A1 EP92910989A EP92910989A EP0584189A1 EP 0584189 A1 EP0584189 A1 EP 0584189A1 EP 92910989 A EP92910989 A EP 92910989A EP 92910989 A EP92910989 A EP 92910989A EP 0584189 A1 EP0584189 A1 EP 0584189A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- grains
- germs
- vag
- silver halide
- 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.)
- Granted
Links
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
- G03C1/0051—Tabular grain 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
- G03C1/015—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
- G03C2200/43—Process
Definitions
- the present invention relates to a process for the preparation of a photographic emulsion containing gelatin and tabular silver halide grains having a narrow grain size distribution.
- “Tabular grain” means a grain delimited by two faces
- the shape index i.e. the ratio of diameter to thickness, is greater than at least 2: 1, and preferably at least 5: 1.
- the diameter is defined as the diameter of a circle having an area equal to the projected area of the grain as it appears on a photomicrograph or on an electron micrograph of an emulsion sample.
- tabular silver halide emulsions Many methods of preparing tabular silver halide emulsions have been described.
- United States patent 4,434,226 describes tabular halide grains having a thickness of less than 0.5 ⁇ m, a diameter of at least 0.6 ⁇ m, an average shape index greater than 8 : 1 and representing at least 50% of the total projected surface of the grains. These grains are prepared by a double jet process at a pBr of between 0.6 and 1.6. This process produces tabular silver halide grains having a wide grain size distribution.
- the dispersity is, unless otherwise indicated, represented by the coefficient of variation on the diameter (VOC), which is the ratio between the standard deviation of the diameter of the grains and the
- French patent 2,534,036 describes a process for the preparation of hexagonal and triangular monodispersed flat grains having a thickness of less than 0.3 ⁇ m, a shape index of at least 5: 1 and representing at least 97% of the total projected surface. seeds.
- This process consists of precipitating fine grains having a diameter of less than 0.15 ⁇ m and subjecting them to physical maturation at a pAg of between 8.4 and 11, in the absence of complexing agent.
- U.S. Patent 4,775,617 describes a process for preparing monodispersed flat grains having a thickness of between 0.5 and 6 ⁇ m, a shape index of between 5: 1 and 30: 1 and a coefficient of variation (VOC) of at least 20%, the tabular grains forming at least 50% of the total projected surface of the grains.
- the process involves growing the grains by controlling the rate of concentration of the silver ion and halide solutions at 50 to 60% of the critical crystal growth rate.
- U.S. Patent 4,722,886 describes a process for preparing tabular grains having a thickness of between 0.05 and 0.5 ⁇ m, an average grain volume of between 0.05 and 1 ⁇ m 3 and a form index greater than 2: 1.
- the emulsion predominantly contains tabular grains.
- the process comprises several stages, the precipitation taking place in the presence of ammonia, which is then neutralized before maturation and growth. Dispersity is calculated by volume, which has no real meaning for flat grains if data on the '
- German patent 3,707,135 describes a process for preparing monodispersed tabular grains having a grain size of 0.2 to 3 ⁇ m, a shape index
- the projected area of hexagonal tabular grains is at least 70% of the total projected area.
- the coefficient of variation (VOC) does not exceed 20% and preferably is less than 15%. In this process, the nucleation temperature is lowered to obtain only hexagonal grains, without triangles.
- the processes for preparing silver halide emulsions which can be used on an industrial scale must have specific characteristics, in particular speed and reproducibility, which make it possible to lower the cost thereof.
- the main characteristics of the present process are the very low stirring and the low concentration of the silver salt solution used to prepare the silver halide seeds during the first stage. We will define below what is meant by
- a continuous external nucleator in which the solutions of Ag + ion and of halide arriving separately in continuous flow, mix in a laminar, non-turbulent manner, the very weak agitation being defined by a Reynolds number lower than 2100.
- the germs formed are then directed to the main basin where the 2nd stage, or maturation, then the 3rd stage, or growth will take place.
- a container is used containing a turbine or propeller stirrer which is rotated very slowly, instead of rotating it very rapidly as is usual in conventional preparations of halide emulsions of 'money.
- the speed of rotation of the agitator is not more than 5% of the maximum values used during normal precipitation. The speed of rotation depends on the apparatus used, in particular its size. More specifically, for a 20 l basin in which the usual agitation is 4,000 rpm, the agitation in step (a) according to the present invention will not be greater than 200 rpm. In reactors of much higher capacity, the agitation is slower, in known manner; the adaptation of a laboratory process to an industrial manufacturing process is within the reach of the technician.
- the stirring speed of the maturation (b) and growth (c) stages is between 4,000 and 5,000 rpm for a 20 l basin.
- the present invention also relates to an emulsion with tabular silver halides prepared by the process described above, this emulsion being
- FIGS 1 to 4 are schematic drawings of useful static nucleators.
- the nucleator of FIG. 1 is a reactor with cylindrical symmetry into which the halide solutions and the silver nitrate solutions are introduced.
- the conical part located at the front of the nucleator allows the fluid to be accelerated.
- the position of the central cone is adjustable to allow the speed of ejection of fluids to be changed from the nucleator.
- a variable length tube, not shown here, extends the nucleator.
- the device of Figure 2 is a T-shaped reactor, in which the fluids are introduced parallel in opposite directions and are ejected
- the fluids can meet a portion of smaller diameter, making it possible to adjust the speed of ejection and possibly to be subjected to a slight stirring.
- the device of FIG. 3 in the form of Y is
- the device of FIG. 4 is similar to the device No. 2 as regards the introduction of the reagents, but the ejection is ensured by one or more rows of holes arranged in a crown, the holes all being of the same diameter and being separated by at least 15 ° angle.
- the nucleators described above contribute to determining an average residence time of the germs, characterized by the average time spent by a fluid element of the Ag nitrate solution between its contact with the salt solution. halide and its exit in the form of silver halide seeds. This average residence time is also dependent on the rates of introduction of the fluids into the nucleator.
- stage (a) of formation of the male germs varies between 10 and 300 seconds.
- the other embodiment of the invention can be carried out in a basin with a conventional agitator which can vigorously stir the emulsion.
- step (a) of the process of the present invention it is made to rotate very slowly, at speeds of less than 200 rpm, for a basin of 20 l, for example at speeds of 20 to 50 rpm .
- the receiving medium in this case is the gelatin solution initially introduced into the basin.
- these homodispersed male nuclei are obtained whatever the nucleation vAg, which is in principle only an average VAg calculated as a function of the concentration of the solutions of silver and halide salts, and of the flow of these solutions.
- These germs are all the more homodisperse as the physico-chemical conditions of the receiving environment of these germs, reduce the possibility of maturation fast grain. These conditions are generally fulfilled if the VAg of the receiving medium is sufficiently high, that is to say greater than -10 mV, for example 30 mV, in which case the duration of the nucleation has no significant influence on the dispersity of the male germs. In the case where the physicochemical conditions of the receiving medium favor maturation, the lengthening of the duration of nucleation will contribute to increase the dispersity of the male seeds.
- the second stage, or maturation makes it possible to remove all the non-male seeds in favor of the male seeds.
- the conditions of maturation must be carefully controlled so as not to destroy the initial homodispersity of the germs, and in particular the VAg and the duration of maturation. A lower VAg gives a more effective maturation, but we must reduce the duration. If the maturation time is too long, the tabular grains begin to destroy themselves and the homodispersity is lost. Optimal ripening conditions can be determined giving the best% grain ratio
- V Ag of maturation is greater than 0 mV, and preferably
- the duration of maturation can vary for example between 20 and 30 minutes for a VAg of maturation greater than 20 mV.
- the length of the tube In the case of the laminar external nucleator, the length of the tube must be taken into account between the place where the fluxes of solutions come into contact and where the germs form, and the place where the germs arrive in the reactor. Indeed, the tube must be considered as a reactor in which the maturation takes place all the more actively the smaller the germs.
- the length of the tube coupled to the rates of introduction of the reagents determines an average residence time in the nucleator which can vary between 0.5 ms and 20 s, depending on the nucleators used.
- the emulsion containing the nucleated germs obtained in step (a) is preferably left on standby with gentle agitation for 1 to 60 seconds between the end of the nucleation (c ' that is to say the end of the addition of
- This strong agitation is of the order of 4,000 to
- halide with concentrations of 0.5M to 4M, with vigorous stirring, at a temperature between 35 and 70 ° C, and with a flow profile which must be controlled to avoid renucleation, but remain close to the speed of critical growth.
- the growth VAg must be greater than + 10 mV, and preferably more than 20 mV, to preserve the initial homodispersity of the nucleated germs.
- the tabular silver halide grains according to the invention can be silver bromide or silver bromoiodide grains. They generally have the form regular or irregular hexagons.
- Figures 5 and 6 are photomicrographs of emulsions prepared according to the invention. It can be seen that these emulsions are very homodisperse and contain only a few small three-dimensional grains.
- Modifying agents may be present during the precipitation of the seeds, either initially in the reactor, or added at the same time as one or more of the salts, according to conventional methods.
- These modifiers can be metallic compounds such as copper, thallium, bismuth, cadmium, zinc, medium chalcogens (i.e. sulfur, selenium and tellurium), gold and noble metals of group VIII, according to the indications given to the patents of United States of America 1 195 432, 1 951 933, 2 448 060, 2
- journal Research Disclosure volume 134, June 1975 publication 13452.
- the journal Research Disclosure and its predecessor Product Licensing Index are published by Industrial Opportunities Limited; Homewell, Havant;
- the silver salt and the bromide can be added to the reactor by surface or sub-surface supply tubes, by
- peptizing concentration of between 0.2 and approximately 10% by mass relative to the total mass of the constituents of the emulsion in the reactor. It is preferable to maintain the concentration of peptiser in the reactor at a value of less than about 6% of the total mass, before and during the formation of the seed grains and preferably also during the
- the vehicle concentration of the emulsion (the vehicle including the binder and the
- the initially formed emulsion may contain approximately 5 to 50 g (and preferably 10 to 30 g) of peptizer per mole of silver bromide.
- a vehicle supplement can be added later to bring the concentration up to 1000 g per mole of silver bromide.
- the finished emulsion is greater than 50 g per mole of silver bromide.
- the vehicle represents approximately 30 to 70% of the mass of the emulsion layer.
- the vehicles which include both binders and peptizers, can be chosen from among the substances
- the preferred peptizers are hydrophilic colloids which can be used alone or in combination with hydrophobic substances.
- Suitable hydrophilic vehicles include substances such as proteins, protein derivatives, cellulose derivatives, for example esters cellulosic, gelatin such as gelatin treated with an alkaline agent (skin or bone gelatin) or gelatin treated with an acidic agent (pig skin gelatin), gelatin derivatives such as acetylated gelatin and phthalylated gelatin. These and other vehicles are described in Research
- Vehicles can be tanned as described in paragraph X.
- Tabular grain emulsions can be mixed with conventional emulsions, as described in paragraph I.
- Tabular grains can be chemically sensitized as described in paragraph III and / or
- Photographic products may contain optical brightening agents
- the photographic products obtained can be products for black and white photography or for color photography, which form silver images and / or dye images by destruction, formation or
- Preferred color photographic products are those which form dye images using color developers and dye forming couplers. To use these products, we can expose them in a usual way, like it is described in paragraph XVIII, then it can be treated as described in paragraph XIX.
- the nucleator is connected to a 20 l basin containing the receiving medium consisting of 6 liters of a gelatin solution at 30 g / 1 containing 1 g / 1 of sodium bromide, having a pH of 5.5, a VAg of + 30 mV and a temperature of 70 ° C, stirred at 4500 rpm.
- a 0.5% gelatin solution containing 0.2 mol / l of potassium bromide is introduced into the nucleator, at a flow rate of 108 ml / min, and a solution containing 0.1 mol / l of silver nitrate at a flow rate of 100 ml / min, the two solutions having a pH of 5.5 and a temperature of 35 ° C, for 90 s.
- nucleator is - 38 mV.
- the solution obtained in the basin is left to wait for maturation for 20 to 30 min, at a temperature of 70 ° C and a pH of 5.5 and stirring at 4500 rpm, at a VAg of 23 mV .
- the germs are then grown by introducing solutions of 1.5 M potassium bromide and 1.5 M silver nitrate into the basin, at 70 ° C. and stirring at 4500 rpm, at increasing flow rates.
- VOC is the coefficient of variation in diameter
- ECD is the average circular diameter in ⁇ m
- % T is the
- Comparative Examples A and B give good VOC (equal to or less than 15%), but very few tabular grains, while Comparative Examples C and D give a high number of tabular grains, but poor VOC .
- Examples 1 to 6 according to the invention give both a percentage of tabular grains greater than 60% and a VOC less than 15%.
- Figure 5 is an electron micrograph at 11,500 magnification of the emulsion of Example 5.
- gelatin 211 g
- sodium bromide are added so as to obtain a VAg of + 30 mV.
- the temperature is brought to 70 ° C. and the stirring speed at 4500 rpm and the emulsion is left to mature for 20 minutes.
- FIG. 6 is an electronic photomicrograph at a magnification of 12,850 of the emulsion of example 8.
- Example 1 The emulsion of Example 1 and a control emulsion of AgBr having a wider grain size distribution are optimally spectrally and chemically sensitized.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9105985 | 1991-05-14 | ||
FR9105985A FR2676554A1 (fr) | 1991-05-14 | 1991-05-14 | Procede d'obtention de grains tabulaires monodisperses. |
PCT/FR1992/000417 WO1992021061A1 (fr) | 1991-05-14 | 1992-05-11 | Procede d'obtention de grains tabulaires monodisperses |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0584189A1 true EP0584189A1 (fr) | 1994-03-02 |
EP0584189B1 EP0584189B1 (fr) | 1994-12-07 |
Family
ID=9412867
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92910989A Expired - Lifetime EP0584189B1 (fr) | 1991-05-14 | 1992-05-11 | Procede d'obtention de grains tabulaires monodisperses |
Country Status (6)
Country | Link |
---|---|
US (1) | US5484697A (fr) |
EP (1) | EP0584189B1 (fr) |
JP (1) | JPH06507255A (fr) |
DE (1) | DE69200851T2 (fr) |
FR (1) | FR2676554A1 (fr) |
WO (1) | WO1992021061A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5549879A (en) * | 1994-09-23 | 1996-08-27 | Eastman Kodak Company | Process for pulse flow double-jet precipitation |
DE19700532A1 (de) * | 1997-01-10 | 1998-07-16 | Agfa Gevaert Ag | Herstellung feinteiliger, homodisperser Suspensionen |
JP3557859B2 (ja) * | 1997-07-15 | 2004-08-25 | コニカミノルタホールディングス株式会社 | ハロゲン化銀写真乳剤、その製造方法およびハロゲン化銀写真感光材料 |
US6372420B1 (en) * | 1999-03-25 | 2002-04-16 | Fuji Photo Film Co., Ltd. | Method for producing silver halide photographic emulsion |
US6443611B1 (en) | 2000-12-15 | 2002-09-03 | Eastman Kodak Company | Apparatus for manufacturing photographic emulsions |
JP2003107608A (ja) | 2001-09-28 | 2003-04-09 | Fuji Photo Film Co Ltd | ハロゲン化銀乳剤の製造方法及び装置 |
US6858381B2 (en) * | 2002-04-26 | 2005-02-22 | Fuji Photo Film Co., Ltd. | Method and apparatus for forming silver halide emulsion particles and method for forming fine particles |
JP4804718B2 (ja) * | 2003-04-28 | 2011-11-02 | 富士フイルム株式会社 | 流体混合装置、及び、流体混合システム |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1356921A (en) * | 1970-04-03 | 1974-06-19 | Agfa Gevaert | Preparation of silver halide emulsions |
BE795745A (fr) * | 1972-02-21 | 1973-08-21 | Eastman Kodak Co | Procede de preparation d'une emulsion photographique aux halogenures d'argent homodispersee |
US3897935A (en) * | 1972-11-13 | 1975-08-05 | Eastman Kodak Co | Apparatus for the preparation of a photographic emulsion |
GB1520976A (en) * | 1976-06-10 | 1978-08-09 | Ciba Geigy Ag | Photographic emulsions |
GB1591608A (en) * | 1976-09-14 | 1981-06-24 | Agfa Gevaert | Method and apparatus suitable for the preparation of silver halide emulsions |
DE2921164A1 (de) * | 1979-05-25 | 1980-12-04 | Agfa Gevaert Ag | Verfahren zur bildung von metallsalzen, photographische materialien und deren verwendung zur herstellung photographischer bilder |
US4386156A (en) * | 1981-11-12 | 1983-05-31 | Eastman Kodak Company | Silver bromide emulsions of narrow grain size distribution and processes for their preparation |
FR2534036B1 (fr) * | 1982-09-30 | 1986-09-05 | Kodak Pathe | Emulsion a grains tabulaires de bromure d'argent, produit photographique le contenant et procede pour le preparer |
JPS59212826A (ja) * | 1983-05-18 | 1984-12-01 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真乳剤の製造方法 |
JPS6218556A (ja) * | 1985-07-18 | 1987-01-27 | Fuji Photo Film Co Ltd | ハロゲン化銀カラ−写真感光材料 |
US4797354A (en) * | 1986-03-06 | 1989-01-10 | Fuji Photo Film Co., Ltd. | Silver halide emulsions comprising hexagonal monodisperse tabular silver halide grains |
US4722886A (en) * | 1986-10-10 | 1988-02-02 | E. I. Du Pont De Nemours And Company | Process for preparing a photographic emulsion containing tabular grains having narrow size distribution |
JP2700677B2 (ja) * | 1988-12-22 | 1998-01-21 | 富士写真フイルム株式会社 | ハロゲン化銀粒子形成時のコントロール方法及び装置 |
US5104786A (en) * | 1990-10-29 | 1992-04-14 | Eastman Kodak Company | Plug-flow process for the nucleation of silver halide crystals |
-
1991
- 1991-05-14 FR FR9105985A patent/FR2676554A1/fr not_active Withdrawn
-
1992
- 1992-05-11 US US08/142,282 patent/US5484697A/en not_active Expired - Fee Related
- 1992-05-11 EP EP92910989A patent/EP0584189B1/fr not_active Expired - Lifetime
- 1992-05-11 JP JP4509850A patent/JPH06507255A/ja active Pending
- 1992-05-11 DE DE69200851T patent/DE69200851T2/de not_active Expired - Fee Related
- 1992-05-11 WO PCT/FR1992/000417 patent/WO1992021061A1/fr active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO9221061A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69200851D1 (de) | 1995-01-19 |
WO1992021061A1 (fr) | 1992-11-26 |
FR2676554A1 (fr) | 1992-11-20 |
DE69200851T2 (de) | 1995-07-20 |
US5484697A (en) | 1996-01-16 |
EP0584189B1 (fr) | 1994-12-07 |
JPH06507255A (ja) | 1994-08-11 |
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