US3637391A - Process for the preparation of silver halide emulsions - Google Patents
Process for the preparation of silver halide emulsions Download PDFInfo
- Publication number
- US3637391A US3637391A US854792A US3637391DA US3637391A US 3637391 A US3637391 A US 3637391A US 854792 A US854792 A US 854792A US 3637391D A US3637391D A US 3637391DA US 3637391 A US3637391 A US 3637391A
- Authority
- US
- United States
- Prior art keywords
- silicic acid
- emulsion
- silver halide
- percent
- sol
- 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
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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
Definitions
- the invention relates to a process for the preparation of silver halide emulsions, in which process precipitation or afterripening is carried out in the presence of silicic acid sols which act as protective colloids.
- the preparation of photographic silver halide emulsions comprises substantially three stages:
- a protective colloid generally gelatin
- aqueous solutions of a silver salt e.g., silver nitrate
- alkali metal halides e.g., sodium bicarbonate
- the substance which is mostly used as a protective colloid and binder for silver halide emulsions is gelatin. No other natural or synthetic binders have achieved any practical importance because it is only with gelatin that the necessary light sensitivity can be achieved.
- the photographic properties of silver halide emulsions e.g., their sensitivity to light the characteristic curve, fog formation, etc., can be altered as desired by the use of certain additives. These properties can also be influenced by modifying the method of preparation. The method of precipitation is of special importance for the graininess of the silver halide emul- SlOn.
- Sensitivity increases of up to about 3 DIN, i.e., of a whole shutter stop, are easily achieved by the process according to the invention without any further alterations to the silver halide emulsion.
- fogging is considerably reduced.
- the emulsions prepared by the process according to the invention provide images which have substantially reduced graininess.
- the characteristic curve of these emulsions shows an extended rectilinear form which is extremely desirable for most photographic processes.
- the usual silicic acid sols are suitable for the process according to the invention, regardless of whether the silicic acid has been prepared by a wet decomposition process or a pyrogenic process.
- the size of the colloidal silicic acid particles in the sol should be relatively small. Particle sizes of up to 100 p and preferably between 7 and 100 p. have been found to be generally suitable.
- silicic acid sols containing up to 20 percent by weight of aluminum oxide related to the solid content.
- the concentration of silicic acid in the silicic acid so] may vary within wide limits.
- concentration and type of silicic acid sol which is suitable for any particular silver halide emulsion can be easily determined by a few simple tests.
- Aqueous silicic acid sols in concentrations of 0.1 to 30 percent have proved to be suitable for the preparation of most silver halide emulsions.
- care must be taken to ensure that the silicic acid particles do not agglomerate to form larger particles which may impair the properties of the emulsion, e.g. due to the formation of a rough surface in the finished silver halide emulsion layer.
- Agglomeration can be easily avoided by adjusting suitably the concentration of alkali metal halide and silver salts during precipitation. If the concentrations of silicic acid are relatively high, relatively dilute salt solutions should be used for precipitation. 0.1 to 1 percent silicic acid sols have proved to be the most advantageous for the process of the invention.
- ethanol 96 percent
- the amount of ethanol necessary for this purposes can vary within wide limits, for example between 20 and 100 ml. and preferably between 40 and 70 ml. per 100 ml. ofa 30 percent aqueous silicic acid sol.
- silicic acid particles by polymerizing in the silicic acid sols any monomers which are sufficiently soluble in water.
- Useful monomers are for example acrylic acid, methacrylic acid and derivatives thereof, such as acryl amide, acrylonitrile, methacryl amide or methacrylonitrile, or vinylsulfonic acid, or mixtures of the monomers mentioned before.
- the polymerization is started by addition of a radical forming compound such as potassium persulfate or azadiisobutyronitrile. After the polymerization step the reaction mixture is dialyzed to remove undesired byproducts and especially the remaining polymerization starter which otherwise would deleteriously affect the photographic properties of the emulsion.
- Amounts of the monomers used for the polymerization which are between 0.5 and 20 percent by weight, and preferably between 0.5 and 2 percent by weight related to the solid content of the sols have proved to be useful.
- the polymerisate is used at least in such a concentration as to avoid agglomeration and at most in such a concentration as to attain improved photographic results, for example, higher sensitivity or finer graininess.
- the same results can also be obtained by addition of a suitable amount of a polymer obtained by homoor copolymerization of the monomers mentioned above.
- the agglomeration can be prevented by addition of polyacrylic acid, polyacryl amide, polyacrylonitrile or polyvinyl alcohol.
- the addition of gum arabic or polyvinyl pyrrolidone, for example has been useful.
- the concentration which is suitable for any particular silver halide emulsion can be easily determined by a few simple tests. In principle these additives are used in the same concentration as the monomers mentioned above.
- the polymers added to or prepared by polymerization in the aqueous silicic acid sols must be sufficiently soluble in this medium.
- the process of the invention is suitable for the preparation of silver chloride, silver bromide, silver iodide or mixed emulsions.
- the usual variations of the process can be easily used for precipitation.
- the aqueous solutions of the silver salt and of the alkali metal halide may be run in simultaneously, but equally well one of the components for precipitation may be introduced first into the reaction vessel.
- Neutral emulsions or ammoniacal emulsions may equally well be prepared by the process according to the invention.
- the silicic acid sol When precipitating the silver halide by the process according to the invention, the silicic acid sol may be used as the only protective colloid or in admixture with gelatin as a protective colloid. In the latter case, the proportion of gelatin to silicic acid may vary within wide limits. Proportions by weight of between 1:0.] and 0.0:l have been found to besuitable in most cases.
- silicic acid sols which have previously been treated with anion exchangers or cation exchangers have proved to be particularly suitable.
- the pH of such silicic acids is 4 or less.
- the pH may then be adjusted to the region of 5 to 7 without any ag glomeration of the silicic acid sol being observed.
- Precipitation is performed preferably at a pH of between 6.0 and 7.0.
- Gelatin in the usual quantities is advantageously used for redispersing the precipitated emulsion before chemical ripening.
- concentration of the silicic acid sol is preferably such that up to 20 percent by weight and preferably up to 10 percent by weight of the total amount of binder in the finished emulsion consists of silicic acid.
- the emulsions can also be optically sensitized with cyanine dyes such as basic or acid carbocyanines, cyanine dyes of the betaine type, rhodacyanine or merocyanine dyes, styryl or oxonol dyes.
- cyanine dyes such as basic or acid carbocyanines, cyanine dyes of the betaine type, rhodacyanine or merocyanine dyes, styryl or oxonol dyes.
- Suitable sensitizers are described by F. M. l-lamer The Cyanine Dyes and related Compounds lnterscience Publishers, 1964).
- the emulsions may also contain chemical sensitizers, e.g., reducing agents such as stannous salts, polyamines such as diethyltriamine or aminomethane sulfinic acids or derivatives thereof such as described in Belgian patent specification No. 547,323 or sulfur compoundsas described in US. Pat. No. 1,574,944, for example allyl thiocyanate, allylthiourea, sodiumsulfate and the like.
- Suitable chemical sensitizers are also salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold, as described in the article by R. Koslowsky, Z. wiss.phot. 46, 65-72 (1959).
- Further suitable 'for chemical sensitization are polyalkylene oxides, especially polyethylene oxide having an average molecular weight of l,000 to 20,000 and derivatives thereof, such as condensation products of alkylene oxides with aliphatic alcohols, glyco
- condensation products of hexitoles, alkyl substituted 'phenols, aliphatic carboxylic acids, aliphatic amines, diamines or amides-The said condensation products have preferably a molecular weight of above 1,000. It is also possible to apply combinations of several chemical sensitizers.
- Particular suitable for the emulsion of the present invention are chemical sensitizers of the thiomorpholine series such as described in French Pat. No. l,506,230.
- the emulsions according to the invention may additionally contain the usual stabilizers, e.g., homopolar or salt-type compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts, and other mercury compounds.
- stabilizers which may be used include azaindenes, especially tetraor pentaazaindenes, in particular those substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr, Z.wiss.phot. 47, 258 (1952).
- Other suitable stabilizers include heterocyclic mercapto compounds, e.g., l-phenyl-5-mercapto-tetrazole, quaternary benzthiazole derivatives and benztriazoles.
- the emulsions may be hardened in the usual manner, for example, with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
- formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
- the emulsions prepared by the process according to the invention can be used for all sorts of different photographic material, e.g., for phototechnical films, for making printed copies or material for taking originals, especially highly sensitive material of this kind. They may also be used for X-ray films, for any type of color photographic material, e.g., material used for the silver dye bleaching process, and for photographic material intended for use in the silver salt diffusion process or any other instant image-forming process.
- EXAMPLE 1 Emulsion] Thirty ml. of a 30 percent aqueous colloidal solution of silicic acid (pH 8.3; particle size about l4 ,4; stabilized with NaOH) are added to a solution of 78 g. of ammonium bromide, 7.2 g. of potassium iodide and 10 g. of gelatin in 1 liter of water. The reaction mixture is adjusted to a pH of 6.8 and heated to 65 C.- A solution of g. of silver nitrate in 1,200 ml. of water, which is at about the same temperature as the solution in the reaction vessel, is then run in the course of 40 minutes. The resulting emulsion is cooled to 30 C. and flocculated by the addition of a concentrated solution of ammonium sulfate.
- the fiocculate is given time to settle, decanted and washed several times with water.
- the washed flocculate is taken up in a solution of g. of gelatin in 1,200 ml. of water.
- the pH is then adjusted to about 6.6, the pAg to 8.9 and the viscosity to about 10 cp.
- Emulsion ll The emulsion is prepared in the same way as emulsion l but without the addition of silicic acid sol.
- Emulsion Ill The emulsion is prepared in the same way as emulsion II but 30 ml. of the silicic acid sol described for emulsion l are added before chemical ripening.
- Emulsion IV The emulsion is prepared in the same way as emulsion ll. Thirty ml. of the silicic acid sol are added after chemical ripening.
- the emulsions are then then processed in identical manner. Ten ml. of a 10 percent aqueous formaldehyde solution as hardener, l2 ml. of a 7.5 percent aqueous saponin solution as wetting agent and 20 ml. of a 1 percent methanolic solution of 4-hydroxy-6-methyl-l,3,3a,7-tetraazaindene as stabilizer are added. The finished casting solutions are applied onto a support of cellulose triacetate.
- the layers are exposed in a conventional sensitometer through a step wedge.
- the exposed samples are developed in a bath of the following composition for 6 minutes, and in a second parallel test for 16 minutes:
- Emulsion V Thirty percent silicic acid sol stabilized with NaOI-I, pH 8.3, particle size about 14 ,u.
- Emulsion VI Fifteen percent, particle size 7 to 9 u.
- Emulsion VII Thirty percent, mixed with A1 sol, pH 9.1, particle size 14 to 15 u.
- Emulsion VIII Thirty percent, stabilized with NaOI-I, pH 9.9, particle size 14 to 15 ,l.
- Emulsion IX Thirty percent, stabilized with NaOI-I, pH 9, particle size 5 IO [.L. Emulsion X Fifteen percent, dispersion of finely divided SiO prepared pyrogenically, particle size to p" Emulsion XI Twenty-eight aqueous dispersion of pyrogenically prepared SiO particle size about 15 u.
- Emulsion XII The emulsion is prepared in the same way as emulsion I of example I, but with a silicic acid sol of the same particle size which had been treated with anionic and cationic exchangers.
- the silicic acid sol has a pH of 3.4. Before it is used as protective colloid in the precipitation, it is adjusted to a pH of 6.8.
- Emulsion XIII The emulsion is prepared in the same way as emulsion I, but precipitation is carried out only in the presence of the silicic acid sol described above, without gelatin. After precipitation, a solution of 10 g. of gelatin in 100 ml. of water is added to enable flocculation to take place.
- the emulsion is processed as described in example 1.
- the results of the sensitometric test are given in table 111 below.
- the comparison emulsion given in the table was prepared in the same way but without the addition of silicic acid sol.
- Emulsion XIV The emulsion is substantially the same as emulsion I of example I.
- Emulsion XV The emulsion is prepared like emulsion XIV, but 2 ml. of a 1 percent aqueous solution of 6-azonia-9-sulphaspiro-5,5-undecane chloride according to French Patent Specification 1,506,230 are added to the precipitation component.
- the emulsion is processed as described in example I.
- the results of the sensitometric test are shown in table IV below.
- emulsion 1 (example 1).
- Emulsion XVII The emulsion is prepared in the same way as emulsion XVI but the silicic acid solis treated with 20 ml. of ethanol (96 percent) before addition to the reaction mixture. Also the same amount of ethanol is added to the emulsion before afterripenmg.
- Emulsions XVIII-XXVII In the preparation of these emulsions is added a silicic acid so] as described for emulsion XVI but in the silicic acid sol have been polymerized before addition various monomers in various amounts given in the table V. After polymerization the solution is dialyzed.
- the silicic acid sol for the preparation of emulsion XIX has been prepared as follows:
- emulsions are casted upon a support, dried, exposed, and processed as described in example 1.
- the agglomeration of silicic acid particles can be tested optically by means of a microscope with a magnification of at least 200, or by examining the roughness of the processed and dried film with the finger. Agglomeration occurs in emulsion XVI. But no agglomeration can be found in emulsions XVII through XXXll.
- a process for making light-sensitive silver halide emulsions comprising the steps of precipitating the silver halide in the presence of a protective colloid, obtaining a suspension to produce an emulsion, washing the emulsion and chemical ripening the improvement consisting of precipitating the silver halide in the presence of colloidal silicic acid sol having a particle size of between and 50 am, said silicic acid sol being a protective colloid.
- the silicic acid sol contains in dissolved form 05-20 percent by weight related to the solid content of gum arabic, polyvinyl alcohol, polyvinyl-pyrrolidone or of a homoor copolymerisate of acrylic acid or of derivatives thereof.
- a process for making light-sensitive silver halide em ulsions comprising the steps of precipitating the silver halide in the presence of a protective colloid, obtaining a suspension to produce an emulsion, washing the emulsion and chemical ripening the improvement consisting of chemical ripening the emulsion in the presence of colloidal silicic acid sol having a particle size of between S and 50 nm., said silicic acid s'ol being a protective colloid.
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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)
- Silicon Compounds (AREA)
- Colloid Chemistry (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19681797254 DE1797254C3 (de) | 1968-09-05 | Verfahren zur Herstellung von Sllberhalogenidemulsionen |
Publications (1)
Publication Number | Publication Date |
---|---|
US3637391A true US3637391A (en) | 1972-01-25 |
Family
ID=5708582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US854792A Expired - Lifetime US3637391A (en) | 1968-09-05 | 1969-09-02 | Process for the preparation of silver halide emulsions |
Country Status (5)
Country | Link |
---|---|
US (1) | US3637391A (de) |
BE (1) | BE738444A (de) |
CH (1) | CH534900A (de) |
FR (1) | FR2017463A1 (de) |
GB (1) | GB1276912A (de) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3877944A (en) * | 1971-11-24 | 1975-04-15 | Agfa Gevaert Ag | Photographic silver salt emulsions comprising polymers with disulfonimide groups |
US4001022A (en) * | 1975-08-13 | 1977-01-04 | Minnesota Mining And Manufacturing Company | Photographic materials comprising developer layers and binders comprising silica sol |
US4046586A (en) * | 1974-08-19 | 1977-09-06 | American Optical Corporation | Stabilized photochromic materials |
US4297439A (en) * | 1978-06-02 | 1981-10-27 | Agfa-Gevaert Ag | Production of photographic silver halide emulsion |
US5013641A (en) * | 1989-12-19 | 1991-05-07 | Eastman Kodak Company | Formation of tabular silver halide emulsions utilizing high pH digestion |
EP0586748A1 (de) * | 1992-09-11 | 1994-03-16 | Agfa-Gevaert N.V. | Filterfarbstoffe für Schnellverarbeitungs-Verwendungen |
US5340613A (en) * | 1993-03-12 | 1994-08-23 | Minnesota Mining And Manufacturing Company | Process for simultaneously coating multiple layers of thermoreversible organogels and coated articles produced thereby |
EP0392092B1 (de) * | 1989-04-11 | 1994-09-14 | Agfa-Gevaert N.V. | Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen |
US5415993A (en) * | 1993-04-26 | 1995-05-16 | Minnesota Mining And Manufacturing Company | Thermoreversible organogels for photothermographic elements |
US5543284A (en) * | 1994-05-09 | 1996-08-06 | Agfa-Gevaert, N.V. | Preparation method of regular silver halide light-sensitive emulsions comprising silver halide crystals rich in chloride and material comprising said emulsions |
US5674675A (en) * | 1991-08-23 | 1997-10-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0831362A1 (de) * | 1996-09-18 | 1998-03-25 | Agfa-Gevaert N.V. | Lichtempfindliches Silberhalogenidmaterial mit Kieselsäure-Schutzkolloid, das Schichten enthält, die kein oder ein Minimum an Gelatine als Bindemittel enthalten |
US20090092538A1 (en) * | 2007-10-08 | 2009-04-09 | Amit Khanolkar | Methods for forming stabilized metal salt particles |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69129148T2 (de) * | 1991-06-11 | 1998-10-08 | Agfa Gevaert Nv | Verfahren zur Herstellung von lichtempfindlichen Silberhalogenidemulsionen |
EP0528476B1 (de) * | 1991-08-15 | 1997-03-05 | Agfa-Gevaert N.V. | Verfahren zur Herstellung eines photographischen Silberhalogenidmaterials |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2626867A (en) * | 1947-12-04 | 1953-01-27 | Du Pont | Light-sensitive photographic element |
US2694637A (en) * | 1951-07-19 | 1954-11-16 | Du Pont | Photographic emulsions containing a silanic sensitizer |
US2752246A (en) * | 1953-06-16 | 1956-06-26 | Du Pont | Process of preparing a light sensitive silver halide emulsion |
DE1267931B (de) * | 1965-07-07 | 1968-05-09 | Rudolf Pfeilmaier | Paste bzw. Loesung fuer die Reinigung und Versilberung |
US3411907A (en) * | 1965-03-04 | 1968-11-19 | Eastman Kodak Co | Photographic compositions containing combination of soft and hard matting agents |
-
1969
- 1969-08-25 GB GB42164/69A patent/GB1276912A/en not_active Expired
- 1969-08-29 CH CH1312569A patent/CH534900A/de not_active IP Right Cessation
- 1969-09-02 US US854792A patent/US3637391A/en not_active Expired - Lifetime
- 1969-09-05 BE BE738444D patent/BE738444A/xx unknown
- 1969-09-05 FR FR6930357A patent/FR2017463A1/fr not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2626867A (en) * | 1947-12-04 | 1953-01-27 | Du Pont | Light-sensitive photographic element |
US2694637A (en) * | 1951-07-19 | 1954-11-16 | Du Pont | Photographic emulsions containing a silanic sensitizer |
US2752246A (en) * | 1953-06-16 | 1956-06-26 | Du Pont | Process of preparing a light sensitive silver halide emulsion |
US3411907A (en) * | 1965-03-04 | 1968-11-19 | Eastman Kodak Co | Photographic compositions containing combination of soft and hard matting agents |
DE1267931B (de) * | 1965-07-07 | 1968-05-09 | Rudolf Pfeilmaier | Paste bzw. Loesung fuer die Reinigung und Versilberung |
Non-Patent Citations (2)
Title |
---|
Photographic Chemistry, 1958, Glafkides, pp. 431 432. * |
The Condensed Chemical Dictionary, Seventh Edition, Rose et al., 1968, p. 843. * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3877944A (en) * | 1971-11-24 | 1975-04-15 | Agfa Gevaert Ag | Photographic silver salt emulsions comprising polymers with disulfonimide groups |
US4046586A (en) * | 1974-08-19 | 1977-09-06 | American Optical Corporation | Stabilized photochromic materials |
US4001022A (en) * | 1975-08-13 | 1977-01-04 | Minnesota Mining And Manufacturing Company | Photographic materials comprising developer layers and binders comprising silica sol |
US4297439A (en) * | 1978-06-02 | 1981-10-27 | Agfa-Gevaert Ag | Production of photographic silver halide emulsion |
EP0392092B1 (de) * | 1989-04-11 | 1994-09-14 | Agfa-Gevaert N.V. | Verfahren zur Herstellung von lichtempfindlichen Silberhalogenid Emulsionen |
US5013641A (en) * | 1989-12-19 | 1991-05-07 | Eastman Kodak Company | Formation of tabular silver halide emulsions utilizing high pH digestion |
US5674675A (en) * | 1991-08-23 | 1997-10-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0586748A1 (de) * | 1992-09-11 | 1994-03-16 | Agfa-Gevaert N.V. | Filterfarbstoffe für Schnellverarbeitungs-Verwendungen |
US5340613A (en) * | 1993-03-12 | 1994-08-23 | Minnesota Mining And Manufacturing Company | Process for simultaneously coating multiple layers of thermoreversible organogels and coated articles produced thereby |
US5378542A (en) * | 1993-03-12 | 1995-01-03 | Minnesota Mining And Manufacturing Company | Process for simultaneously coating multiple layers of thermoreversible organogels and coated articles produced thereby |
US5415993A (en) * | 1993-04-26 | 1995-05-16 | Minnesota Mining And Manufacturing Company | Thermoreversible organogels for photothermographic elements |
US5543284A (en) * | 1994-05-09 | 1996-08-06 | Agfa-Gevaert, N.V. | Preparation method of regular silver halide light-sensitive emulsions comprising silver halide crystals rich in chloride and material comprising said emulsions |
EP0831362A1 (de) * | 1996-09-18 | 1998-03-25 | Agfa-Gevaert N.V. | Lichtempfindliches Silberhalogenidmaterial mit Kieselsäure-Schutzkolloid, das Schichten enthält, die kein oder ein Minimum an Gelatine als Bindemittel enthalten |
US20090092538A1 (en) * | 2007-10-08 | 2009-04-09 | Amit Khanolkar | Methods for forming stabilized metal salt particles |
US9872501B2 (en) | 2007-10-08 | 2018-01-23 | Johnson & Johnson Vision Care, Inc. | Methods for forming stabilized metal salt particles |
Also Published As
Publication number | Publication date |
---|---|
DE1797254B2 (de) | 1976-07-22 |
FR2017463A1 (de) | 1970-05-22 |
BE738444A (de) | 1970-03-05 |
CH534900A (de) | 1973-03-15 |
DE1797254A1 (de) | 1971-07-29 |
GB1276912A (en) | 1972-06-07 |
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