US3600182A - Photographic gelatins - Google Patents
Photographic gelatins Download PDFInfo
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- US3600182A US3600182A US766317A US3600182DA US3600182A US 3600182 A US3600182 A US 3600182A US 766317 A US766317 A US 766317A US 3600182D A US3600182D A US 3600182DA US 3600182 A US3600182 A US 3600182A
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- United States
- Prior art keywords
- gelatin
- catalase
- photographic
- silver
- emulsion
- 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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- 108010010803 Gelatin Proteins 0.000 title abstract description 30
- 229920000159 gelatin Polymers 0.000 title abstract description 30
- 235000019322 gelatine Nutrition 0.000 title abstract description 29
- 235000011852 gelatine desserts Nutrition 0.000 title abstract description 29
- 102000016938 Catalase Human genes 0.000 abstract description 27
- 108010053835 Catalase Proteins 0.000 abstract description 27
- 239000000839 emulsion Substances 0.000 abstract description 24
- 239000008273 gelatin Substances 0.000 abstract description 24
- 229910052709 silver Inorganic materials 0.000 abstract description 22
- 239000004332 silver Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- -1 silver halide Chemical class 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- HMJGQFMTANUIEW-UHFFFAOYSA-N 5-phenylsulfanyl-2h-tetrazole Chemical compound C=1C=CC=CC=1SC=1N=NNN=1 HMJGQFMTANUIEW-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- XCGQJCSSCTYHDV-UHFFFAOYSA-N mercury(1+);sulfane Chemical compound S.[Hg+] XCGQJCSSCTYHDV-UHFFFAOYSA-N 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 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
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- 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
- the invention concerns photographic gelatins with improved photographic properties, in particular with an improved stabilization of silver images contained therein, i.e., of latent images from developable silver nuclei as well as of visible images of metallic silver.
- Gelatin is still the most important binder for silver halide emulsion coatings, though many attempts have been made to replace this binder with other synthetic substances.
- Gelatin being a natural product, represents, as one of its disadvantages, a limited reproducibility in its production. Depending on raw materials and manufacturing processes used, the gelatin produced has different prop erties, and only a mixture of different gelatins makes it possible to obtain a product suitable for the production of photographic coatings with more or less uniform properties.
- synthetic binders offer the advantage that they can be produced with far more uniform properties.
- synthetic binders which, as to their photographic properties, could be compared to natural gelatin.
- gelatin in this respect is its sensitivity increasing effect on the light sensitivity of silver halides. This effect is usually ascribed to the presence of sulphur compounds as ripening agents, which considerably increase the sensitivity of silver halide grains. Furthermore, gelatin can stabilize metallic silver, in particular latent silver images against the oxidative effect of atmospheric oxygen.
- gelatin is an excellent binder for light sensitive photographic coatings, it is desirable to further improve gelatins, in particular to provide a more uniform production of photographically highly active gelatin types.
- the purpose of the invention is to develop gelatins for photographic silver halide coatings with improved properties.
- Gelatins made according to the invention have a catalase activity of more than 10 international effectiveness units, preferably between 10 and 100 effectiveness units/ gram.
- Such gelatin types stabilize extraordinarily the latent ice image. Furthermore, the finished silver image becomes considerably more stable as to density and tone.
- the catalase is added to the photographic emulsion at any time, preferably after chemical ripening. The same effect can be obtained if a finished silver halide emulsion coating is bathed in an aqueous catalase solution. Furthermore, it is possible to add the desired quantity of catalase to the gelatin prior to its use in the production of photographic material.
- the catalase is used in form of an aqueous solution, buffered in respect of pH value.
- aqueous solutions are the usual form of catalase for use. They contain between 10 and 10 effectiveness units of catalase per liter. They can be produced according to known methods, such as that of K. G. Stern, Hoppe Seylers Zeitschrift fiir Physio strige Chemie (Journal for Physiological Chemistry), vol. 212 (1932), p. 207.
- commercial catalase preparations of bacterial origin can be used for this purpose.
- the catalase concentration which can be varied within certain limits, according to the photographic requirements, can easily be determined through simple tests.
- Catalase can be used in any desired silver halide emulsion.
- Silver chloride, silver bromide or mixtures thereof can be used as silver halides, possibly with a slight content of silver iodide up to 10 mol. percent.
- the emulsions can also contain chemical sensitizers, for instance reducing agents such as stannous halides, polyamines such as di-ethylene triamine, sulphur compounds as described in U.S. Pat. No. 1,574,944.
- chemical sensitizers for instance reducing agents such as stannous halides, polyamines such as di-ethylene triamine, sulphur compounds as described in U.S. Pat. No. 1,574,944.
- the indicated emulsions can also contain salts of noble metals, such as ruthenium, rhodium, palladium, iridium, platinum or gold salts as described in the article by R. Koslowsky, Z. Wiss. Phot., vol. 46, pp. 6572 (1951).
- the emulsions can also contain poly-alkylene oxides, in particular polyethylene oxides and derivatives thereof, as chemical sensitizers.
- the emulsions made according to the invention can contain the usual stabilizers, such as homopolar or saltlike compounds of mercury with aromatic or heterocyclic rings, e.g., mercaptotriazole, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
- Other stabilizers are azaindenes, preferably tetraor pentazaindenes, in particular those substituted by hydroxyl or amino groups. Such compounds are described in the article of Birr, Z. Wiss. Phot., vol. 47, pp. 2-58 (1952).
- heterocyclic mercapto compounds such as phenyl mercaptotetrazol, quaternary benzothiazole derivatives, benzotriazole and similar substances can be used as stabilizers.
- the emulsions can be hardened in the usual way, for instance with formaldehyde or aldehydes substituted with halogen which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes and other similar compounds.
- formaldehyde or aldehydes substituted with halogen which contain a carboxyl group such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes and other similar compounds.
- EXAMPLE 1 A highly sensitive silver bromide-gelatin emulsion, containing approximately 6 mol. percent silver iodide, is spread on a cellulose triacetate film base. For photographic coating, the usual photographic gelatin is used.
- the film sample thus prepared is divided into two parts. One series of strips is bathed for about 2 minutes in a 1% solution of technical catalase. The other series remains without treatment for purposes of comparison.
- Both series are exposed in a conventional sensitometer for 10 seconds behind a grey step wedge, and then subjected for varying periods storage at 25 C. and 60% relative humidity.
- the emulsions thus produced are exposed, as in Example 1, in a sensitometer for 10* seconds behind a grey step wedge and then subjected for varying periods to a 25 C. and 60 C. relative humidity atmosphere.
- a highly sensitive AgCl/AgBr gelatin emulsion is coated on a coated paper as the emulsion carrier.
- the emulsion is covered with a protective gelatin surface coating of 1.5 1. thickness.
- ml. of a 1% catalase solution is added to 1 kg. of coating solution for the protective surface coating (1.8% aqueous gelatin solution).
- the same emulsion is coated with a protective surface coating containing no catalase.
- Example 2 The material is exposed and developed as indicated in Example 2. Three sensitometer strips (approximately 4 cm. wide) of the materials to be compared are placed in desiccator, on the bottom of which a container with 50 ml. of a 5% hydrogen peroxide solution is placed.
- Gelatin associated with silver halide in a photographic light-sensitive composition said gelatin containing catalase in amounts of more than 10 International Effectiveness Units per gram.
Abstract
PHOTOGRAPHIC MATERIAL HAVING A GELATIN-SILVER HALIDE EMULSION LAYER OF WHICH THE GELATIN CONTAINING CATALASE OF MORE THAN 10 INTERNATIONAL ACTIVITY UNITS PER GRAM.
Description
United States Patent 3,600,182 PHOTOGRAPHIC GELATINS Reinhard Matejec and Rudolf Meyer, Leverkusen, and Bruno Miicke, Cologne-Buchheim, Germany, assignors to Agfa-Gevaert Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Oct. 9, 1968, Ser. No. 766,317 Int. Cl. G03c 1/04 U.S. Cl. 96114.7 2 Claims ABSTRACT OF THE DISCLOSURE Photographic material having a gelatin-silver halide emulsion layer of which the gelatin containing catalase of more than international activity units per gram.
The invention concerns photographic gelatins with improved photographic properties, in particular with an improved stabilization of silver images contained therein, i.e., of latent images from developable silver nuclei as well as of visible images of metallic silver.
Gelatin is still the most important binder for silver halide emulsion coatings, though many attempts have been made to replace this binder with other synthetic substances. Gelatin, being a natural product, represents, as one of its disadvantages, a limited reproducibility in its production. Depending on raw materials and manufacturing processes used, the gelatin produced has different prop erties, and only a mixture of different gelatins makes it possible to obtain a product suitable for the production of photographic coatings with more or less uniform properties. Compared with this, synthetic binders offer the advantage that they can be produced with far more uniform properties. On the other hand, it was not possible heretofore to produce synthetic binders which, as to their photographic properties, could be compared to natural gelatin. The advantage of gelatin in this respect is its sensitivity increasing effect on the light sensitivity of silver halides. This effect is usually ascribed to the presence of sulphur compounds as ripening agents, which considerably increase the sensitivity of silver halide grains. Furthermore, gelatin can stabilize metallic silver, in particular latent silver images against the oxidative effect of atmospheric oxygen.
Though, as pointed above, gelatin is an excellent binder for light sensitive photographic coatings, it is desirable to further improve gelatins, in particular to provide a more uniform production of photographically highly active gelatin types.
The purpose of the invention is to develop gelatins for photographic silver halide coatings with improved properties.
It has been found that the photographic properties of gelatin considerably improve the stabilizing effect on latent images of silver nuclei and in visible images, and that, depending on its use, these properties can be brought to the desired level by adding catalase to the silver halide emulsion coating.
Gelatins made according to the invention, have a catalase activity of more than 10 international effectiveness units, preferably between 10 and 100 effectiveness units/ gram.
By definition, an international effectiveness unit is the quantity of catalase which, within one minute at 25 C., decomposes one micromol of H O i.e., which develops, within one minute, from an H 0 solution 1.12 10 cm. of O (p=1atm.).
Such gelatin types stabilize extraordinarily the latent ice image. Furthermore, the finished silver image becomes considerably more stable as to density and tone.
The catalase is added to the photographic emulsion at any time, preferably after chemical ripening. The same effect can be obtained if a finished silver halide emulsion coating is bathed in an aqueous catalase solution. Furthermore, it is possible to add the desired quantity of catalase to the gelatin prior to its use in the production of photographic material.
Generally, the catalase is used in form of an aqueous solution, buffered in respect of pH value. Such solutions are the usual form of catalase for use. They contain between 10 and 10 effectiveness units of catalase per liter. They can be produced according to known methods, such as that of K. G. Stern, Hoppe Seylers Zeitschrift fiir Physiologische Chemie (Journal for Physiological Chemistry), vol. 212 (1932), p. 207. Furthermore, commercial catalase preparations of bacterial origin can be used for this purpose. The catalase concentration, which can be varied within certain limits, according to the photographic requirements, can easily be determined through simple tests.
Catalase can be used in any desired silver halide emulsion. Silver chloride, silver bromide or mixtures thereof can be used as silver halides, possibly with a slight content of silver iodide up to 10 mol. percent.
The emulsions can also contain chemical sensitizers, for instance reducing agents such as stannous halides, polyamines such as di-ethylene triamine, sulphur compounds as described in U.S. Pat. No. 1,574,944. For purposes of chemical sensitization, the indicated emulsions can also contain salts of noble metals, such as ruthenium, rhodium, palladium, iridium, platinum or gold salts as described in the article by R. Koslowsky, Z. Wiss. Phot., vol. 46, pp. 6572 (1951).
The emulsions can also contain poly-alkylene oxides, in particular polyethylene oxides and derivatives thereof, as chemical sensitizers.
The emulsions made according to the invention can contain the usual stabilizers, such as homopolar or saltlike compounds of mercury with aromatic or heterocyclic rings, e.g., mercaptotriazole, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Other stabilizers are azaindenes, preferably tetraor pentazaindenes, in particular those substituted by hydroxyl or amino groups. Such compounds are described in the article of Birr, Z. Wiss. Phot., vol. 47, pp. 2-58 (1952). Furthermore, heterocyclic mercapto compounds, such as phenyl mercaptotetrazol, quaternary benzothiazole derivatives, benzotriazole and similar substances can be used as stabilizers.
The emulsions can be hardened in the usual way, for instance with formaldehyde or aldehydes substituted with halogen which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes and other similar compounds.
EXAMPLE 1 A highly sensitive silver bromide-gelatin emulsion, containing approximately 6 mol. percent silver iodide, is spread on a cellulose triacetate film base. For photographic coating, the usual photographic gelatin is used.
The film sample thus prepared is divided into two parts. One series of strips is bathed for about 2 minutes in a 1% solution of technical catalase. The other series remains without treatment for purposes of comparison.
Both series are exposed in a conventional sensitometer for 10 seconds behind a grey step wedge, and then subjected for varying periods storage at 25 C. and 60% relative humidity.
After this, the strips are developed with the following developer composition:
The usual fixing, washing and drying then follow.
The stabilizing effect on the developed latent image in the material with catalase-containing gelatin is shown in the following density chart:
CHART 1 Developed Developed Developed immediately after 8 after 28 afterwards days days Wedge Sample Sample Sample step Conbathed Conbathed Conbathed in No. trol in catalase trol in catalase trol catalase EXAMPLE 2 Using an ordinary photographic gelatin, a AgCl/ AgBr-mixed grain gelatin emulsion is produced containing approximately 20 mol. percent AgCl and 20 mol. percent AgBr. After chemical ripening with thiosulfate, the emulsion is divided into two parts. One part is mixed with com. of a 0.1% catalase solution per liter emulsion, the other part being used as a control for comparison. Each of the two emulsions is then coated on barytacoated paper as the emulsion carrier.
The emulsions thus produced are exposed, as in Example 1, in a sensitometer for 10* seconds behind a grey step wedge and then subjected for varying periods to a 25 C. and 60 C. relative humidity atmosphere.
After this, the materials are developed with the following developer composition for 2 minutes at 20 C.:
G. p-Methylaminophenol 2 Hydroquinone 4 Sodium sulfite 25 Sodium carbonate 18.5 Potassium bromide 2 followed by the usual fixing, washing and drying steps.
The following density chart shows the stabilizing effect of the added catalase:
4 EXAMPLE 3 A highly sensitive AgCl/AgBr gelatin emulsion is coated on a coated paper as the emulsion carrier. The emulsion is covered with a protective gelatin surface coating of 1.5 1. thickness. Before coating, ml. of a 1% catalase solution is added to 1 kg. of coating solution for the protective surface coating (1.8% aqueous gelatin solution). In a parallel experiment, the same emulsion is coated with a protective surface coating containing no catalase.
The material is exposed and developed as indicated in Example 2. Three sensitometer strips (approximately 4 cm. wide) of the materials to be compared are placed in desiccator, on the bottom of which a container with 50 ml. of a 5% hydrogen peroxide solution is placed.
In the material without catalase, a change occurs in the color of the silver image due to the influence of the H 0 vapor, from neutral black to yellow-brown after 12 hours, and to red-brown after 24 hours. The change in the color is first visible in the wedge steps having a lower silver image density. The silver image of the test emulsion containing catalase in the protective surface coating shows no change of color and remains neutral black.
We claim:
1. Gelatin associated with silver halide in a photographic light-sensitive composition, said gelatin containing catalase in amounts of more than 10 International Effectiveness Units per gram.
2. The gelatin according to claim 1 wherein said catalase is present in amounts ranging from 10 to International Effectiveness Units per gram.
References Cited UNITED STATES PATENTS 2,965,484 12/1960 Tulagin et al. 9619X FOREIGN PATENTS 811,907 4/1959 Great Britain 96-94 1,115,625 5/1968 Great Britain 96114.5
OTHER REFERENCES Hamm, F. A. et al., The Electron Microscopy of Photographic Grains, Specimen Preparation Techniques and Applications, Journal of Applied Physics, vol. 24, No. 12, December 1953, pp. 1495-1502.
WILLIAM D. MARTIN, Primary Examiner M. R. LUSIGNAN, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US76631768A | 1968-10-09 | 1968-10-09 |
Publications (1)
Publication Number | Publication Date |
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US3600182A true US3600182A (en) | 1971-08-17 |
Family
ID=25076079
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US766317A Expired - Lifetime US3600182A (en) | 1968-10-09 | 1968-10-09 | Photographic gelatins |
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US (1) | US3600182A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7354733B2 (en) * | 2001-03-29 | 2008-04-08 | Cellect Technologies Corp. | Method for sorting and separating living cells |
-
1968
- 1968-10-09 US US766317A patent/US3600182A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7354733B2 (en) * | 2001-03-29 | 2008-04-08 | Cellect Technologies Corp. | Method for sorting and separating living cells |
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