US3655412A - Process for the production of dispersions of colloidal silver - Google Patents
Process for the production of dispersions of colloidal silver Download PDFInfo
- Publication number
- US3655412A US3655412A US776272A US3655412DA US3655412A US 3655412 A US3655412 A US 3655412A US 776272 A US776272 A US 776272A US 3655412D A US3655412D A US 3655412DA US 3655412 A US3655412 A US 3655412A
- Authority
- US
- United States
- Prior art keywords
- silver
- gelatin
- dispersions
- nitrate
- salt
- 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
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 50
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title description 5
- 108010010803 Gelatin Proteins 0.000 claims abstract description 33
- 229920000159 gelatin Polymers 0.000 claims abstract description 33
- 235000019322 gelatine Nutrition 0.000 claims abstract description 33
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 33
- 239000008273 gelatin Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 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 abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 48
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000003287 optical effect Effects 0.000 claims description 16
- -1 alkali metal sulfite Chemical class 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical compound CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 15
- 230000007935 neutral effect Effects 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 9
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001429 visible spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- CQZWDPFHLZOQBQ-UHFFFAOYSA-N 5-methyl-2-sulfanyl-3h-thiadiazole Chemical compound CC1=CNN(S)S1 CQZWDPFHLZOQBQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000009498 subcoating Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/8255—Silver or silver compounds therefor
Definitions
- This invention relates to a process for the production of colloidal dispersions of silver, and more particularly, to dispersions of silver which absorb light in the visible spectrum having wave lengths longer than the wave length of blue light.
- black dispersions of colloidal silver can be used as antihalation layers on the back of a multilayer color film for the purpose of preventing halation caused by the reflection of rays of light from the surface of the film support.
- Various silver dispersions have also been suggested for use in making neutral grey optical filters, optical wedges, or yellow filter layers in light-sensitive multilayer photographic color films for the purpose of shielding certain emulsion layers from blue light.
- an antihalation layer used in photographic materials in particular, for use in multilayer color films, to be neutral in color, or to have a sufficiently high reflection opti cal density to light of the visible spectrum, so that a panchromatic film may be adequately protected from halation effects by such layer.
- Such an antihalation layer should also have a sufficiently high transmission optical density to light of the visible spectrum so that a panchromatic film will also be protected from fogging by light incident to the back of the film.
- the antihalation layer have no deteriorating effect, such as desensitization or fogging, upon the panchromatic emulsion layer adjacent thereto.
- the antihalation layer must also be capable of being completely bleached with conventional processing solutions.
- colloidal silver dispersions prepared by these methods have little deteriorating effects on adjacent emulsion layers, and can be bleached completely by conventional processing baths, they have disadvantages.
- the transmission optical densities of these dispersions are not neutral or the reflection densities are not high enough to make satisfactory antihalation layers from them for panchromatic films.
- Dispersions of colloidal silver which are not neutral in color are neither satisfactory for neutral density grey filters nor for optical wedges.
- black colored dispersions are particularly desirable for making antihalation layers on panchromatic films, it has not been a simple matter to produce such dispersions without creating particles which are so coarse that they settle out of the dispersions.
- the silver dispersed in the gelatin may be further coated on a support to yield a layer having a transmission optical density of at least 0.8 as measured with light having a wave length of 650 nm., 550 nm., and of 440 nm.
- a further object of the invention is to provide a process for making such dispersions of silver in a stable and reproducible manner.
- a still further object of the invention is to provide a means for producing an antihalation layer which has both high reflection and transmission optical densities and, has no deteriorating effects upon the adjacent photographic emulsion layers.
- neutral black or slightly bluish black dispersions of colloidal silver having the heretofore described above desirable characteristics are produced by, for example, first forming a bath of a simple water soluble silver salt dissolved in an aqueous solution of a hydrophilic protective colloid, such as gelatin, and then mixing therewith a reducing agent in the presence of at least 0.2 mole of an alkali metal sulphite and from 0.005 to 0.7 mole of a water soluble manganous salt, per mole of the silver salt. It is preferred to use an excess of the reducing agent.
- the dispersions are then either chilled, shredded and washed with cold water, or coagulated by adding thereto suitable flocculating agents, such as those described in US. Pat. No. 2,982,652 and in U.S. Pat. No. 2,489,341, and finally separated from the resultant supernatant liquid and washed with cold water.
- suitable flocculating agents such as those described in US. Pat. No. 2,982,652 and in U.S. Pat. No. 2,489,341, and finally separated from the resultant supernatant liquid and washed with cold water.
- water soluble polymers ordinarily employed in the production of light-sensitive photographic silver halide emulsions such as gelatin, polyvinyl alcohol, water soluble cellulose derivatives and so forth, may be employed.
- Photographic gelatins especially lime-processed gelatins, contain minute amounts of alkali earth metal ions such as calcium or magnesium ions.
- alkali earth metal ions such as calcium or magnesium ions.
- the manganous salts which may be employed in the present invention are those capable of being dissolved in water at 20 C. at a rate of not less than 0.1 mole per liter and further which have anions, which, in the presence of silver ions, do not cause the precipitation of a sparingly soluble silver salt, for example, manganous nitrate and manganous acetate.
- the dispersions are formed at a temperature from 40 to 65 C. and within an elevated pH range of from about 7 to 10, by use of a suitable alkali such as caustic alkali, sodium carbonate,
- potassium carbonate sodium borate
- sodium metaborate potassium metaborate
- sodium phosphate etc.
- reducing agents which may be used according to our invention are those known to the art as organic developing agents, for example, hydroquinone, toluhydroquinone, catechol, monomethylaminophenol, l-phenyl-3-pyrazolidone, paraphenylenediamine, ascorbic acid and so on.
- the black dispersions of silver obtained according to the present invention may further have added thereto, preferably prior to the washing procedure, thiol compounds or compounds capable of readily forming thiol compounds through decomposition thereof, in order to improve the stability on storage of the finished dispersions.
- thiol compounds or compounds capable of readily forming thiol compounds through decomposition thereof in order to improve the stability on storage of the finished dispersions.
- Suitable compounds are 2- mercaptoimidazole, 2-mercaptobenzoimidazole, Z-mercaptobenzoxazole, S-carboethoxy-2-mercapto-4-methylthiazole, 3-mercaptol ,2,4-triazole, 2-mercapto-5methylthiadiazole, and l-phenyl-S-mercaptotetrazole.
- the black dispersions of colloidal silver obtained according to the present invention may be used for making antihalation layers for color negative films, color reversal films, color print films, color positive films, color paper, and so forth, by uniformly coating and drying said dispersions onto a support which has previously been given a subcoating, the thickness of the antihalation layers being in the range of from about 1 to 10 microns.
- the reducing agent is added to a freshly or simultaneously formed mixture of a soluble silver salt and an alkali metal sulphite in an aqueous solution of a hydrophilic protective colloid, in the presence of a suitable amount of manganous ions and within an elevated pH range of from about 7 to l0.
- the following examples are of methods which illustrate, but do not limit, the present invention.
- EXAMPLE I To l parts of a 24 percent aqueous solution of limeprocessed inert bone photographic gelatin there were added parts of a 1 molar aqueous solution of sodium carbonate with stirring and keeping the temperature in the range of 3540 C. When the aqueous sodium carbonate solution was completely mixed with the gelatin solution, 3 parts of a l molar aqueous solution of manganous nitrate was added thereto. Then, 50 parts of a percent aqueous solution of silver nitrate were added at a constant rate for 30 seconds.
- the transmission optical density was about 1.38 at all wave lengths of 420 700 nm. when coated at a concentration of 0.7 grams of silver per square meter and the reflectance was about 3.8 percent to all wave lengths of light in the visible spectrum.
- EXAMPLE 2 A 5 aqueous solution of lime-processed inert bone photographic gelatin was passed through mixed beds of ion exchange resins, Amberlite lRl and IRA-400, at 38 C., to
- dispersions of colloidal silver were prepared in a like manner as mentioned above with the exception that 4 parts of a 1 molar aqueous solution of calcium nitrate was added in place of the manganous nitrate of Example 2. This mixture was coated onto a transparent film base at a concentration of 0.70 gram of silver per square meter.
- the transmission optical density and reflectance of the dispersions of colloidal silver are tabulated below.
- EXAMPLE 3 To 200 parts of a 20 percent aqueous solution of inert bone photographic gelatin were added, while stirring vigorously and keeping the temperature at 35-40 C., 8 parts of a l molar aqueous solution of sodium carbonate and 7 parts of a 1 molar aqueous solution of caustic potassium. To this, from 0.5 to 20 parts of a 1 molar aqueous solution of manganous nitrate and 25 parts of a 20 percent aqueous solution of silver nitrate were added simultaneously. After 30 seconds, a reducing solution which consisted of 3.5 parts of sodium sulfite and 1.3 parts of hydroquinone in 90 parts of water was added.
- the transmission optical density and reflectance are tabulated below.
- the amount of silver salt reducing agent is not critical and desirable amounts are from 0.25 to 1.50 moles per mole of silver salt.
- a method of preparing a black dispersion of silver in gelatin which comprises mixing an aqueous alkaline solution of gelatin with an aqueous solution of silver nitrate and a manganese salt in a ratio of from 340 to 1,360 grams of gelatin per mole of silver nitrate, and from 0.005 to 0.7 mole of said manganese salt per mole of said silver nitrate, said manganese salt being capable of being dissolved in water at 20 C.
- water soluble organic compound capable of reducing silver salt to silver colloid is hydroquinone, toluhydroquinone, catechol, monomethylaminophenol, l-phenyl-3-pyrazolidone, paraphenylenediamine or ascorbic acid.
- a method of preparing a black dispersion of silver in gelatin which comprises mixing an aqueous alkaline solution of gelatin with an aqueous solution of silver nitrate and a manganese salt selected from the group consisting of manganese nitrate and manganese acetate in a ratio of from 340 to 1360 grams of gelatin per mole of silver nitrate and from 0.005 to 0.7 mole of said manganese salt per mole of silver nitrate; and reducing the silver nitrate by adding to the resulting mixture at least 0.2 mole, per mole of silver nitrate, of an alkali metal sulfite and from 0.25 to 1.5 moles, per mole of silver nitrate, of a water-soluble reducing agent selected from the group consisting of hydroquinone, toluhydroquinone, catechol, monomethylaminophenol, l-phenyl-3-pyrazolidone, paraphenylenediamine and ascorbic acid, at a
- a supported stable silver dispersion in gelatin prepared by the method as claimed in claim 1 wherein when said dispersion is coated on a support so as to yield a layer containing from about 0.65 to about 0.75 grams of silver per square meter, said layer having a transmission optical density of at least 0.8 as measured with light having wave lengths of the group consisting of 650 nm., 550 nm. and 440 nm.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Colloid Chemistry (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7350267 | 1967-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3655412A true US3655412A (en) | 1972-04-11 |
Family
ID=13520079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US776272A Expired - Lifetime US3655412A (en) | 1967-11-15 | 1968-11-15 | Process for the production of dispersions of colloidal silver |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3655412A (enrdf_load_stackoverflow) |
| BE (1) | BE723841A (enrdf_load_stackoverflow) |
| DE (1) | DE1809214A1 (enrdf_load_stackoverflow) |
| FR (1) | FR1594774A (enrdf_load_stackoverflow) |
| GB (1) | GB1248213A (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094811A (en) * | 1975-12-30 | 1978-06-13 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of silver dispersions for filter layers and antihalation layers |
| US4429038A (en) | 1981-07-31 | 1984-01-31 | Agfa Gevaert Aktiengesellschaft | Process for concentrating yellow silver sols |
| US4605609A (en) * | 1983-09-09 | 1986-08-12 | Mitsubishi Paper Mills, Ltd. | Image receiving material with low calcium gelatin |
| US5167875A (en) * | 1988-10-26 | 1992-12-01 | Agea-Gevaert N. V. | Silver sulphide sol with ultrafine particle size |
| US6214299B1 (en) | 1999-06-01 | 2001-04-10 | Robert J. Holladay | Apparatus and method for producing antimicrobial silver solution |
| US20060182813A1 (en) * | 1999-06-01 | 2006-08-17 | Holladay Robert J | Colloidal silver composition having microbial properties |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1185540B (it) * | 1985-03-18 | 1987-11-12 | Minnesota Mining & Mfg | Materiale fotofrafico agli alogenuri d'argento per sviluppo tannante procedimento per produrre un'immagine in rilievo |
| US6043013A (en) * | 1998-01-29 | 2000-03-28 | Eastman Kodak Company | Color photographic element containing elemental silver and heterocyclic thiol in a non-light sensitive layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2921914A (en) * | 1957-02-13 | 1960-01-19 | Gen Aniline & Film Corp | Preparation of blue colloidal silver dispersions for antihalo layer |
| US3459563A (en) * | 1964-11-09 | 1969-08-05 | Fuji Photo Film Co Ltd | Process for the production of black colloidal-silver dispersion |
-
1968
- 1968-11-14 FR FR1594774D patent/FR1594774A/fr not_active Expired
- 1968-11-14 BE BE723841D patent/BE723841A/xx unknown
- 1968-11-15 GB GB54453/68A patent/GB1248213A/en not_active Expired
- 1968-11-15 DE DE19681809214 patent/DE1809214A1/de active Pending
- 1968-11-15 US US776272A patent/US3655412A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2921914A (en) * | 1957-02-13 | 1960-01-19 | Gen Aniline & Film Corp | Preparation of blue colloidal silver dispersions for antihalo layer |
| US3459563A (en) * | 1964-11-09 | 1969-08-05 | Fuji Photo Film Co Ltd | Process for the production of black colloidal-silver dispersion |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094811A (en) * | 1975-12-30 | 1978-06-13 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of silver dispersions for filter layers and antihalation layers |
| US4429038A (en) | 1981-07-31 | 1984-01-31 | Agfa Gevaert Aktiengesellschaft | Process for concentrating yellow silver sols |
| US4605609A (en) * | 1983-09-09 | 1986-08-12 | Mitsubishi Paper Mills, Ltd. | Image receiving material with low calcium gelatin |
| US5167875A (en) * | 1988-10-26 | 1992-12-01 | Agea-Gevaert N. V. | Silver sulphide sol with ultrafine particle size |
| US6214299B1 (en) | 1999-06-01 | 2001-04-10 | Robert J. Holladay | Apparatus and method for producing antimicrobial silver solution |
| US6743348B2 (en) | 1999-06-01 | 2004-06-01 | Robert J. Holladay | Apparatus and method for producing antimicrobial silver solution |
| US20060182813A1 (en) * | 1999-06-01 | 2006-08-17 | Holladay Robert J | Colloidal silver composition having microbial properties |
| US8535728B2 (en) | 1999-06-01 | 2013-09-17 | American Silver, Llc | Colloidal silver composition having antimicrobial properties |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1248213A (en) | 1971-09-29 |
| BE723841A (enrdf_load_stackoverflow) | 1969-04-16 |
| DE1809214A1 (de) | 1969-08-14 |
| FR1594774A (enrdf_load_stackoverflow) | 1970-06-08 |
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