US3153593A - Manufacture of silver halide emulsions - Google Patents
Manufacture of silver halide emulsions Download PDFInfo
- Publication number
- US3153593A US3153593A US192988A US19298862A US3153593A US 3153593 A US3153593 A US 3153593A US 192988 A US192988 A US 192988A US 19298862 A US19298862 A US 19298862A US 3153593 A US3153593 A US 3153593A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- gelatin
- parts
- emulsion
- water
- 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
- 239000000839 emulsion Substances 0.000 title claims description 55
- -1 silver halide Chemical class 0.000 title claims description 54
- 229910052709 silver Inorganic materials 0.000 title claims description 50
- 239000004332 silver Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title description 5
- 108010010803 Gelatin Proteins 0.000 claims description 47
- 239000008273 gelatin Substances 0.000 claims description 47
- 229920000159 gelatin Polymers 0.000 claims description 47
- 235000019322 gelatine Nutrition 0.000 claims description 47
- 235000011852 gelatine desserts Nutrition 0.000 claims description 47
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 27
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 26
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000002609 medium Substances 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- 238000005406 washing Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000005070 ripening Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 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 description 5
- 239000000126 substance Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100505735 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cot-2 gene Proteins 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- WTKUDAMSULHEKV-UHFFFAOYSA-N [Se](C#N)C#N.[K] Chemical compound [Se](C#N)C#N.[K] WTKUDAMSULHEKV-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KOWWOODYPWDWOJ-LVBPXUMQSA-N elatine Chemical compound C([C@]12CN(C3[C@@]45OCO[C@]44[C@H]6[C@@H](OC)[C@@H]([C@H](C4)OC)C[C@H]6[C@@]3([C@@H]1[C@@H]5OC)[C@@H](OC)CC2)CC)OC(=O)C1=CC=CC=C1N1C(=O)CC(C)C1=O KOWWOODYPWDWOJ-LVBPXUMQSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- RQVOBHDSEHUCDG-UHFFFAOYSA-M gold(1+);thiocyanate Chemical compound [Au]SC#N RQVOBHDSEHUCDG-UHFFFAOYSA-M 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- FYOWZTWVYZOZSI-UHFFFAOYSA-N thiourea dioxide Chemical class NC(=N)S(O)=O FYOWZTWVYZOZSI-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- G03C1/015—Apparatus or processes for the preparation of emulsions
Definitions
- the formed silver halide dispersion is ripened which means that the dispersion is kept for a certain time at a certain temperature in order to obtain the desired grain size and grain distribution.
- the dispersion is first jellified by cooling.
- the formed gel is noodled or finely divided in another way and the salts present are extracted from the noodles with water at low temperature by dialysis.
- the washed emulsion is melted by heating whereupon gelatin and other ingredients such as chemical sensitizers are added. Thereupon the emulsion is chemically ripened.
- optical sensitizers, color couplers, hardeners, anti-fogging agents, wetting agents, matting agents, etc. can be added.
- This process has the great disadvantage of needing considerable time for setting, noodling and washing. Moreover, this process has to be carried out in the presence of a relative large amount of binding agent which cannot be decreased at will.
- a concentration of at least 4% of binding agent is necessary.
- a relatively large amount of light-sensitive silver halide per unit of area is necessary.
- Such emulsions can be concentrated by evaporating the water present whereby, however, the ratio of binding agent to light-sensitive salt remains unchanged.
- more concentrated emulsion is only obtained together with an increased viscosity which hinders the coating of the emulsion so that, rather than concentrating the emulsion too much, it is usually preferable to apply several emulsion layers one upon another in order to obtain the desired amount of silver salt per unit of area.
- the gelation and the noodling of the above mentioned photographic emulsion can be avoided by coagulating this emulsion either by adding a large amount of a water miscible organic solvent wherein the binding agent does not dissolve or by salting out the binding agent by the adding of salts such as lead, titanium, thorium, zirconium, ammonium, barium, calcium, sodium and zinc salts.
- salts such as lead, titanium, thorium, zirconium, ammonium, barium, calcium, sodium and zinc salts.
- gelatin content of the dispersion is not higher than 2% and the weight ratio of gelatin to silver nitrate (calculated on an equivalent weight basis to the silver halide) varies between A and 7 and (2)
- the gelatin silver halide coprecipitate is hardened before the washing step by treating it with a concentrated aqueous solution of ammonium sulfate.
- the emulsions prepared in such circumstances are not decreased in sensitivity.
- a part of the ammonium sulfate can be formed in situ, in the preparation of an ammoniacal emulsion during the coprecipitating of the gelatin and the silver halide, by adding, together with the concentrated solution of ammonium sulfate, sulfuric acid while the pH of the medium may not fall below pH 7.
- the sulfuric acid is preferably added as a mixture with the concentrated ammonium sulfate.
- the concentration of the ammonium sulfate varies preferably between 5 and 20% at the end of the precipitation. In the hardening stage the concentration of the ammonium sulfate amounts preferably to between 7 and 40%.
- Distilled water, demineralized water and tap water preferably with a French degree of hardness not higher than 45 can be used as wash water.
- the draining off of the supernatant liquid after cot2 precipitation of the gelatin and the silver halide is preferably carried out until the precipitate remaining amounts to about to /s part of the original volume.
- the process according to the invention has, in comparison with the process of the U.S. patent specification 2,618,556, the advantage of avoiding a decrease of sensitivity of the ammoniacal emulsions by precipitating with acids below a pH of 7.
- the amount of gelatin used for the preparation according to the present invention of photographic lightsensitive silver halide emulsions can vary between 2 and g. per 100 g. of silver nitrate and depends on the size of the silver halide grains while the gelatin concentration of the silver halide dispersion before precipitating preferably does not exceed 3% by weight of the water present. A gelatin concentration from 0.5 to 2% is to be preferred.
- the formed precipitate consists of flocculent particles of gelatin containing silver halide crystals dispersed therein, so that the several crystals stay separated from each other.
- the hardened gelatin particles of the precipitate are in a finely divided form so that they can be easily and rapidly washed with water, preferably at low temperature (:10" C.). After washing the precipitate is easily dispersed in water by heating and thereupon the desired amount of binding agent is added.
- the final amount of binding agent which is added to the light-sensitive salts can be chosen at pleasure so that emulsions can be obtained with a high amount of light-sensitive silver salt without increasing the content of gelatin and that a large amount of silver salts can be coated with less viscous emulsions onto relatively smaller surfaces.
- These emulsions with easily adjustable concentrations are especially suited for special coating techniques such as air-knife coating and extrusion.
- the desired grain distribution of the silver halide is obtained.
- the light-sensitivity of the silver halide crystals can be increased by chemical sensitization.
- the chemical sensitizers are mostly added after wash ing the emulsion. They may also be added during the precipitation of the silver halide or during the Ostwald ripening for instance when an active gelatin is used as dispersing agent for the silver halide.
- the emulsion can be ripened with active gelatin or sulfur compounds can be added to the silver halide emulsion such as allyl isothiocyanate, allyl thiourea, sodium thiosulfate or potassium selenocyanide.
- sulfur compounds can be added to the silver halide emulsion such as allyl isothiocyanate, allyl thiourea, sodium thiosulfate or potassium selenocyanide.
- the emulsions can also be sensitized with reducing agents such as tin salts or imino-aminomethane sulfinic acid compounds (German patent specification 1,020,864, filed April 28, 1956).
- reducing agents such as tin salts or imino-aminomethane sulfinic acid compounds (German patent specification 1,020,864, filed April 28, 1956).
- the highi-sensitive negative emulsions prepared according to the invention can especially be sensitized with gold (I) thiocyanate and sodium thiosulfate as described in French patent application 893,935, filed April 10, 1962.
- ingredients may be added such as optical sensitizing dyestuifs, stabilizers, fog inhibiting agents, color couplers, hardening agents, wetting agents and matting agents.
- Example 1 300 parts of silver nitrate are dissolved in 2900 parts of distilled water and then at 40 C., while vigorously stirring, added in 2 min. to a solution of 250 parts of potassium bromide, 45 parts of gelatin and 5 parts of potassium iodide in 1200 parts of water.
- the mixture is washed for another four to five times; each time with 4000 parts of water and the supernatant solution is each time decanted till a volume of 1200 parts is left. After the last washing and decanting stages 600 parts of distilled water and 250 parts of gelatin are added.
- the mixture is stirred at 45 C. for 1 hr. and the emulsion is diluted with distilled water up to 3000 parts. Finally, the emulsion is chemically ripened at The emulsion is coated onto a cellulose ester support. A fog-free photographic material is obtained.
- Example 2 250 parts of silver nitrate are dissolved in a mixture of 200 parts of concentrated ammonium hydroxide and 220 parts of water. This solution is then at once added to a solution of 570 parts of potassium'bromide, 10 parts of potassium iodide and 28 parts of gelatin in 2300 parts of water. Immediately thereafter a solution of 250 parts of silver nitrate in 220 parts of water and 200 parts of ammonium hydroxide are added in 5 min. The temperature of these solutions amounts to 52 C. The physical ripening takes place in 35 min. at 55 C. Then, while vigorously stirring 1300 parts of a 50% aqueous solution of ammonium sulfate is added.
- a precipitate of silver bromide and gelatin is formed which is allowed to settle for min.
- the supernatant mother-lye is decanted till a volume of 500 parts is left in the reaction flask.
- 500 parts of a 50% aqueous solu tion of ammonium sulfate are added.
- the mixture is stirred for another 20 min. and then four times washed with 300 parts of water followed each time by decanting till a volume of 500 parts is left in the vessel.
- the thus obtained emulsion is coated onto a cellulose triacetate support.
- a contrasty photographic material is obtained.
- Example 3 100 parts of silver nitrate dissolved in 85 parts of water and 82 parts of concentrated ammonium hydroxide are added in 1 min. to a solution of 130 parts of potassium bromide, 5 parts of potassium iodide and 20 parts of gelatin in 880 parts of distilled water. The temperature of the solutions amounts to 50 C. After about 5 min. a solution of 150 parts of potassium bromide in 300 parts of water are added and then a solution of 150 parts of silver nitrate in 130 parts of distilled water and 125 parts of concentrated ammonium hydroxide are added in 4 min. The pH of the emulsion amounts at this moment to about 10. The emulsion is allowed to digest at 55 C. for 30 min.
- Washing is repeated for 4 to 6 times till the conductivity of the water is reached.
- a process for the manufacture of high sensitive neutral and ammoniacal silver halide emulsions comprising: (1) Preparing a silver halide dispersion by reacting a water-soluble halide with silver nitrate in a medium selected from the group consisting of neutral and ammoniacal aqueous media, said medium containing gelatin in an amount not in excess of about 2% and within the range of 2-25% of said silver nitrate, (2) Introducing into said dispersion a concentrated solution of ammonium sulfate in an amount sufiicient to co-precipitate said gelatin and silver halide but not suificient to decrease the pH of said medium below about pH 7,
- step (3) The process of claim 1 wherein said ammonium sulfate is introduced into said dispersion in step (2) in an amount sufficient to give a concentration of said ammonium sulfate of about 5-20%.
- step (4) 4. The process of claim 1 wherein said additional ammonium sulfate is admixed in step (4) in an amount sutficient to give a concentration thereof of about 740%.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE2040625 | 1961-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3153593A true US3153593A (en) | 1964-10-20 |
Family
ID=3864747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US192988A Expired - Lifetime US3153593A (en) | 1961-05-08 | 1962-05-07 | Manufacture of silver halide emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3153593A (en, 2012) |
| BE (1) | BE603491A (en, 2012) |
| DE (1) | DE1148867B (en, 2012) |
| GB (1) | GB1008694A (en, 2012) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3436220A (en) * | 1964-11-27 | 1969-04-01 | Gaf Corp | Preparation of photographic silver halide emulsions utilizing polyoxalkylenated gelating derivatives |
| US3620752A (en) * | 1969-03-12 | 1971-11-16 | Tatsuro Matsuo | Precipitating silver halide in 0.5 to 3 percent weight aqueous gelatin solution |
| US5972591A (en) * | 1990-12-20 | 1999-10-26 | Eastman Kodak Company | Thickener for delivery of photographic emulsions |
| US9174871B2 (en) | 2012-11-02 | 2015-11-03 | Empire Technology Development Llc | Cement slurries having pyranose polymers |
| US9212245B2 (en) | 2012-12-04 | 2015-12-15 | Empire Technology Development Llc | High performance acrylamide adhesives |
| US9238774B2 (en) | 2012-11-02 | 2016-01-19 | Empire Technology Development Llc | Soil fixation, dust suppression and water retention |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2126516A (en) * | 1934-09-15 | 1938-08-09 | Szasz Geza | Photographic process |
| US2618556A (en) * | 1947-11-19 | 1952-11-18 | Eastman Kodak Co | Process for preparing photographic emulsions |
| US3007796A (en) * | 1959-02-25 | 1961-11-07 | Gen Foods Corp | Process for preparing photographic emulsions |
| US3031304A (en) * | 1958-08-20 | 1962-04-24 | Albert J Oliver | Fine grain nuclear emulsion |
| US3067035A (en) * | 1959-04-01 | 1962-12-04 | Du Pont | Gelatin-anion soap complex dispersion in polyvinyl alcohol photographic emulsions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE528741A (en, 2012) * | 1953-05-11 | |||
| BE558500A (en, 2012) * | 1956-06-19 |
-
0
- BE BE603491D patent/BE603491A/xx unknown
-
1961
- 1961-08-01 DE DEG32843A patent/DE1148867B/de active Pending
-
1962
- 1962-05-07 US US192988A patent/US3153593A/en not_active Expired - Lifetime
- 1962-05-08 GB GB17712/62A patent/GB1008694A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2126516A (en) * | 1934-09-15 | 1938-08-09 | Szasz Geza | Photographic process |
| US2618556A (en) * | 1947-11-19 | 1952-11-18 | Eastman Kodak Co | Process for preparing photographic emulsions |
| US3031304A (en) * | 1958-08-20 | 1962-04-24 | Albert J Oliver | Fine grain nuclear emulsion |
| US3007796A (en) * | 1959-02-25 | 1961-11-07 | Gen Foods Corp | Process for preparing photographic emulsions |
| US3067035A (en) * | 1959-04-01 | 1962-12-04 | Du Pont | Gelatin-anion soap complex dispersion in polyvinyl alcohol photographic emulsions |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3436220A (en) * | 1964-11-27 | 1969-04-01 | Gaf Corp | Preparation of photographic silver halide emulsions utilizing polyoxalkylenated gelating derivatives |
| US3620752A (en) * | 1969-03-12 | 1971-11-16 | Tatsuro Matsuo | Precipitating silver halide in 0.5 to 3 percent weight aqueous gelatin solution |
| US5972591A (en) * | 1990-12-20 | 1999-10-26 | Eastman Kodak Company | Thickener for delivery of photographic emulsions |
| US9174871B2 (en) | 2012-11-02 | 2015-11-03 | Empire Technology Development Llc | Cement slurries having pyranose polymers |
| US9238774B2 (en) | 2012-11-02 | 2016-01-19 | Empire Technology Development Llc | Soil fixation, dust suppression and water retention |
| US9212245B2 (en) | 2012-12-04 | 2015-12-15 | Empire Technology Development Llc | High performance acrylamide adhesives |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1008694A (en) | 1965-11-03 |
| DE1148867B (de) | 1963-05-16 |
| BE603491A (en, 2012) |
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