US2614928A - Method of preparing photographic emulsions - Google Patents
Method of preparing photographic emulsions Download PDFInfo
- Publication number
- US2614928A US2614928A US768475A US76847547A US2614928A US 2614928 A US2614928 A US 2614928A US 768475 A US768475 A US 768475A US 76847547 A US76847547 A US 76847547A US 2614928 A US2614928 A US 2614928A
- Authority
- US
- United States
- Prior art keywords
- gelatin
- derivative
- silver halide
- silver
- 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
- 238000000034 method Methods 0.000 title claims description 42
- 239000000839 emulsion Substances 0.000 title description 71
- 229920000159 gelatin Polymers 0.000 claims description 174
- 239000008273 gelatin Substances 0.000 claims description 173
- 108010010803 Gelatin Proteins 0.000 claims description 144
- 235000019322 gelatine Nutrition 0.000 claims description 144
- 235000011852 gelatine desserts Nutrition 0.000 claims description 144
- 229910052709 silver Inorganic materials 0.000 claims description 105
- 239000004332 silver Substances 0.000 claims description 105
- -1 SILVER HALIDE Chemical class 0.000 claims description 96
- 239000006185 dispersion Substances 0.000 claims description 82
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 18
- 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 description 17
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229940014259 gelatin Drugs 0.000 description 164
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 28
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 239000000908 ammonium hydroxide Substances 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 229940094035 potassium bromide Drugs 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 125000005594 diketone group Chemical group 0.000 description 7
- 229960001516 silver nitrate Drugs 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 235000007715 potassium iodide Nutrition 0.000 description 4
- 229960004839 potassium iodide Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GJEDSIHWCPPJFN-UHFFFAOYSA-N diethyl 2,3-diacetylbutanedioate Chemical compound CCOC(=O)C(C(C)=O)C(C(C)=O)C(=O)OCC GJEDSIHWCPPJFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229940083608 sodium hydroxide Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical class CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- MFZUXRKTKZKWSS-UHFFFAOYSA-N benzene;sulfuryl dichloride Chemical class ClS(Cl)(=O)=O.C1=CC=CC=C1 MFZUXRKTKZKWSS-UHFFFAOYSA-N 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical class CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 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
- G03C1/04—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
- This invention relates to the preparation of photographic emulsions having silver halide as the sensitive element in which the silver halide is prepared in dispersed form in a gelatin derivative.
- the gelatin derivative-silver halide dis persion is coagulated and washed.
- This, invention also includes the products obtained thereby washed silver-halide grains u ng gelatin or gela tin derivative as the vehicle erefor.
- the most common'method of preparing silverhalide dispersions is by reacting a water-soluble and the emulsions obtained by re-dispersing the f salt, such as silver nitrate and a water-solub1e halide, such as potassium bromide in an aqueous solution of gelatin. There is formed thereby a' dispersion of the silver halide in an aqueous solu-- tion of gelatin, which solution also contains salts resulting as a by-product of the. reaction.
- the A emulsion maker hasin the past been limited in the scope of his operations by the physical properties peculiar to that material.
- Our invention is based upon the discovery that gelatin derivatives are useful as peptizers for dispersions of silver halide and that those derivatives are acidcoagulable and will envelop the silver grains when so precipitated.
- the method of our invention avoids the limitations which have previously characterized the preparation of silver-halide dispersions and is valuable, for exvhanding thepossible(conditions for the manufacture of photo raphic silver halide emulsions of difierent speeds, contrast, andother photographic characteristics.
- our invention offers a simple meansof preparing emulsions of high silver concentration,' this being especially valu able in the manufacture of photographic films bearing large quantities of silver per unitarea.
- Gelatin derivatives are prepared byreacting.
- gelatin with a reagent such as asulfonyl chloride, a carboxylic acid chloride, a, carboxylic acid anhydride, an aromatic isocyanate, or a 1,4 diketone at a pH of8-1l or more imparted by the addition of asuitable base, such 'as sodiumhydroxide or ammonium hydroxide, preferably at a temperature of 2060 C.
- a suitable base such 'as sodiumhydroxide or ammonium hydroxide
- resulting product may be employeddirectly i'nour invention without separating it from the solution employed as dispersing agents for silver halide have the property of enveloping the silver-halide grains upon acidulation of the mass and that the resulting insoluble material consisting of silverhalide grains enveloped by the gelatin derivatives may. be washed free of salts or any other watersoluble materials which may be present therein.
- To effect coagulation it is desirable to acidify the mass to a pH of approximately 4.5 or less. When inert salts are present at relatively high concentration, the per range for this acid coagulation phenomenon may extend as low as 3.
- the silver halide may be prepared in an aqueous solution of gelatin as the peptizer, and the gelatin thus present may .changes'of .water. .--method,1,the coagulum may be redispersedin be converted into the derivative prior toacidifying and washing.
- the gelatin derivative is employed as the protective colloid that material is employed in substantially the same quantity as that of the gelatin usually used in'preparing silver halide emulsions.
- the silver halide maybe prepared by any of the normal methods for emulsification of the silver halides 'for examplegby introducing a stream of an aqueous-solution-of silver nitrate and a stream of an aqueous. solution:
- an alkali metal halide such as potassium-bromide
- an alkali metal halide such as potassium-bromide
- acid is. added ..in.-.a..sufficient. amount to lower the pH: to, less ..than. 4.5, the; range. of pH depending ,uponthe amountof salt present as explainedabove.
- the coagulum may. now be. separated. from, the liquid by any one .ofseveral. techniques. In the. simplest form this rsupernatant motherv liquor may be removed'from .the receptacle .in which. the .mass .is. contained by A means .of..a siphon and the, coagulum may be rinsed with water to remove excess insoluble salts. .Thecoagulum after this. washing operation :consists ..of, silver halide, the gelatin derivative, .any. other water-insoluble. materials whichv are ,present,-and .a small amount of residual soluble salt dissolved. in water trapped in. the. coagulum.
- thiscoagulum may be useddirectly without'further washing. for instance, in the, preparation of emulsions; for the ;.-coating ofpaperor. other permeable supports.
- preparationof .emulsionslfor ,lthe coating. of ifilmorglass: plates, however,1it may be. desirable .,.to reduce further the content .of solubletsalts -.which may be present. .This may be ,done. by any one. of:severa1. methods. I. For.
- The: number of. rinses which. are neces- -sary to reduce the saltcontent of thecoagulum to the desiredpoi-nt may be determined by experi- -ment,-.but usually..is.within. the range of. 1 to 4
- the coagulum which has been washed by any onexofithe'.three' general methods outlined above may then be.redispersed to form photographic emulsions suitable for the subsequent finishing .10
- gelatin derivative instead of normalgelatinmay beemployed as the vehicle in the formation of the photographic emulsion.
- The'mixtureof coagulum, watenzggelatinand any other desired reagents is stirred at approximately 4:0 C. for a time" suiTicient to: effect aicomplete redispersal of .the coagulum, usually requiring ten to twenty-minutes.
- the emulsionobtained has properties comparable to those of the best types of washed" emulsions and'responds readily to chemical sensitizationmr .iafter ripening .and optical sensitization ofthe types employed upon photographic emulsions. generally.
- The. emulsions. prepared iniaccordance with our invention may be coated onto a support, using the techniques which arestandard in the emulsion coating art.
- the silver-halide gelatin derivative coagulum. mayv be washed toremove insoluble salts by. either offlthe two .methcids. outlined above.
- soluble halide such as potassium bromide
- diketones posses the characteristic of water solubility at pH values above approximately 4.5 and below approximately 4.0, providing, of course,
- salts are absent.
- these derivatives are relatively water-insoluble.
- the pH range of insolubility in water is broadened by the presence of neutral
- the derivative obtained by reacting benzene sulfonyl chloride with gelatin is insoluble in aqueous solutions over a pH range extending from 3 to 4.5 if a concentration of potassium nitrate of at least 0.1 normal is present.
- in electrolyte is usually present in the form of potassiurn nitrate resulting from the double decomposition reaction between silver nitrate and a In some soluble halide also be present. Under such conditions the adjustment of pH in the first coagulation is not particularly critical.
- any acid may be employed which will give the desiredpI-I in the mass and which will not deleteriously affect the photographic material.
- Dilute aqueous sulfuric acid has been found to be particularly useful for this purpose.
- acetic acid or phosphoric acid are useful for this purpose if for some reason sulfuric acid is not available.
- gelatin derivatives In the preparation of gelatin derivatives the gelatin in aqueous solution is treated with a solution of the reagent in a suitable solvent, prefer- Some reagents which are useful in this connection are acetone, dioxane, isopropyl alcohol, and the like. of thecornpounds which aresuitable for use in preparing gelatin derivatives useful in the process of our invention are as follows:
- the, coagulum prepared by the use of gelatin derivatives is especially suitable for preparation of driedemulsions since it may be obtained in a state nearly free of excess water and, therefore, the drying operation is simplified and rendered less expensive.
- the coagulum may be obtained in the suitable physical form for the purpose, and the dried emulsion may readily be redispersed in water containing appropriate alkali.
- the washed coagulum prepared from the dicarboxylic acid anhydride derivatives, such as phthalic anhydride is especially useful.
- the coagulation operation may be carried out either after the preparation of silver halide to remove watersoluble salts or after a heat treatment with appropriate chemical'sensitizers so that coagulated silver-halidetgrains' 'areiobtainedbefore or after having been brought to optimum photographic speed.
- These grains maybedriedat eitherv stage .in the cycle without harming their properties when finally made up in the emulsion,
- gelatin derivatives which. may be employed in accordance with ourinvention may be either derivatives of a high viscosity gelatin or, if desired, they maybe derivatives of gelatin which has been hydrolyzed. or reduced in viscosity.
- Our invention is..not. critical as to the gelatin which is employedin preparing the derivatives to be used in our invention or process including gelatin derivatives generally in .the preparation of washed emulsions by coagulation washing methods.
- Example 1.-100 g.,of silver 'nitrate weredissolved in 900 cc. of distilled waterat 25 C. 80g. of potassium bromide, 1 g. of potassium. iodide and 25 g. of gelatin weredissolved in another 900 cc. of distilled water. Thetemperature was adjusted to 50 C. and the silvernitrate solution was added to the bromide-gelatin solution over a period of approximately ten minutes with vigorous stirring. The temperature was maintained at 50 C. The mass was then stirred for ten minutes at 50 Qand then cooled t 40 C. The pH was adjusted to. 9.5 by the addition of dilute ammonium hydroxide and 3 cc. of benzene 'su-lfonyl chloride in 40 cc. of dry acetone were added. The "mass-was stirred at 40 C. for five minutes; Sulfuric acid was then added to. ad-
- the mother. liquor was decanted oh, and the silver halide disper- "sion' waswa'shedtwice with distilled water at -'20' C. There was then added to the mass 150 g. of gelatin in solution in 1500 cc. of distilled water, and the mass was stirred at 40C. Ammonia was added to bring the emulsion pH to 615, and stirring was continued until all of the solid matter was completely dispersed in the "liquid. The resulting emulsion was then processed'and coated as is'usual for photographic emulsions;
- EwampZe The use 0] them-carbony benzene suijonyl derivative of gelatin for making silverhalidedispersions:
- potassum bromide was added.
- the emulsion was finished by heating at C. for 20-40 minutes and was then coated onto glass plates where theemulsion layer was-dried and tested sensitometrically by'exposure in .a sensitometer and development. in. a photographic developer.
- the emulsion showed normal .sensi-tometriccharacteristics.
- the emulsion was prepared as in Example-3 using this furoyl .halide derivativeof gelatin as the peptizing agent. .After the silver-halide grains had been thoroughly washed, the emulsion was cooled to 35, the .pI-I.w,as.lowered..to..3 with dilute sulfuric. acid, the coagulumwas washed, rinsed with three changes .of .cold water and then made up withthe desired quantities of gelatin and water.
- The-.coagulated silverhalide grains and gelatin derivative. were readily dispersed-at a pH of 6-7; The emulsion was made up with an. aqueous solution of gelatin. The pH was adjustedand potassium bromide was added as described herein.
- the emulsion was finished by- .heating at..65. C. for...a.- short time a and was coated on film support which was dried and tested photographically. The emulsion showed normal sensitometric characteristics.
- Example 5 The use of the phthalz'c anhydride derivative of gelatin in making silver-halide dispersz'ons:
- the gelatin derivative was prepared by the method described in Example 3 except that g. of phthalic anhydrideiin 35 cc. of dry acetone was used instead of the benzoyl chloride.
- the silver-halide dispersion was prepared by adding to a solution of80 g. of potassium bromide 1 g. of potassium iodide and g. of the gelatin derivative in 900 cc. of distilled water at 50 C., a solution of 100 g. of silver nitrate in 900 cc. of distilled water at 50 C. all over a period of ten minutes.
- the temperature of the resulting mass was then maintained at 50 C. for another ten minutes.
- the silver-halide dispersion was then cooled to C. and dilute surfuric acid was added thereto to bring the pH to 3.
- the clear supernatant liquid formed upon standing was decanted.
- Dilute ammonium hydroxide was then added to adjust the pH to 3.8-4.2 at which point the gelatin derivative and silver halide settled to the bottom of the container.
- the silverhalide dispersion was made up with gelatin and water and with proper finishing gives an emulsion having normal sensitometric characteristics.
- the washed coagulum consisting of silver-halide grains and the gelatin derivative may be dried.
- the dried coagulum it may be employed by soaking in water for a time whereupon it may be readily dispersed at a pH of approximately 6 or 7.
- the maleic anhydride derivative of gelatin was prepared in the same manner as described in Example 3 except that 4 g. of maleic anhydride was employed in reacting upon the gelatin instead of the benzoyl chloride.
- the emulsion was prepared by mixing a solution of 80 g. of potassium bromide, l g. of potassium iodide and 25 got gelatin in 900 cc. of distilled water at 50 C. and adding over a period of ten minutes a solution of 100 g. of silver nitrate in 300' cc. of distilled water at the same temperature.
- the temperature of the dispersion was maintained at 50 C. for an additional ten minutes, was then cooled to 35 C. and dilute sulfuric acid was added to impart a pH of 3.0.
- the coagulum settled to the bottom of the container, the supernatant liquid was decanted, and a volume of water equal to the original volume was added.
- the temperature was adjusted to 35 C. and while stirring the pH was adjusted to 6-8 with dilute ammonium hydroxide.
- the coagulum was thus redispersed in water.
- Dilute sulfuric acid was added to impart a pH of 3.8-4.2 whereupon the coagulum again settled.
- the liquid was decanted, and the silver-halide dispersion was mixed with an aqueous gelatin.
- the resulting emulsion was coated on film base and tested for photographic characteristics. Normal sensitometric characteristics were obtained therefrom on finishing.
- Example 7 Use of the phenyl ureido derivative of gelatin in preparing silver-halide dispersions: A silver-halide dispersion was preparedby;
- the gelatin derivative prepared may be employed as the dispersing colloid during the silver halide precipitation.
- the coagulation procedures in both cases are identical.
- Example 9-A gelatin derivative was prepared in the same manner as in Example 3 except that diethyl diacetyl succinate was added before rais-' ing the pH to 10, and the reaction time was six hours, the diethyl diacetyl succinate being employed instead of benzoyl chloride.
- the silverhalide dispersion was prepared as described in that example using the diethyl succinate derivative of gelatin as the dispersing colloid. After the temperature of the dispersion had been maintained at 50 C. for ten minutes, the emulsion was cooled to 35 C. and dilute sulfuric acid was added to impart a pH of. 3.
- -I n amethod of preparing washed silver halide-dispersions, thesteps which comprise mixtogether a-water-soluble silver salt and a water-soluble halide salt in an aqueous solution of 'a gelatin-derivative whose presence renders the-dispersioncoagulable at 'a pH within the range of pH- 3-4:.5, which derivative is selected from the group consisting of the aromatic sulfonyl chloride-derivatives of gelatin, the carboxylic acid chloride derivatives of gelatin, the carboxylic acid anhydride derivatives of gelatin.
- a'method of preparing washed silver halide dispersions the steps which comprise n'i'ixing-together a water-soluble silver salt and a water-soluble'halide salt in an aqueous solution of-"an'aromatic sulfonyl chloride derivative of gelatinwhose presence renders the dispersion coagulable' at a pll within the range of pH 3-4.5, coagulatingthe dispersion of silver halide in gelatin derivative thusformed'by adjusting to said-"pH wherebysilver halide-gelatin derivative grains are formed and subsequently separating the" silver halide-gelatin derivative grains thus formed fromthe liquid portion of the mass.
- a method'of preparingwash'ed silver halide dispersions the steps which comprise mixingiutogether a water-soluble silver salt and a water-soluble halide salt in an aqueous solution or a carboxylic acid anhydride derivative of; gelatin whose presence renders the dispersion coagulable at a pH within the range or pH 3-4151, coagulating-the dispersion of silver halide in gelatin derivative thus formed by adjusting to said pH whereby silver halide-gelatin deriva- 12 tive grains are formed andsubsequently-separating the silver halide-gelatin derivative grains thus formed from the liquid portion of the. mass.
- a method of preparing washed silver halide dispersions the steps which comprise mixing together a water-soluble silver salt and a water-soluble halide salt in an aqueous.-solu-' tion of 1,4 diketone derivative of gelatin whosepresence renders the dispersion coagulable ata pH within the range of pH 3-4.5, coagulating the dispersion of silver halide in gelatin'derivative thus formed by adjusting to said pH whereby silver halide-gelatin derivative grains are formed and subsequently separating the silver halide-gelatin derivative grains thus formed from the liquid portion of the mass.
- a method of preparing washed silver halide dispersions the steps which comprise mixing together a water-soluble silver salt and a water-soluble halide salt in an aqueous solution of the benzoyl chloride derivative of gelatin whose presence renders the dispersion coagulable at a pH within the range of pH 3-4.5, coagulating the dispersion of silver halide in gelatin derivative thus formed by adjusting to said pH whereby silver halide-gelatin derivative grains are formed and subsequently separating the silver halide-gelatin derivative grains thus formed from the liquid portion of the'mass.
- a method of preparing washed silver halide dispersions the steps which comprise mixing together a water-soluble silver salt and a water-soluble halide salt in an aqueous solution of the phthalic anhydride derivative of gelatin whose'presence renders the dispersion coagulable at a pH within the range of pH 3-4.5, coagulating the dispersion of silver halide in gelatin derivative thus formed by adjusting to said pH whereby silver halide-gelatin derivative grains are formed and subsequently separating thesilver halide-gelatin derivative grains thus formed from the liquid portion of the mass.
- a method of preparing a gelatino-silver halide emulsion which comprises preparing a silver halide dispersion by mixing together a water-soluble silver salt and a Water-soluble halide in an aqueous solution of a phthalicanhydride derivative of gelatin whose presence renders the dispersion obtained coagulable at a pH within the range of pH 3-4.5, coagulating the dispersion of silver halide in gelatin derivative by adjusting to said pH whereby silver halide-gelatin, derivative grains are formed, separating the thus-formed silver halide-gelatin derivative grains from the liquid portion of the mass and subsequently mixing those grains with gelatin and water as a protective colloid for the silver halide whereby a photosensitive emulsion is formed.
- a method of preparing washed silver halide dispersions the steps which comprise mixing together a water-soluble silver salt and a water-soluble halide salt in an aqueous solution of a gelatin derivative whose presence renders the dispersion coagulable at a pH within the range of pH 3-4.5, which derivative is selected from the group consisting of the aromatic sulfonyl chloride derivatives of gelatin, the carboxylic acid chloride derivatives of gelatin, the carboxylic acid anhydride derivatives of gelatin, the aromatic isocyanate derivatives of gelatin and the 1,4 diketone derivatives of gelatin, coagulating the dispersion of silver halide in gelatin derivative by adjusting to said pH whereby silver halide-gelatin derivative grains are formed, separating those grains from the liquid portion of the mass, redispersing the grains thus obtained in water at an elevated pH followed by adjusting the pH of the solution to that which will coagulate the silver halide dispersion which pH is within the range of 3-4.5, and
- a method of preparing washed silver halide dispersions the steps which comprise mixing together a water-soluble halide salt and a water-soluble silver salt in an aqueous solution of a phthalic anhydride derivative of gelatin, whose presence renders the dispersion thus obtained coagulable at a pH within the range of pH 3-4.5, coagulating the dispersion of silver halide in gelatin derivative by adjusting to said pH whereby silver halide-gelatin derivative grains are formed, separating those grains from the liquid portion of the mass, redispersing those grains in water at an elevated pH followed by adjusting the solution to a pH which will coagulate the silver halide dispersion. which pH is within the range of 3-4.5 and separating the thus-formed silver halide-gelatin derivative grains from the liquid portion of the mass.
- a method of preparing a gelatino-silver halide emulsion which comprises pre aring a silver halide dispersion by mixing together a water-soluble silver salt and a water-soluble halide in an aqueous solution of a gelatin derivative whose presence renders the dispersion coagulable at a pH within the range or pH 3-4.5,
- silver halide dispersions the steps which comprise mixing together a water-soluble silver salt and a water-soluble halide salt in an aqueous solution of a maleic anhydride derivative of gelatin Whose presence renders the dispersion coagulable at a pH within the range of 3-4.5, coagulating the dispersion of silver halide in gelatin derivative thus formed by adjustin to said pH whereby silver halide-gelatin derivative grains are formed, and subsequently separating the thus-formed grains from the liquid portion of the mass.
- a method of preparing a washed gelatinosilver halide photographic emulsion which comprises preparing a silver halide dispersion by mixing together a water-soluble silver salt and a water-soluble halide in an aqueous solution of a gelatin derivative whose presence renders the dispersion coagulable at a pH within the range of pH 3-4.5, which derivative is selected from the group consisting of the aromatic sulfonyl chloride derivatives of gelatin, the carboxylic acid chloride derivatives of gelatin, the carboxylic acid anhydride derivatives of gelatin, the aromatic isocyanate derivatives of gelatin and the 1,4 diketone derivatives of gelatin coagulating the dispersion of silver halide in gelatin derivative thus formed by adjusting to said pI-I whereby silver halidegelatin derivative grains are formed, separating the thus-formed grains from the liquid portion of the mass, redispersing those grains in water at a dispersing pH therefor, followed by adjusting the pH of the solution
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE484325D BE484325A (en:Method) | 1947-08-13 | ||
US768475A US2614928A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
US768476A US2614929A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
GB7273/48A GB649545A (en) | 1947-08-13 | 1948-03-09 | Improvements in the production of photographic emulsions |
GB7274/48A GB649546A (en) | 1947-08-13 | 1948-03-09 | Improvements in the production of photographic emulsions |
FR980386D FR980386A (fr) | 1947-08-13 | 1948-08-11 | Procédé perfectionné de préparation d'émulsions photographiques et procufits enrésultant |
US303394A US2728662A (en) | 1947-08-13 | 1952-08-08 | Method of preparing photographic emulsions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US768475A US2614928A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
US768476A US2614929A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2614928A true US2614928A (en) | 1952-10-21 |
Family
ID=27118058
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US768475A Expired - Lifetime US2614928A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
US768476A Expired - Lifetime US2614929A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US768476A Expired - Lifetime US2614929A (en) | 1947-08-13 | 1947-08-13 | Method of preparing photographic emulsions |
Country Status (4)
Country | Link |
---|---|
US (2) | US2614928A (en:Method) |
BE (1) | BE484325A (en:Method) |
FR (1) | FR980386A (en:Method) |
GB (2) | GB649545A (en:Method) |
Cited By (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2725294A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with polyanhydrides |
US2725295A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with organic acid chlorides |
US2768079A (en) * | 1954-01-25 | 1956-10-23 | Eastman Kodak Co | Method of preparing washed photographic emulsions |
US2787545A (en) * | 1955-01-17 | 1957-04-02 | Eastman Kodak Co | Method of preparing photographic emulsions by coagulating with gelatin graft polymers |
US2956880A (en) * | 1957-01-04 | 1960-10-18 | Eastman Kodak Co | Preparation of washed emulsions and gelatin derivatives employed as peptizers in their preparation |
DE1171264B (de) * | 1962-05-31 | 1964-05-27 | Polaroid Corp | Verfahren zur Herstellung photo-graphischer Silberhalogenidemulsionen nach dem Ausflockungsverfahren |
DE1191225B (de) * | 1960-06-10 | 1965-04-15 | Polaroid Corp | Verfahren zur Herstellung von photographischen Ausflockungsemulsionen |
US3201250A (en) * | 1959-01-12 | 1965-08-17 | Eastman Kodak Co | Dimensionally stable gelatincontaining film product |
US3223528A (en) * | 1960-07-18 | 1965-12-14 | Vrancken Marcel Nicolas | Gelatin derivatives and photographic silver halide emulsion layers |
DE1242448B (de) * | 1960-06-10 | 1967-06-15 | Polaroid Corp | Verfahren zur Herstellung photographischer Silberhalogenidemulsionen mittels Ausflockung |
US3328257A (en) * | 1962-02-20 | 1967-06-27 | Gevaert Photo Prod Nv | Preparation of microcapsules |
US3480440A (en) * | 1965-06-11 | 1969-11-25 | Agfa Gevaert Ag | Hardening of photographic gelatin-containing layers |
JPS4841734A (en:Method) * | 1971-09-27 | 1973-06-18 | ||
US3873322A (en) * | 1972-05-12 | 1975-03-25 | Agfa Gevaert | Method of preparing photographic silver halide emulsions |
US3881934A (en) * | 1970-06-05 | 1975-05-06 | Agfa Gevaert Nv | Removal of dissolved products from a precipitate |
US3884701A (en) * | 1972-08-03 | 1975-05-20 | Agfa Gevaert Nv | Method of preparing silver halide emulsions |
JPS5188223A (en:Method) * | 1975-01-07 | 1976-08-02 | ||
EP0115351A2 (en) | 1983-01-28 | 1984-08-08 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material |
EP0201027A2 (en) | 1985-04-30 | 1986-11-12 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0202784A2 (en) | 1985-04-23 | 1986-11-26 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
EP0375522A3 (en) * | 1988-12-16 | 1990-10-10 | Sanofi S.A. | Fluorinated gelatin and process for its preparation |
US4990439A (en) * | 1988-08-03 | 1991-02-05 | Konica Corporation | Silver halide light-sensitive photographic material |
US5411849A (en) * | 1992-12-10 | 1995-05-02 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0691569A1 (en) | 1994-07-04 | 1996-01-10 | Kodak-Pathe | Photographic emulsion with improved sensitivity |
US5492803A (en) * | 1995-01-06 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Hydrazide redox-dye-releasing compounds for photothermographic elements |
US5492804A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5492805A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
EP0698817A1 (en) | 1994-08-22 | 1996-02-28 | Agfa-Gevaert N.V. | Assortment of silver halide photographic industrial X-ray films and method of processing said assortment |
EP0768570A1 (en) | 1995-10-09 | 1997-04-16 | Konica Corporation | Image forming method |
WO1998010939A1 (de) * | 1996-09-14 | 1998-03-19 | Deutsche Gelatine-Fabriken Stoess Ag | Aufzeichnungsmaterial für die thermische bildaufzeichnung |
US5891615A (en) * | 1997-04-08 | 1999-04-06 | Imation Corp. | Chemical sensitization of photothermographic silver halide emulsions |
US5928857A (en) * | 1994-11-16 | 1999-07-27 | Minnesota Mining And Manufacturing Company | Photothermographic element with improved adherence between layers |
US5939249A (en) * | 1997-06-24 | 1999-08-17 | Imation Corp. | Photothermographic element with iridium and copper doped silver halide grains |
US5977190A (en) * | 1998-01-14 | 1999-11-02 | Eastman Kodak Company | Process for deionizing and concentrating emulsions |
US5994049A (en) * | 1997-08-28 | 1999-11-30 | Eastman Kodak Company | Water-soluble non-interactive polymers and surfactant micelles for desalting and concentrating silver halide photographic emulsions |
US6004740A (en) * | 1997-08-28 | 1999-12-21 | Eastman Kodak Company | Water-soluble non-interactive carboxyl polymers for desalting and concentrating silver halide photographic emulsions |
US6117624A (en) * | 1993-06-04 | 2000-09-12 | Eastman Kodak Company | Infrared sensitized, photothermographic article |
US6171707B1 (en) | 1994-01-18 | 2001-01-09 | 3M Innovative Properties Company | Polymeric film base having a coating layer of organic solvent based polymer with a fluorinated antistatic agent |
EP1364802A2 (en) | 2002-05-21 | 2003-11-26 | FERRANIA S.p.A. | Receiving sheet for ink-jet printing |
US7468241B1 (en) | 2007-09-21 | 2008-12-23 | Carestream Health, Inc. | Processing latitude stabilizers for photothermographic materials |
US7524621B2 (en) | 2007-09-21 | 2009-04-28 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
US7622247B2 (en) | 2008-01-14 | 2009-11-24 | Carestream Health, Inc. | Protective overcoats for thermally developable materials |
CN101256346B (zh) * | 2008-02-04 | 2010-09-29 | 黄山银江科技有限公司 | 一种激光照排胶片的生产方法 |
WO2012035314A1 (en) | 2010-09-17 | 2012-03-22 | Fujifilm Manufacturing Europe Bv | Photographic paper |
WO2015148028A1 (en) | 2014-03-24 | 2015-10-01 | Carestream Health, Inc. | Thermally developable imaging materials |
WO2016073086A1 (en) | 2014-11-04 | 2016-05-12 | Carestream Health, Inc. | Image forming materials, preparations, and compositions |
WO2016195950A1 (en) | 2015-06-02 | 2016-12-08 | Carestream Health, Inc. | Thermally developable imaging materials and methods |
WO2017123444A1 (en) | 2016-01-15 | 2017-07-20 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
WO2021213762A1 (en) | 2020-04-24 | 2021-10-28 | Fujifilm Manufacturing Europe Bv | Photographic paper |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US2728662A (en) * | 1947-08-13 | 1955-12-27 | Eastman Kodak Co | Method of preparing photographic emulsions |
US2863769A (en) * | 1954-09-03 | 1958-12-09 | Du Pont | Process of preparing silver halide dispersions |
US2982652A (en) * | 1957-06-18 | 1961-05-02 | Gevaert Photo Prod Nv | Preparation of photographic emulsions |
BE573515A (en:Method) * | 1957-12-04 | |||
US3138461A (en) * | 1960-06-10 | 1964-06-23 | Polaroid Corp | Process for preparing silver halide emulsions containing gelatin derivatives |
NL297840A (en:Method) * | 1962-09-13 | |||
US3359110A (en) * | 1964-04-13 | 1967-12-19 | Eastman Kodak Co | Use of organic amides as anti-coagulants in emulsions prepared by the gelatin derivative coagulation wash procedure |
GB1535042A (en) * | 1975-04-09 | 1978-12-06 | Agfa Gevaert | Preparation of photographic silver halide emulsions |
DE3828312A1 (de) * | 1988-08-20 | 1990-03-01 | Agfa Gevaert Ag | Herstellung einer silberhalogenidemulsion |
JP2838533B2 (ja) * | 1989-04-03 | 1998-12-16 | コニカ株式会社 | ハロゲン化銀写真感光材料 |
US5273873A (en) * | 1990-12-06 | 1993-12-28 | Eastman Kodak Company | Control of surface iodide using post precipitation KC1 treatment |
US5399480A (en) * | 1993-09-14 | 1995-03-21 | Eastman Kodak Company | Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains |
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US1844716A (en) * | 1929-04-19 | 1932-02-09 | Eastman Kodak Co | Process of making photographic emulsions |
GB479419A (en) * | 1936-07-10 | 1938-02-04 | Kodak Ltd | Improvements in ripening and hardening photographic emulsions |
GB537256A (en) * | 1939-09-13 | 1941-06-16 | Eastman Kodak Co | Process employing non-diffusing compounds for use in colour photography and other photographic processes |
GB580504A (en) * | 1944-07-04 | 1946-09-10 | Cecil Waller | Improvements in or relating to the production of photographic silver halide emulsions |
-
0
- BE BE484325D patent/BE484325A/xx unknown
-
1947
- 1947-08-13 US US768475A patent/US2614928A/en not_active Expired - Lifetime
- 1947-08-13 US US768476A patent/US2614929A/en not_active Expired - Lifetime
-
1948
- 1948-03-09 GB GB7273/48A patent/GB649545A/en not_active Expired
- 1948-03-09 GB GB7274/48A patent/GB649546A/en not_active Expired
- 1948-08-11 FR FR980386D patent/FR980386A/fr not_active Expired
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US1844716A (en) * | 1929-04-19 | 1932-02-09 | Eastman Kodak Co | Process of making photographic emulsions |
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Cited By (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2725294A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with polyanhydrides |
US2725295A (en) * | 1952-07-17 | 1955-11-29 | Eastman Kodak Co | Hardening of gelatin with organic acid chlorides |
US2768079A (en) * | 1954-01-25 | 1956-10-23 | Eastman Kodak Co | Method of preparing washed photographic emulsions |
US2787545A (en) * | 1955-01-17 | 1957-04-02 | Eastman Kodak Co | Method of preparing photographic emulsions by coagulating with gelatin graft polymers |
US2956880A (en) * | 1957-01-04 | 1960-10-18 | Eastman Kodak Co | Preparation of washed emulsions and gelatin derivatives employed as peptizers in their preparation |
US3201250A (en) * | 1959-01-12 | 1965-08-17 | Eastman Kodak Co | Dimensionally stable gelatincontaining film product |
DE1191225B (de) * | 1960-06-10 | 1965-04-15 | Polaroid Corp | Verfahren zur Herstellung von photographischen Ausflockungsemulsionen |
DE1242448B (de) * | 1960-06-10 | 1967-06-15 | Polaroid Corp | Verfahren zur Herstellung photographischer Silberhalogenidemulsionen mittels Ausflockung |
US3223528A (en) * | 1960-07-18 | 1965-12-14 | Vrancken Marcel Nicolas | Gelatin derivatives and photographic silver halide emulsion layers |
US3328257A (en) * | 1962-02-20 | 1967-06-27 | Gevaert Photo Prod Nv | Preparation of microcapsules |
DE1171264B (de) * | 1962-05-31 | 1964-05-27 | Polaroid Corp | Verfahren zur Herstellung photo-graphischer Silberhalogenidemulsionen nach dem Ausflockungsverfahren |
US3480440A (en) * | 1965-06-11 | 1969-11-25 | Agfa Gevaert Ag | Hardening of photographic gelatin-containing layers |
US3881934A (en) * | 1970-06-05 | 1975-05-06 | Agfa Gevaert Nv | Removal of dissolved products from a precipitate |
JPS4841734A (en:Method) * | 1971-09-27 | 1973-06-18 | ||
US3873322A (en) * | 1972-05-12 | 1975-03-25 | Agfa Gevaert | Method of preparing photographic silver halide emulsions |
US3884701A (en) * | 1972-08-03 | 1975-05-20 | Agfa Gevaert Nv | Method of preparing silver halide emulsions |
JPS5188223A (en:Method) * | 1975-01-07 | 1976-08-02 | ||
EP0115351A2 (en) | 1983-01-28 | 1984-08-08 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material |
EP0202784A2 (en) | 1985-04-23 | 1986-11-26 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0201027A2 (en) | 1985-04-30 | 1986-11-12 | Konica Corporation | Silver halide photographic light-sensitive material |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
US4990439A (en) * | 1988-08-03 | 1991-02-05 | Konica Corporation | Silver halide light-sensitive photographic material |
EP0375522A3 (en) * | 1988-12-16 | 1990-10-10 | Sanofi S.A. | Fluorinated gelatin and process for its preparation |
US5411849A (en) * | 1992-12-10 | 1995-05-02 | Konica Corporation | Silver halide photographic light-sensitive material |
US6117624A (en) * | 1993-06-04 | 2000-09-12 | Eastman Kodak Company | Infrared sensitized, photothermographic article |
US6171707B1 (en) | 1994-01-18 | 2001-01-09 | 3M Innovative Properties Company | Polymeric film base having a coating layer of organic solvent based polymer with a fluorinated antistatic agent |
US5492804A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5492805A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
US5705676A (en) * | 1994-06-30 | 1998-01-06 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5696289A (en) * | 1994-06-30 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
EP0691569A1 (en) | 1994-07-04 | 1996-01-10 | Kodak-Pathe | Photographic emulsion with improved sensitivity |
EP0698817A1 (en) | 1994-08-22 | 1996-02-28 | Agfa-Gevaert N.V. | Assortment of silver halide photographic industrial X-ray films and method of processing said assortment |
US5928857A (en) * | 1994-11-16 | 1999-07-27 | Minnesota Mining And Manufacturing Company | Photothermographic element with improved adherence between layers |
US5492803A (en) * | 1995-01-06 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Hydrazide redox-dye-releasing compounds for photothermographic elements |
EP0768570A1 (en) | 1995-10-09 | 1997-04-16 | Konica Corporation | Image forming method |
WO1998010939A1 (de) * | 1996-09-14 | 1998-03-19 | Deutsche Gelatine-Fabriken Stoess Ag | Aufzeichnungsmaterial für die thermische bildaufzeichnung |
US5891615A (en) * | 1997-04-08 | 1999-04-06 | Imation Corp. | Chemical sensitization of photothermographic silver halide emulsions |
US5939249A (en) * | 1997-06-24 | 1999-08-17 | Imation Corp. | Photothermographic element with iridium and copper doped silver halide grains |
US6060231A (en) * | 1997-06-24 | 2000-05-09 | Eastman Kodak Company | Photothermographic element with iridium and copper doped silver halide grains |
US5994049A (en) * | 1997-08-28 | 1999-11-30 | Eastman Kodak Company | Water-soluble non-interactive polymers and surfactant micelles for desalting and concentrating silver halide photographic emulsions |
US6004740A (en) * | 1997-08-28 | 1999-12-21 | Eastman Kodak Company | Water-soluble non-interactive carboxyl polymers for desalting and concentrating silver halide photographic emulsions |
US5977190A (en) * | 1998-01-14 | 1999-11-02 | Eastman Kodak Company | Process for deionizing and concentrating emulsions |
EP1364802A2 (en) | 2002-05-21 | 2003-11-26 | FERRANIA S.p.A. | Receiving sheet for ink-jet printing |
US7524621B2 (en) | 2007-09-21 | 2009-04-28 | Carestream Health, Inc. | Method of preparing silver carboxylate soaps |
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Also Published As
Publication number | Publication date |
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GB649545A (en) | 1951-01-31 |
BE484325A (en:Method) | |
FR980386A (fr) | 1951-05-11 |
US2614929A (en) | 1952-10-21 |
GB649546A (en) | 1951-01-31 |
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