US3429708A - Accelerator for chemical ripening - Google Patents
Accelerator for chemical ripening Download PDFInfo
- Publication number
- US3429708A US3429708A US552945A US3429708DA US3429708A US 3429708 A US3429708 A US 3429708A US 552945 A US552945 A US 552945A US 3429708D A US3429708D A US 3429708DA US 3429708 A US3429708 A US 3429708A
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- US
- United States
- Prior art keywords
- emulsion
- gelatin
- ripening
- added
- coagulation
- Prior art date
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- 230000005070 ripening Effects 0.000 title claims description 12
- 239000000126 substance Substances 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims description 22
- 108010010803 Gelatin Proteins 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000008273 gelatin Substances 0.000 claims description 16
- 229920000159 gelatin Polymers 0.000 claims description 16
- 235000019322 gelatine Nutrition 0.000 claims description 16
- 235000011852 gelatine desserts Nutrition 0.000 claims description 16
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 229920002307 Dextran Polymers 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- KWMLJOLKUYYJFJ-GASJEMHNSA-N (2xi)-D-gluco-heptonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C(O)=O KWMLJOLKUYYJFJ-GASJEMHNSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- FZWBNHMXJMCXLU-BLAUPYHCSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-BLAUPYHCSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 7
- 229960001855 mannitol Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000010356 sorbitol Nutrition 0.000 description 5
- 229960002920 sorbitol Drugs 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- -1 halide salt Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 241000242759 Actiniaria Species 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229960002086 dextran Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
Definitions
- the invention is concerned with the ripening of photographic emulsions and in particular is based on the discovery that certain polyhydroxy compounds, added at a certain point in emulsion preparation can increase the rate of ripening of such emulsions.
- silver nitrate is added in the desired concentration with the rate of addition, temperature and so on, being dependent on the particular emulsion product to be obtained. Generally, the silver is precipitated as the halide in this step.
- the partial emulsion so prepared is then heated to carry out a first ripening step. Additional gelatin is later added and finally, after the mixture has been set to a gel by chilling, it is broken up and washed to remove the excess salts.
- Breaking up to a condition finely divided enough for effective washing may be accomplished by a number of techniques, for example, by extrusion through a die to give slender threads (noodles) of gelatin, by a coagulation Wash technique employing generally organic wetting agent-type materials in which the gelatin is loosely coagulated and separated for washing, or by a precipitation technique ⁇ generally using inorganic salts, in which the gelatin is precipitated as relatively large particles suitable for washing. In both these latter techniques relatively dilute gelatin solutions are employed.
- the emulsion After washing, the emulsion generally is reconstituted by agitation and the addition of further gelatin and Water.
- the reconstituted emulsion is allowed to digest for a period of time and then other ripening agents for pH adjustment, sensitization, stabilization, etc. are added and mixture allowed to stand for a period of time.
- coating finals such as surfactants and wetting agents may be added before application of the emulsion to photographic sheet material.
- Polyhydroxy compounds of higher molecular Weights such as the dextranes and other sugar derivatives are known to affect the covering power and in some systems also the rate of development When added as coating finals.
- the molecular weight of these compounds ranges from about 300 to as much as 100,000. The effects are only noticeable if a certain minimum amount of more of the material is present. The lower limit is normally based on the gelatin present in the emulsion.
- a distinct disadvantage of the aforementioned compounds is their detrimental effect on the coating and hardening properties of the emulsions when added in such large amounts.
- each batch of coagulated gelatin 50 grams of ripening gelatin is added and each finished emulsion is given a conventional after-ripening at 50 C. before being coated on a photographic medium, exposed and developed.
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
Description
Feb. 25, 1969 ACCELERATOR FOR CHEMICAL G. H. KLINGER ET AL RIPENING Filed May 25, 1966 United States Patent O 6 Claims The invention is concerned with the ripening of photographic emulsions and in particular is based on the discovery that certain polyhydroxy compounds, added at a certain point in emulsion preparation can increase the rate of ripening of such emulsions.
Emulsions sensitive to light and other actinie radiation are conventionally prepared for photographic application by first soaking a part of the gelatin required for the emulsion formula in Water, completing its solution and then adding soluble halide salt, usually with addition of ammonia. Such halide salts may be straight chlorides, bromides or iodides, usually in the alkali metal form or may be chlorobromide, bromoiodide, etc., mixtures. Generally, mixtures of about 2-10 mole percent of alkali iodide and 90-98 mole percent of alkali metal or ammonium bromide or from 10-30 mole percent of alkali metal or ammonium chloride and 70-90 mole percent of alkali metal bromide are preferred.
To the resulting solution, silver nitrate is added in the desired concentration with the rate of addition, temperature and so on, being dependent on the particular emulsion product to be obtained. Generally, the silver is precipitated as the halide in this step. The partial emulsion so prepared is then heated to carry out a first ripening step. Additional gelatin is later added and finally, after the mixture has been set to a gel by chilling, it is broken up and washed to remove the excess salts. Breaking up to a condition finely divided enough for effective washing may be accomplished by a number of techniques, for example, by extrusion through a die to give slender threads (noodles) of gelatin, by a coagulation Wash technique employing generally organic wetting agent-type materials in which the gelatin is loosely coagulated and separated for washing, or by a precipitation technique `generally using inorganic salts, in which the gelatin is precipitated as relatively large particles suitable for washing. In both these latter techniques relatively dilute gelatin solutions are employed.
After washing, the emulsion generally is reconstituted by agitation and the addition of further gelatin and Water. The reconstituted emulsion is allowed to digest for a period of time and then other ripening agents for pH adjustment, sensitization, stabilization, etc. are added and mixture allowed to stand for a period of time. Following this after-ripening, coating finals, such as surfactants and wetting agents may be added before application of the emulsion to photographic sheet material.
Polyhydroxy compounds of higher molecular Weights, such as the dextranes and other sugar derivatives are known to affect the covering power and in some systems also the rate of development When added as coating finals. The molecular weight of these compounds ranges from about 300 to as much as 100,000. The effects are only noticeable if a certain minimum amount of more of the material is present. The lower limit is normally based on the gelatin present in the emulsion. A distinct disadvantage of the aforementioned compounds is their detrimental effect on the coating and hardening properties of the emulsions when added in such large amounts.
It has now 4been found that such polyhydroxy compounds may be used in much lower amounts and still achieve their effects when added before or during the pre-wash coagulation of the emulsion. Also, the addition lCe of these materials before or during the coagulation has been found to speed the after-ripening step, apparently by increasing the rate of ripening.
The polyhydroxy compounds useful in this invention generally have a molecular weight of about 180-300,000 and are organic materials having a sufficient number of hydroxyl or other polar groups to assure water solubility. As mentioned, low-value sugars and sugar derivatives such as pentaerythrytol, sorbitol, d-mannitol, dextran and glucoheptanoic acid are preferred. The amount of active agent employed is generally about 2-4% of the total gelatin present in the finished emulsion. If the same amount of a given polyhydroxy compound is added after the washing is completed, little or no effect is observed on the rate of ripening. It has been found that even compounds of low molecular weight with an excellent water solubility are not removed during the washing of the emulsion subsequent to coagulation.
The following examples of the process of this invention are to be considered illustrative only and not limiting.
Batches of gelatin emulsion were made containing 22 gra-ms KI, 680 grams NH4Br and 40 grams gelatin to 3600 mls. of water. Silver solutions containing 1000 grams AgNO3, 180 mls. of 10% NHO3 and 900 mls. of 28% NH3 in 5200 mls. of water were also prepared and added, during the course of l5 minutes, to the gelatin solution. Each mixture was allowed to digest for 5 minutes at 50. Then 8 grams of sodium polystyrene sulfonate coagulant as a l5 perecent aqueous solution and 2.5 grams of polyhydroxy compound, as reported in Table I below, were added. The silver halide crystals were precipitated and the coagulated mixture washed to remove excess salts. To each batch of coagulated gelatin, 50 grams of ripening gelatin is added and each finished emulsion is given a conventional after-ripening at 50 C. before being coated on a photographic medium, exposed and developed.
Representative results of sensitometric tests and measurements of fog and speed are given in Table I.
TABLE I After- Compound Ripening Fog Dm Speed Time at 0.2 (minutes) Blank 30 06 15 60 08 72 11 09 l. 83 52 d-Mannitol 30 08 27 60 09 1. 44 39 90 11 3. 16 85 Sorbitol 30 07 44 11. 5
60 08 1. 42 46 90 10 3. 44 110 Dextran 30 07 22 60 l0 l. 92 68 90 18 4+ 170 Pentaerythrytol 30 O7 60 10 60 14 l. 52 120 90 14 2. l5 220 Glucuheptanoic acid 30 .08 .92 45 60 14 1. 77 195 90 29 2. 04 260 The results of these runs are shown graphically in the drawings, where, in FIGURE l, the speed of the resulting photographic medium is shown in relation to after-ripening time of the emulsion while in FIGURE 2 fog is shown in relation to after-ripening time. The results obtained with -mannitol were essentially identical with those shown for sorbitol.
It can be readily seen that the use of all of the agents of the runs resulted in increased speed of the photographic medium while fog was not significantly increased, especially when using the 60 minute after-ripened products. The sorbitol and the mannitol were of particular value in the 90 minutes after-ripened product, without too significant an increase in fog.
3 4 What is claimed is: 5. The process of claim 1 in which the compound is 1. In a process for preparing a light-sensitive gelatinpentaerythrytol. silver halide emulsion including precipitation, digestion, A6. The process of claim 1 in which the compound is coagulation, washing and ripening periods, the step which glucoheptanoic acid.
comprises adding to the emulsion, lbefore the end of the coagulation step, about 2 to 4%, based on the weight of 5 References Cited the gelatin, of a water-soluble polyhydroxy compound UNITED STATES PATENTS having a molecular weight of about 180 to 300,000 and 3,063,838 11/1962 Jennings 96 107 XR selected from the group consisting of a d-mannitol, sorbi- 3,085,009 4 /1963 Chambers 96 107 tol, dextran, pentaerythrytol and glucoheptanoic acid. 10 3,272,631 9/ 1966 Garrett et al. 96-107 2. The process of claim 1 in which the compound is d-mannitol. I. TRAVIS BROWN, Prz'm'ary Examiner.
3. The process of claim 1 in which the compound is RONALD H' SMITH, Assistant Examnm sor-bitol.
4. The process of claim 1 in which the compound is 15 U.S. C1X.R. dextran. 96-107, 114
Claims (1)
1. IN A PROCESS FOR PREPARING A LIGHT-SENSITIVE GELATINSILVER HALIDE EMULSION INCLUDING PRECIPITATION, DIGESTION, COAGULATION, WASHING AND RIPENING PERIODS, THE STEP WHICH COMPRISES ADDING TO THE EMULSION, BEFORE THE END OF THE COAGULATION STEP, ABOUT 2 TO 4%, BASED ON THE WEIGHT OF THE GELATIN, OF A WATER-SOLUBLE POLYHYDROXY COMPOUND HAVING A MOLECULAR WEIGHT OF ABOUT 180 TO 300,000 AND SELECTED FROM THE GROUP CONSISTING OF A D-MANNITOL, SORBITOL, DEXTRAN, PENTAERYTHRYTOL AND GLUCOHEPTANOIC ACID.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55294566A | 1966-05-25 | 1966-05-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3429708A true US3429708A (en) | 1969-02-25 |
Family
ID=24207472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US552945A Expired - Lifetime US3429708A (en) | 1966-05-25 | 1966-05-25 | Accelerator for chemical ripening |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3429708A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071681A (en) * | 1997-05-20 | 2000-06-06 | Konica Corporation | Method for producing silver halide photographic light-sensitive material |
| US6174660B1 (en) * | 1998-07-21 | 2001-01-16 | Konica Corporation | Silver halide photographic light-sensitive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063838A (en) * | 1958-11-21 | 1962-11-13 | Du Pont | Photographic emulsions and elements containing dextran |
| US3085009A (en) * | 1961-01-16 | 1963-04-09 | Du Pont | Photographic emulsions and elements containing a water soluble mannan |
| US3272631A (en) * | 1964-01-03 | 1966-09-13 | Du Pont | Haze reduction of photographic emulsions containing a covering power agent |
-
1966
- 1966-05-25 US US552945A patent/US3429708A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3063838A (en) * | 1958-11-21 | 1962-11-13 | Du Pont | Photographic emulsions and elements containing dextran |
| US3085009A (en) * | 1961-01-16 | 1963-04-09 | Du Pont | Photographic emulsions and elements containing a water soluble mannan |
| US3272631A (en) * | 1964-01-03 | 1966-09-13 | Du Pont | Haze reduction of photographic emulsions containing a covering power agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071681A (en) * | 1997-05-20 | 2000-06-06 | Konica Corporation | Method for producing silver halide photographic light-sensitive material |
| US6174660B1 (en) * | 1998-07-21 | 2001-01-16 | Konica Corporation | Silver halide photographic light-sensitive material |
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