US2494068A - Photographic relief image - Google Patents
Photographic relief image Download PDFInfo
- Publication number
- US2494068A US2494068A US674037A US67403746A US2494068A US 2494068 A US2494068 A US 2494068A US 674037 A US674037 A US 674037A US 67403746 A US67403746 A US 67403746A US 2494068 A US2494068 A US 2494068A
- Authority
- US
- United States
- Prior art keywords
- silver
- image
- gelatin
- bromide
- relief image
- 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
- 229910052709 silver Inorganic materials 0.000 claims description 38
- 239000004332 silver Substances 0.000 claims description 38
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- 108010010803 Gelatin Proteins 0.000 claims description 20
- 229920000159 gelatin Polymers 0.000 claims description 20
- 239000008273 gelatin Substances 0.000 claims description 20
- 235000019322 gelatine Nutrition 0.000 claims description 20
- 235000011852 gelatine desserts Nutrition 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000007844 bleaching agent Substances 0.000 claims description 13
- 238000004061 bleaching Methods 0.000 claims description 9
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- -1 silver halide Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- OKNLBTNZLUNRDW-UHFFFAOYSA-N hydrogen peroxide;hydrobromide Chemical compound Br.OO OKNLBTNZLUNRDW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 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
- 239000000020 Nitrocellulose Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
Definitions
- This invention relates to photography and particularly to a method of forming photographic relief images.
- relief images- can be formed in silver halide emulsion layers by treating the developed silver halide layer with a hydrogen peroxide etch bath containing bromide ions and thereby removing the developed silver image together with the gelatin in theregions of the silver image.
- This method of forming ;a relief image is particularly useful where a positive relief image is to be formed from a positive color transparency since the positive relief image can be formeddirectly. It has been noted that the dissolution of the gelatin surrounding the silver grains takes place only when the hydrogen peroxide etch bath is strongly acid. If an etch bath is used which is not strongly acid, bleaching will take place but no dissolution of the gelatin will result. I
- This method differs from the usual hydrogen peroxide etch process in that the gelatin is not removed by the etch bath but is only softened and is removed as a separate step by washing with hot water.
- This method has the advantage that the resulting image is sharper than the image obtained by the usual hydrogen peroxide etch process. Furthermore, the etching solution does not become sludged with silver bromide and dissolved gelatin and can be reused many times. By Washing off with hot water, the relief is left immediately clean and ready for drying. The usual etch method leaves a residue which washes off slowly.
- a further advantage is that the relief can be processed in a shorter time than is customary with the usual hydrogen peroxide etching process and by remaining in a hardened condition, a positive image is less subject to damage.
- An average gelatino-silver halide emulsion which might be used according to my process could be hardened to a melting point of approximately 180 F. However, a change in balance of acidity can be made toaccommodate emulsions of other degrees of hardness.
- the emulsion is coated on the usual support of cellulose acetate,
- cellulose nitrate or synthetic resin may-be coated on a paper support.
- the emulsion may be blue-sensitive or panchromatic and is exposed in the usual way, for example, to a positivecolor transparency. Separation images may be made for use in the imbibition process by exposing through primary color filters if a panchromatic material is used. The emulsion is developed in the usual way to forma negative silver image leaving residual silver halide in the unexposed portions of the layer. The residual. silver bromide may be removed by fixing at this stage or may remain in the layer for removal at a later stage. 7
- the layer is treated with a v hydrogen-peroxide-bromide bleach bath having a pH ofapproximately 2.6 to 3.0.
- the pH of the bleach bath is adjusted to the hardness of the particular emulsion which is used. If the emulsion is extremely hard, the pl-I would be low but if the emulsion is only moderately hard, the pH would be higher.
- the following formulas are suitable for use according to my invention.
- bromides such as sodium or ammonium may be used.
- Acids other than acetic acid such as sulfuric acid or hydrochloric may be employed, the pH being adjusted within the range specified above. 7
- the emulsion After bleaching of the silver image, the emulsion is washed for 1 minute with water at a, temperature of approximately F. to wash off the gelatin in the region of the silver image.
- the positive relief image is then in a condition for use in an imbibition process or other process for which a relief image is suitable.
- the method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer to form a silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide-bromide bleach bath havin a pH of approximately 2.6 to 3.0, without dissolving but with softening the gelatin in the region of the silver image, hardening said emulsion prior to said bleaching as a step in the process, washing off the gelatin softened by the bleach bath in warm water, to form a positive gelatino-silver halide relief image.
- the method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer hardened to a melting point of approximately 180 F. to form a, silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide-bromide bleach bath having a pH of approximately 2.6 to 3.0, said bleach bath softening the gelatin in the region of the silver image without dissolvin it, and washing off the gelatin softened by the bleach bath in warm water to form a positive gelatinc silver halide relief image.
- the method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer to form a silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide bleach bath containing approximately grams per liter of potassium bromide and having a pH of approximately 2.6 to 3.0, hardening said emulsion to a melting point of approximately 180 F. prior to said bleaching as a step in the process, said bleach bath softening the gelatin in the region of the silver image without dissolving it, and washing off the gelatin softened by the bleach bath in warm water to form a positive gelatino-silver halide relief image.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patented Jan. 10, 1950 2,494,068 frrro'roemrnrc RELIEF IMAGE Robert P; Speck, Rochester, N. Y., assignonto- Eastman Kodak Company, Rochester, N, Y a corporation of New Jersey No Drawing. Application June 3, 1946,
Serial No. 674,037
3 Claims.
This invention relates to photography and particularly to a method of forming photographic relief images.
It is known that relief images-can be formed in silver halide emulsion layers by treating the developed silver halide layer with a hydrogen peroxide etch bath containing bromide ions and thereby removing the developed silver image together with the gelatin in theregions of the silver image. This method of forming ;a relief image is particularly useful where a positive relief image is to be formed from a positive color transparency since the positive relief image can be formeddirectly. It has been noted that the dissolution of the gelatin surrounding the silver grains takes place only when the hydrogen peroxide etch bath is strongly acid. If an etch bath is used which is not strongly acid, bleaching will take place but no dissolution of the gelatin will result. I
I have found that if a hardened gelatino silver halide emulsion is used, a hydrogen peroxide bath of the proper degree of acidity will bleach the silver image to silver bromide and simultaneously soften the gelatin in the regions of the silver image. The gelatin in the areas of the residual silver halide is not seriously affected by this treatment. (Some small degree of softening takes place, but the gelatin remains mostly insoluble in hot water.) The softened negative gelatin, that is, the gelatin in the regions of the original silver image can then be washed off in hot water leaving a hard positive image. The residual silver halide of the positive image can be removed in the usual manner, or may be allowed to remain, or be developed after flashing, in a tanning developer to give the gelatin desirable dye transferring characteristics.
This method differs from the usual hydrogen peroxide etch process in that the gelatin is not removed by the etch bath but is only softened and is removed as a separate step by washing with hot water.
This method has the advantage that the resulting image is sharper than the image obtained by the usual hydrogen peroxide etch process. Furthermore, the etching solution does not become sludged with silver bromide and dissolved gelatin and can be reused many times. By Washing off with hot water, the relief is left immediately clean and ready for drying. The usual etch method leaves a residue which washes off slowly. A further advantage is that the relief can be processed in a shorter time than is customary with the usual hydrogen peroxide etching process and by remaining in a hardened condition, a positive image is less subject to damage.
An average gelatino-silver halide emulsion which might be used according to my process could be hardened to a melting point of approximately 180 F. However, a change in balance of acidity can be made toaccommodate emulsions of other degrees of hardness. The emulsion is coated on the usual support of cellulose acetate,
cellulose nitrate or synthetic resin or may-be coated on a paper support.
The emulsion may be blue-sensitive or panchromatic and is exposed in the usual way, for example, to a positivecolor transparency. Separation images may be made for use in the imbibition process by exposing through primary color filters if a panchromatic material is used. The emulsion is developed in the usual way to forma negative silver image leaving residual silver halide in the unexposed portions of the layer. The residual. silver bromide may be removed by fixing at this stage or may remain in the layer for removal at a later stage. 7
After development of the silver image, the layer is treated with a v hydrogen-peroxide-bromide bleach bath having a pH ofapproximately 2.6 to 3.0. The pH of the bleach bath is adjusted to the hardness of the particular emulsion which is used. If the emulsion is extremely hard, the pl-I would be low but if the emulsion is only moderately hard, the pH would be higher. The following formulas are suitable for use according to my invention.
Example 1 Copper sulfate grams 33 Potassium bromide do 10 Acetic acid (28% solution) cc. 13
Hydrogen peroxide (25% solution) cc. Water to 1 liter.
Example 2 Copper sulfate grams 50 Potassium bromide do 15 Acetic acid (28% solution) oc. 15 Potassium alum grams 15 Water to .1 liter.
For use, three parts of this formula are added to 1 part of 8% hydrogen peroxide solution.
With both of these formulas, softening of the emulsion in the region of the silver image takes place in approximately 1 minutes at a temperature of 68 F.
In place of potassium bromide in the bleach bath, other bromides such as sodium or ammonium may be used. Acids other than acetic acid such as sulfuric acid or hydrochloric may be employed, the pH being adjusted within the range specified above. 7
After bleaching of the silver image, the emulsion is washed for 1 minute with water at a, temperature of approximately F. to wash off the gelatin in the region of the silver image. The positive relief image is then in a condition for use in an imbibition process or other process for which a relief image is suitable.
The examples included herein are illustrative only and my invention is to be taken as limited only by the scope of the appended claims.
I claim:
1. The method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer to form a silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide-bromide bleach bath havin a pH of approximately 2.6 to 3.0, without dissolving but with softening the gelatin in the region of the silver image, hardening said emulsion prior to said bleaching as a step in the process, washing off the gelatin softened by the bleach bath in warm water, to form a positive gelatino-silver halide relief image.
2. The method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer hardened to a melting point of approximately 180 F. to form a, silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide-bromide bleach bath having a pH of approximately 2.6 to 3.0, said bleach bath softening the gelatin in the region of the silver image without dissolvin it, and washing off the gelatin softened by the bleach bath in warm water to form a positive gelatinc silver halide relief image.
3. The method of forming a photographic relief image which comprises developing a gelatino-silver halide emulsion layer to form a silver image therein, bleaching the silver to silver bromide in a hydrogen peroxide bleach bath containing approximately grams per liter of potassium bromide and having a pH of approximately 2.6 to 3.0, hardening said emulsion to a melting point of approximately 180 F. prior to said bleaching as a step in the process, said bleach bath softening the gelatin in the region of the silver image without dissolving it, and washing off the gelatin softened by the bleach bath in warm water to form a positive gelatino-silver halide relief image.
ROBERT P. SPECK.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS OTHER REFERENCES Luppo-Cramer, Neue Untersuchungen USW CXV. Uber Die Reaktion USW, Photo. Korres. 48, pages 466 to 471 (1911), pages 466 and 467 especially cited (copy in S. L.).
Henney & Dudley, Handbook of Photography, McGraw-Hill Book Company, 1939,, page, 342, cited (copy in Div. 67).
Claims (1)
1. THE METHOD OF FORMING A PHOTOGRAPHIC RELIEF IMAGE WHICH COMPRISES DEVELOPING A GELATINO-SILVER HALIDE EMULSION LAYER TO FORM A SILVER IMAGE THEREIN, BLEACHING THE SILVER TO SILVER BROMIDE IN A HYDROCARBON PEROXIDE-BROMIDE BLEACH BATH HAVING A PH OF APPROXIMATELY 2.6 TO 3.0, WITHOUT DISSOLVING BUT WITH SOFTENING THE GELATIN IN THE REGION OF THE SILVER IMAGE, HARDENING SAID EMULSION PRIOR TO SAID BLEACHING AS A STEP IN THE PROCESS, WASHING OFF THE GELATIN SOFTENED BY THE BLEACH BATH IN WARM WATER, TO FORM A POSITIVE GELATINO-SILVER HALIDE RELIEF IMAGE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US674037A US2494068A (en) | 1946-06-03 | 1946-06-03 | Photographic relief image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US674037A US2494068A (en) | 1946-06-03 | 1946-06-03 | Photographic relief image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2494068A true US2494068A (en) | 1950-01-10 |
Family
ID=24705066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US674037A Expired - Lifetime US2494068A (en) | 1946-06-03 | 1946-06-03 | Photographic relief image |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2494068A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3264107A (en) * | 1961-09-08 | 1966-08-02 | Ciba Ltd | Baths suitable for rehalogenating metallic silver in photographic materials |
| US3372028A (en) * | 1961-01-10 | 1968-03-05 | Panacolor Inc | Color process utilizing a single layer silver halide emulsion |
| US3447923A (en) * | 1964-06-08 | 1969-06-03 | Gevaert Photo Prod Nv | Color photographic process |
| US3634083A (en) * | 1968-01-22 | 1972-01-11 | Itek Corp | Photographic process for producing relief images by extended physical development |
| US3747525A (en) * | 1967-09-08 | 1973-07-24 | Agfa Gevaert Nv | Treating a developed gelatin silver halide emulsion layer element with acetic acid and dischromate ions |
| US4370396A (en) * | 1980-02-15 | 1983-01-25 | Fuji Photo Film Co., Ltd. | Process for producing color filter plates |
| US5716767A (en) * | 1995-12-29 | 1998-02-10 | Agfa-Gevaert Ag | Bleaching bath for photographic black-&-white material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR423150A (en) * | 1910-02-07 | 1911-04-08 | Edouard Belin | Gelatin-based photo printing process and its applications in photomechanical industries |
| US1938290A (en) * | 1932-05-07 | 1933-12-05 | Hurst Ralph Emerson | Photomechanical printing |
| US1939947A (en) * | 1931-02-13 | 1933-12-19 | George E Baxter | Color film and method of making same |
| US2058396A (en) * | 1933-03-13 | 1936-10-27 | Elton N Baker | Photoink printing |
| US2068879A (en) * | 1933-09-09 | 1937-01-26 | Cambridge Trust Company | Photographic relief process |
| US2120441A (en) * | 1935-04-06 | 1938-06-14 | Naamlooze Vennootschap Nl Lab | Process for applying silver halide colloid layers without distortion on future printing forms |
-
1946
- 1946-06-03 US US674037A patent/US2494068A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR423150A (en) * | 1910-02-07 | 1911-04-08 | Edouard Belin | Gelatin-based photo printing process and its applications in photomechanical industries |
| US1939947A (en) * | 1931-02-13 | 1933-12-19 | George E Baxter | Color film and method of making same |
| US1938290A (en) * | 1932-05-07 | 1933-12-05 | Hurst Ralph Emerson | Photomechanical printing |
| US2058396A (en) * | 1933-03-13 | 1936-10-27 | Elton N Baker | Photoink printing |
| US2068879A (en) * | 1933-09-09 | 1937-01-26 | Cambridge Trust Company | Photographic relief process |
| US2120441A (en) * | 1935-04-06 | 1938-06-14 | Naamlooze Vennootschap Nl Lab | Process for applying silver halide colloid layers without distortion on future printing forms |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3372028A (en) * | 1961-01-10 | 1968-03-05 | Panacolor Inc | Color process utilizing a single layer silver halide emulsion |
| US3264107A (en) * | 1961-09-08 | 1966-08-02 | Ciba Ltd | Baths suitable for rehalogenating metallic silver in photographic materials |
| US3447923A (en) * | 1964-06-08 | 1969-06-03 | Gevaert Photo Prod Nv | Color photographic process |
| US3747525A (en) * | 1967-09-08 | 1973-07-24 | Agfa Gevaert Nv | Treating a developed gelatin silver halide emulsion layer element with acetic acid and dischromate ions |
| US3634083A (en) * | 1968-01-22 | 1972-01-11 | Itek Corp | Photographic process for producing relief images by extended physical development |
| US4370396A (en) * | 1980-02-15 | 1983-01-25 | Fuji Photo Film Co., Ltd. | Process for producing color filter plates |
| US5716767A (en) * | 1995-12-29 | 1998-02-10 | Agfa-Gevaert Ag | Bleaching bath for photographic black-&-white material |
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