US1305962A - crabtree - Google Patents
crabtree Download PDFInfo
- Publication number
- US1305962A US1305962A US1305962DA US1305962A US 1305962 A US1305962 A US 1305962A US 1305962D A US1305962D A US 1305962DA US 1305962 A US1305962 A US 1305962A
- Authority
- US
- United States
- Prior art keywords
- image
- dye
- colored
- silver
- copper
- 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
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- 239000000975 dye Substances 0.000 description 76
- 229910052709 silver Inorganic materials 0.000 description 42
- 239000004332 silver Substances 0.000 description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 40
- 238000000034 method Methods 0.000 description 28
- 150000002500 ions Chemical class 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 150000001879 copper Chemical class 0.000 description 14
- 229910001431 copper ion Inorganic materials 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-M Sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000981 basic dye Substances 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WSSJONWNBBTCMG-UHFFFAOYSA-N Homosalate Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000282979 Alces alces Species 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 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
- 239000001263 FEMA 3042 Substances 0.000 description 2
- 229960003975 Potassium Drugs 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K Potassium citrate Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 240000003670 Sesamum indicum Species 0.000 description 2
- 229940033123 Tannic Acid Drugs 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N Tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000003638 reducing agent Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 239000011791 tripotassium citrate Substances 0.000 description 2
- 235000015870 tripotassium citrate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
Definitions
- My invention relates to the production of colored images. More particularly it relates to the mordanting of dyes onto,inorganic compounds which ma be dispersed or distributed through a sultable transparent medium in the form of images.
- I inorganic compounds which ma be dispersed or distributed through a sultable transparent medium in the form of images.
- a dye may be adsorbed thereon in correspondence with the original image, thus giving a colored image havingapproximately the same form and gradation as the original picture.
- the inorganic part of such coloredpicture may be further treated or removed.
- Flat or. even tones may be similarly changed into colored tints suitable for light filters or general light-modifying purposes.
- a flat or. even tone in the picture bemg but the image of an object having a flat or even tone, I shall use the word image generically to include flat tones as well as the more usual graded images.
- the objects of my invention are to effect these results, carry out such a process, and obtain such a product by steps that will be under good control, that will be rapid, that will yield pictures having good gradation,
- a silver and a copper salt being capable of acting as a mordant to dyes, especially basic dyes or amino derivatives.
- This resulting image may be considered as a secondary image.
- the bleached image is immersed in a suitable dye bath until sufficient dye is adsorbed or mordanted and the picture is thus colored.
- I may dissolve away or fix out the silver salt Wholly or partially, leaving an image of dye associated with the copper salt alone or with some of the silver salt. I may also convert the dye image into a lake.
- the film is rinsed free fromlthe excess of the bleaching solution, and is then immersed in a bath of a suitable dye.
- a suitable dye The type of dye which may be employed is illustrated in the following list,
- the film After dyeing, the film is washed until the highlights are sufficiently free from dye.
- the dye image can often be treated to form a lake, some reagents such as 0.25% tannic acid and 0.25% sodium acetate being added to the fixing bath.
- the colored images may beobtained in a state of great transparency also by using a very fine grained primary or silver image, it being generally true that the finer the grains in the original image, the more brilliant and transparent will be the final results. Hence, it is possible to avoid using a fixing bath.
- the dye is adsorbed chiefly on the copperf til a secondary image containing a mordant ferrocyanid, and the silver ferrocyanid is dlssolved out-by the thiosulfate bath. While this .appears to be what takes place, a
- mordanting salt was formed substantially in correspondence or proportion to the original image and since the dye was adsorbed substantially in proportion to the mordanting salt the dyed image will have a gradation similar to that of the original image.
- the process of producing a colored image which comprises, forming an image containing copper ferrocyanid capable of acting as a mordant and treating said image containing copper ferrocyanid with a suitable dye until sufiicient dye is ,mordanted by said copper ferrocyanid to produce a colored image.
- the process of producing a colored image which comprises, forming an image containing a copper salt capable of acting as a mordant and treating said image con-.
- the process of producing a colored image from a silver image which comprises, treating said silver image in a bath containing copper ions and ferricyanid ions to form a secondary image containing anmrdant, rinsing, treating said secondary image with a suitable dye until suflicient dye is mordanted by said secondary image to produce a colored image, washing out soluble salts and unmordanted dye from said image, and treating said image with a bath containing a solvent for silver salts.
- An article of manufacture comprising a transparent body containing a colored image which includes a copper salt associ: ated with a dye.
- An article of manufacture comprising a transparent colloid layer containing a colored image which includes copper ferrocyanid and a dye mordanted thereby.
- An article of manufacture comprising a layer of gelatin on a transparent base, said layer containing a colored image including copper ferrocyanid, silver ferrocyanid, and an adsorbed dye.
- a motion picture positive film comprising a flexible transparent base, a transparent gelatin layer thereon and a colored image in said gelatin including copper ferrocyanid and a dye mordanted thereby.
- a colored photographic image consisting of a copper-toned and mordant-dyed image.
- a colored photograph comprising a colloid layer containing a copper-toned red image and combined therewith a selectively mordant-dyed image.
Description
Parana enrich.
JOHN I. CRABTREE, OF ROCHESTER, NEW YORK, ASSIGNOR TO EASTMAN KODAK COMPANY, OF ROCHESTER, NEW YORK, A CORPORATION OF NEW YORK.
COLORED IMAGE AND PROCESS OF PRODUCING THE SAME.
No Drawing.
To all whom it may concern:
Be it known that I, JoHNI. CRABTREE, a resident of Rochester, in the county of Monroe and State of New York, have invented certain new and useful Improvements in C01- ored Images and Processes of Producing the Same, of which the followingis a specification.
My invention relates to the production of colored images. More particularly it relates to the mordanting of dyes onto,inorganic compounds which ma be dispersed or distributed through a sultable transparent medium in the form of images. For example, I
may add to or modify the image of a photographic picture so that a dye will be adsorbed thereon in correspondence with the original image, thus giving a colored image havingapproximately the same form and gradation as the original picture. The inorganic part of such coloredpicture may be further treated or removed. Flat or. even tones may be similarly changed into colored tints suitable for light filters or general light-modifying purposes. A flat or. even tone in the picture bemg but the image of an object having a flat or even tone, I shall use the word image generically to include flat tones as well as the more usual graded images. i v
The objects of my invention are to effect these results, carry out such a process, and obtain such a product by steps that will be under good control, that will be rapid, that will yield pictures having good gradation,
' that will not injure or'impair the Wearing qualities of the product, that will produce stable, clear and brilliant colors, and that will admit ofready duplication of effects. Other objects will hereinafter appear.
Since images made up of silver particles suspended in gelatin are most commonl met with in photographic practice, I wil describe as an example of my invention, its application to a, silver image. Generally stated, I treat or bleach the orig nal or primary image in a suitable bath until there is present Specification of Letters Patent.
Patented June 3, 1919.
Application filed January 25, 1917. Serial No. 144,557.
therein a silver and a copper salt, the latter being capable of acting as a mordant to dyes, especially basic dyes or amino derivatives. This resulting image may be considered as a secondary image. The bleached image is immersed in a suitable dye bath until sufficient dye is adsorbed or mordanted and the picture is thus colored. In certain cases I may dissolve away or fix out the silver salt Wholly or partially, leaving an image of dye associated with the copper salt alone or with some of the silver salt. I may also convert the dye image into a lake.
To specifically illustrate my method I will describe the coloring of the silver images in motion-picture positive film 'The film is immersed in any suitable or preferred fluidv treating apparatus in,a bleaching bath such as,
Cupric sulfate. 12 gr. Potassium ferri'cyanid 12 gr. Potassium citrate 75 gr. Ammonium carbonate "a 6 gr. Water to 1 lite This bleaching bath may be varied by substituting ingredients which will furnish equivalent ions. For example sodium salts may be used in place of the potassium salts.
After the film images have been bleached to the characteristic brown or copper tone, the film is rinsed free fromlthe excess of the bleaching solution, and is then immersed in a bath of a suitable dye. The type of dye which may be employed is illustrated in the following list,
ing' the highlights. Where desired, with some dyes, such as methyl green, a little acid may be added (say 0.1% acetic acid) to accelerate the dyeing and to prevent the formation of a scum on the film. The speed of the action is also increased somewhat by a higher temperature. The end point of the dyeing action is recognized by the disagpearance of the copper tone from the 'sha ows of the image, although no serious results occur from a longer treatment.
After dyeing, the film is washed until the highlights are sufficiently free from dye.
diffused when the silver salt is wholly or partially dissolved away, the dye image can often be treated to form a lake, some reagents such as 0.25% tannic acid and 0.25% sodium acetate being added to the fixing bath. I
The colored images may beobtained in a state of great transparency also by using a very fine grained primary or silver image, it being generally true that the finer the grains in the original image, the more brilliant and transparent will be the final results. Hence, it is possible to avoid using a fixing bath.
To give extra brilliancy to filmthat is to be projected, I may only partially bleach the black and white image in the first instance and subsequently fix out the same. The effeet is to tone the lighterparts of the image andd leave the shadows only partially colore The theory of What takes place in the example of my process given above, appears to be that the copper and ferricyanid ions react with the minute silver particles of the original image to form an image composed of both insoluble copper ferrocyanid and silver ferrocyanid, the sliver acting as a reducing agent with respect tothe ferricyanid.
The dye is adsorbed chiefly on the copperf til a secondary image containing a mordant ferrocyanid, and the silver ferrocyanid is dlssolved out-by the thiosulfate bath. While this .appears to be what takes place, a
knowledge of the exact theory of the reactions is obviously not indispensable to carrying, out my invention in practice. The colored film was found by comparative tests to beunimpaired in wearing qualities and,
,by attending to the manipulative details given hereinabove, effects .could be duplicated with certainty. Since the mordanting salt was formed substantially in correspondence or proportion to the original image and since the dye was adsorbed substantially in proportion to the mordanting salt the dyed image will have a gradation similar to that of the original image.
I claim:
1. The process of producing a colored image which comprises, forming an image containing copper ferrocyanid capable of acting as a mordant and treating said image containing copper ferrocyanid with a suitable dye until sufiicient dye is ,mordanted by said copper ferrocyanid to produce a colored image. v
2. The process of producing a colored image which comprises, forming an image containing a copper salt capable of acting as a mordant and treating said image con-.
taining said salt with a suitable dye until sufficient dye is mordanted by said copper salt to produce a colored image.
3. The process of converting a primary image into a colored image which comprises, forming in substantial proportion to the primary image a secondary image containing a copper salt capable of acting as a mordant and treating said secondary image containing the copper salt with a suitable dye until sufficient dye is mordanted by saidcopper salt to produce a colored image.
4. The process of producing a colored image from a metallic image which oomprises, treating said metallic image in a bath containing copper ions and ferricyanid ions to form a secondary image containing a mordant, treatin said secondary image with a suitable ye until suflicient dye is mordanted by said secondary'image to produce a colored image.
' 5. The process of producing a colored image from a silver image which comprises, treating said silver image in a bath containing copper ions and ferricyanid ions to form a secondary image containing a mordant, treating sald secondary image with a suitable basic dye until; sufficient dye is mordanted by said secondary image to produce a colored image.
6. The process of producing a colored image from a-silver image which comprises, treating 'said silver image in a bath containing copper ions and ferricyanid ions unis formed, treating said secondary image with a. dilute bath of a basic dye containing a' dilute acid until sufficient dye is mordanted by said secondary image to produce a colored image.
7. The process of producing a colored image from a silver image which comprises, treating said silver image in a bath containing copper ions and ferricyanid ions to form a secondary image containing anmrdant, rinsing, treating said secondary image with a suitable dye until suflicient dye is mordanted by said secondary image to produce a colored image, washing out soluble salts and unmordanted dye from said image, and treating said image with a bath containing a solvent for silver salts.
8. The process of producing a colored image from a primary silver image which comprises, treating said silver image in a bath containing copper ions and ferricyanid ions to form a secondary image containing a mordant but stopping the treatment before all the silver inthe' densest parts of the primary image is reached by said ions, rinsing to check further action by said ions, treating with a suitable dye until suflicient dye is mordanted by said secondary image, washing, and fixing the image.
9. The process of obtaining a very transparent colored. image which comprises,
treating a very-fine grained metallic primary lmage with a bath containing copper ions and ferricyanid ions to form a secondary image containing a; mordant, treating said secondary image with a suitable dye until sufiicient dye is adsorbed by said secondary image to produce a very transparent colored image.
10. The process of producing a colored image from a silver image which comprises, treating said silver image in a bath containing copper ions and ferricyanid ions to form a secondary image containing a mordant, treating said secondary image with a suitable dye until suflicient dye is mordanted by said secondary image to produce a colored image, washing, and treating in a bath containing a solvent for silver salts and a substance which reacts with the dye to form a lake. n
11. An article of manufacture comprising a transparent body containing a colored image which includes a copper salt associ: ated with a dye.
12. An article of manufacture comprising a transparent colloid layer containing a colored image which includes copper ferrocyanid and a dye mordanted thereby.
13. An article of manufacture comprising a layer of gelatin on a transparent base, said layer containing a colored image including copper ferrocyanid, silver ferrocyanid, and an adsorbed dye.
14. A motion picture positive film comprising a flexible transparent base, a transparent gelatin layer thereon and a colored image in said gelatin including copper ferrocyanid and a dye mordanted thereby.
15. A colored photographic image consisting of a copper-toned and mordant-dyed image. v
16. A colored photograph comprising a colloid layer containing a copper-toned red image and combined therewith a selectively mordant-dyed image.
17 The method of producing a color photographic image consisting in copper-toning a silver image and subjecting it to a bath of soluble dye capable of being selectively mordanted by the copper image. 7
JOHN 1. CRABTREE.
Witnesses W. F. MANHOLD, R. L. STINCHFIELD.
Publications (1)
Publication Number | Publication Date |
---|---|
US1305962A true US1305962A (en) | 1919-06-03 |
Family
ID=3373489
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US1305962D Expired - Lifetime US1305962A (en) | crabtree |
Country Status (1)
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US (1) | US1305962A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178290A (en) * | 1960-07-06 | 1965-04-13 | Ciba Ltd | Photographic layers suitable for the silver dyestuff bleaching method |
US4568633A (en) * | 1985-01-02 | 1986-02-04 | Eastman Kodak Company | Photographic elements and processes utilizing imagewise reduction of ferric ions |
US6265140B1 (en) * | 1997-02-24 | 2001-07-24 | Tridstore Ip, Llc | Silver halide material for optical memory devices with luminescent reading and methods for the treatment thereof |
-
0
- US US1305962D patent/US1305962A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178290A (en) * | 1960-07-06 | 1965-04-13 | Ciba Ltd | Photographic layers suitable for the silver dyestuff bleaching method |
US4568633A (en) * | 1985-01-02 | 1986-02-04 | Eastman Kodak Company | Photographic elements and processes utilizing imagewise reduction of ferric ions |
US6265140B1 (en) * | 1997-02-24 | 2001-07-24 | Tridstore Ip, Llc | Silver halide material for optical memory devices with luminescent reading and methods for the treatment thereof |
US6960426B2 (en) | 1997-02-24 | 2005-11-01 | D Data Inc. | Silver halide material for optical memory devices with luminescent reading and methods for the treatment thereof |
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