US2713305A - Photographic dye transfer process - Google Patents
Photographic dye transfer process Download PDFInfo
- Publication number
- US2713305A US2713305A US405342A US40534254A US2713305A US 2713305 A US2713305 A US 2713305A US 405342 A US405342 A US 405342A US 40534254 A US40534254 A US 40534254A US 2713305 A US2713305 A US 2713305A
- Authority
- US
- United States
- Prior art keywords
- image
- silver
- dye
- receiving sheet
- 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 23
- 229910052709 silver Inorganic materials 0.000 claims description 41
- 239000004332 silver Substances 0.000 claims description 41
- -1 SILVER HALIDE Chemical class 0.000 claims description 38
- 239000000839 emulsion Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000981 basic dye Substances 0.000 claims description 12
- 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 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000004043 dyeing Methods 0.000 claims description 7
- 238000005213 imbibition Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 6
- 229910021612 Silver iodide Inorganic materials 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 229940045105 silver iodide Drugs 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 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 4
- 239000002253 acid Substances 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 229940107698 malachite green Drugs 0.000 description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QCGOYKXFFGQDFY-UHFFFAOYSA-M 1,3,3-trimethyl-2-[3-(1,3,3-trimethylindol-1-ium-2-yl)prop-2-enylidene]indole;chloride Chemical compound [Cl-].CC1(C)C2=CC=CC=C2N(C)\C1=C\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C QCGOYKXFFGQDFY-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GRPFBMKYXAYEJM-UHFFFAOYSA-M [4-[(2-chlorophenyl)-[4-(dimethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C(=CC=CC=1)Cl)=C1C=CC(=[N+](C)C)C=C1 GRPFBMKYXAYEJM-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- MCTQNEBFZMBRSQ-UHFFFAOYSA-N (3-amino-4-phenyldiazenylphenyl)azanium;chloride Chemical compound Cl.NC1=CC(N)=CC=C1N=NC1=CC=CC=C1 MCTQNEBFZMBRSQ-UHFFFAOYSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical class C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- QQOPAWAPLFHEEP-UHFFFAOYSA-M [7-(dimethylamino)-2-methylphenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].O1C2=CC(N(C)C)=CC=C2N=C2C1=CC(=[N+](CC)CC)C(C)=C2 QQOPAWAPLFHEEP-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 description 1
- 229940023020 acriflavine Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DTJAPYHTDACJJX-UHFFFAOYSA-N bis[3-methyl-4-(methylamino)phenyl]methylideneazanium;chloride Chemical compound Cl.C1=C(C)C(NC)=CC=C1C(=N)C1=CC=C(NC)C(C)=C1 DTJAPYHTDACJJX-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
- G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/142—Dye mordant
Definitions
- This invention relates to a photographic dye transfer process of particular use in color photography.
- bromoil transfer of Pinatype depends on difierential attraction of wet tanned and untanned gelatin for greasy inks, or for certain types of dyes. These processes are notoriously diflicult to control; the Pinatype process is no longer in use, and bromoil transfer is used only in a very limited way for artistic effects.
- the process includes bleaching a developed silver image in a fixed-out emulsion layer to silver halide in a well known manner, then treating the silver halide image thus obtained with a basic dye in the presence of a water soluble halide salt such as an alkali metal chloride, bromide or iodide. As a result, the dye becomes adsorbed on the negatively charged silver halide image.
- the dyed silver halide image can then be used for making a multiplicity of imbibition dye prints by merely pressing the image into contact with a mordanted receiving sheet in the presence of a soluble silver salt.
- the function of the silver salt is to reverse the charge on the silver halide and allow dilfusion of the dye to the receiving sheet.
- a normal silver image is formed in an emulsion by exposure and development in a standard developer such as a Metol-hydroquinone developer followed by fixing and washing.
- the resulting element appears substantially as shown in greatly enlarged cross-sectional view in Stage 1 of the drawings ICC Acridine Yellow (Color Index 785) Auramine G (Color Index 656) Auramine 0 (Color Index 655) Capriblau GON (Color Index 876) Chrysoidine Y (Color Index 20) Methylene Blue GX (Color Index 922) New Fast Green 2B (Color Index 659) Rhoduline Blue 6GA (Color Index 658) Thiofiavine T (Color Index 815) Malachite Green (Color Index 657) Acrifiavine (Color Index 790) Astraphloxine FF (Schultz-Lehmann 930)
- the dyeing of the silver image with the basic dye is carried out in the presence of a salt containing an anion which is absorbed by the silver
- soluble iodide salt such as an alkali-metal idoide. It appears essential that the anion of the salt such as iodide can be present when dyeing the silver halide image in order to maintain satisfactory absorption of the basic dye on the silver halide.
- the dyed element is shown in Stage 3 of the drawings as containing the image 14 of silverhalide on which the dye has been absorbed.
- a receiving sheet is prepared, for example, by coating on a paper or film support a gelatin layer containing a mordant for the basic dye to be transferred.
- Suitable mordants for the basic dyes are, for example, silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, a styrene-maleic anhydride copolymer (1 to l), polyvinyl phthalate, sulfonated polystyrene, or other high molecular weight anionic material which combines with the cation of the basic dye.
- suitable mordants for the basic dyes include alkali metal or amine salts of compounds having the general formulas:
- R is a radical having a molecular weight of the order of 350 or larger, e. g.
- Stage 4 simulates the appearance of the receiving sheet after transfer thereto of the dye image from the element of Stage 3, according to which layer 15 is the support, such as paper, carrying a thin hydrophilic organic colloid coating 16, such as gelatin, containing the mordant and soluble silver salt and to which .the dye image 17 has transferred by imbibition.
- layer 15 is the support, such as paper, carrying a thin hydrophilic organic colloid coating 16, such as gelatin, containing the mordant and soluble silver salt and to which .the dye image 17 has transferred by imbibition.
- Repeated transfers can be made from the same element containing the silver halide image by merely washing the element with dilute acid to remove the soluble silver salt and again treating with the basic dye solution in the presence of soluble iodide salt followed by transferring the dye'to a mordanted receiving sheet in the presence of soluble silver salt.
- the amount of dye adsorbed by the silver halide image is so high that the amount of dye needed for maximum density in a final image can be transferred from a silver halide image which had an optical density of about 1.0
- Example I Color-separation images meprepared on a suitable emulsion (forexa-mple, a fine-grained sound recording or' duplicating negative film), and developing to a gamma of 'abont- 0.5. After normal fixing and washing, these images are converted to silver iodide by bathing for two minutes at 7 F. in'a solution of 20 g. K3Fe(CN)s and 20 g. KI in 1.0 liter of water. The film is then washed in running water for five minutes. image is dyed for 1% minutes in a bath of cc. glacial acetic acid, 0.30 g. KI and 5.0 g. Malachite Green or Rhoduline Blue 66A in 1.0 liter -of 'water. It is then washed in at least two changes of a solution of 10 g.
- a typical receiving sheet may contain 20 g. of the sodium salt of phosphotungstic acid per 100 g. of deashed gelatin, coated at 0.42 g. gelatin per square foot. This sheet is soaked for three minutes in a solution "of '10 g. acetic acid and 17 g. silver nitrate per liter of water and the excess removed. The cyan dyed image is rolled into contact with the receiving sheet; transfer is complete in three minutes or less. The red separation image is then removed and washed in three change s-of acetic acid '10 g. per liter, to remove silver nitrate, before dyeing again. The receiving sheet is re.-
- the green'separation negative is dyed and transferred like the red, except that Astraphloxine FF is used instead of. Malachite Green.
- the receiving sheet and separation image are-washed and reconditioned as before.
- the blue separation image is transferred in the same way except Acrifl'avine'is used asthe dye.
- the receiving sheet with the complete image is washed thoroughly in The red separation .1:
- dilute acid to remove excess silver salt and dried.
- the transfer should be carried out under light from which ultraviolet and violet have been removed although white light can be used momentarily to. judge color balance.
- An alternative method for removing soluble silver salts from the separation images after transfer is to bathe in one or more changes of a solution of 20 g. sodium sulfite in 1.0 liter of water, followed by washing in water. The image can then be dyed as described above.
- Example II A receiving sheet is prepared as follows:
- the solution for coating was prepared by adding the above to a solution of 40 g. gelatin, 0.6 g. saponin (spreading agent), 0.3 g. mucochloric acid (hardening agent),
- the final solution was coated on a film base of cellulose acetate at 1 lb. dry gelatin per 600 sq. ft.
- a silver image in gelatin on film base was bleached 2 minutes in 1% potassium iodide-l% potassium ferricyanide solution in water to produce a silver iodide image. After washing in running water 2 minutes, the sample was bathed 2 minutes in a water solution containing 0.25% Malachite Green, 1 acetic acid, 12% ethanol, and 0.05% potassium iodide. A 3-minute wash in running water followed, leaving an image consisting of dye adsorbed to silver iodide.
- the receiving sheet (mordanted blank prepared above)" was conditioned by treating first 2 minutes in a hardening bath consisting of 0.5 g. sodium hexametaphosphate, 5.0 g. sodium bisulfite, 5.0 g. sodium carbonate monohydrate, 1.0 g. potassium bromide, g. sodium sulfate and 20 cc. formalin (40%) made up to one liter with water. This was followed by a l-minute water wash and a 3-minute bath in 0.1 N silver nitrate in 1% acetic acid. 7
- the wet imagesample was rolled into contact with the wet, treated receiving sheet and after 2 minutes removed.
- the receiving sheet, containing the transferred image was washed in running water 1 minute and dried.
- a photographic reproduction process which comprises oxidizing a silver image contained in a developed and fixed silver halide emulsion layer, to a silver halide image, dyeing the silver halid image with a basic dye in the presence of a water'soluble halide salt, washing excess dye and halide salt from the emulsion layer, pressing the emulsion layer'while moist into contact with a moist mordanted receiving sheet in the presence of a water-soluble silver salt to transfer the dye image-wise I from the silver halide image to the receiving sheet by imbibition.
- a photographic reproduction process which comprises oxidizing a silver image contained in a developed and fixed silver halide emulsion layer, to a silver iodide V image, dyeing the silver iodide image with a basic dye in the presence of an alkali metal iodide, washing excess dye and alkali metal iodide from the emulsion layer, pressing the'emulsion layer while moist into contact with a moist mordanted receiving sheet in the presence of silver nitrate to transfer the dyeimagewise from the silver iodide image to the receiving sheet by imbibition.
- a photographic reproduction process which comprises preparing a set of silver color-separation records 'in fixed-out silver halide emulsion layers on separate supports, oxidizing each silver color-separation record to 5.
- the process of claim 1 wherein the water-soluble silver halide, dyeing the silver halide records thus formed halide salt is an alkali metal chloride. respectively with subgractively colored basic dyes in the 6.
- the process of claim 1 wherein the water-soluble presence of an alkaliimetal iodide, washing excess dye halide salt is an alkali metal bromide. and alkali metal iodide from each dyed silver halide 5 7.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Coloring (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent PHOTOGRAPEHC DYE TRANSFER PROCESS Henry C. Yutzy and Burt H. Carroll, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application January 21, 1954, Serial No. 405,342
7 Claims. (Cl. NIL-149.1)
This invention relates to a photographic dye transfer process of particular use in color photography.
A number of methods for monochrome and color photography by transfer of dye images have been devised. Most of these depend on the formation of a relief image in gelatin by a variety of means which have one point in common, the exposure of an emulsion containing such a high concentration of dye or pigment that the exposure varies rapidly with the distance to which light has penetrated the emulsion. By means such as a tanning developer, a tanning bleach bath, or an etch bath regulated by concentration of silver, the gelatin of the emulsion at points containing a critical concentration of silver is either tanned or made soluble, so that on development with hot water a relief image is formed in varying thicknesses of gelatin. This is used to absorb dye which is transferred to a receiving sheet. These relief processes have been and are used on a large scale commercially, but they have several difi'iculties. In the first place, the high light-absorption of the emulsion greatly decreases its sensitivity, and, combined with the hot Water development, gives a very unfavorable relation of speed to definition. The images are physically soft, and all types of these processes are difficult to control, especially with the precision necessary for three-color photography. When used for cine film or other small images, the relief image may give difficulty of contact with the blank.
Another type of transfer process, represented by bromoil transfer of Pinatype, depends on difierential attraction of wet tanned and untanned gelatin for greasy inks, or for certain types of dyes. These processes are notoriously diflicult to control; the Pinatype process is no longer in use, and bromoil transfer is used only in a very limited way for artistic effects. I
We have discovered a process of transferring dye images by imbibition from planar surfaces, which employs a silver image formed in an ordinary silver halide emulsion layer which need not contain a dye or pigment to lessen emulsion speed. The process includes bleaching a developed silver image in a fixed-out emulsion layer to silver halide in a well known manner, then treating the silver halide image thus obtained with a basic dye in the presence of a water soluble halide salt such as an alkali metal chloride, bromide or iodide. As a result, the dye becomes adsorbed on the negatively charged silver halide image. The dyed silver halide image can then be used for making a multiplicity of imbibition dye prints by merely pressing the image into contact with a mordanted receiving sheet in the presence of a soluble silver salt. The function of the silver salt is to reverse the charge on the silver halide and allow dilfusion of the dye to the receiving sheet.
According to the process, a normal silver image is formed in an emulsion by exposure and development in a standard developer such as a Metol-hydroquinone developer followed by fixing and washing. The resulting element appears substantially as shown in greatly enlarged cross-sectional view in Stage 1 of the drawings ICC Acridine Yellow (Color Index 785) Auramine G (Color Index 656) Auramine 0 (Color Index 655) Capriblau GON (Color Index 876) Chrysoidine Y (Color Index 20) Methylene Blue GX (Color Index 922) New Fast Green 2B (Color Index 659) Rhoduline Blue 6GA (Color Index 658) Thiofiavine T (Color Index 815) Malachite Green (Color Index 657) Acrifiavine (Color Index 790) Astraphloxine FF (Schultz-Lehmann 930) The dyeing of the silver image with the basic dye is carried out in the presence of a salt containing an anion which is absorbed by the silver halide, e. g., soluble iodide salt such as an alkali-metal idoide. It appears essential that the anion of the salt such as iodide can be present when dyeing the silver halide image in order to maintain satisfactory absorption of the basic dye on the silver halide. The dyed element is shown in Stage 3 of the drawings as containing the image 14 of silverhalide on which the dye has been absorbed.
A receiving sheet is prepared, for example, by coating on a paper or film support a gelatin layer containing a mordant for the basic dye to be transferred. Suitable mordants for the basic dyes are, for example, silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, a styrene-maleic anhydride copolymer (1 to l), polyvinyl phthalate, sulfonated polystyrene, or other high molecular weight anionic material which combines with the cation of the basic dye. Further examples of suitable mordants for the basic dyes include alkali metal or amine salts of compounds having the general formulas:
wherein R is a radical having a molecular weight of the order of 350 or larger, e. g.
5-[2-(2,4-di-te rt amylphenoxy)phenylcarbamyl]-1,3 benzene sodium disulfonate 3- [4- (2,4-di-tert-amylphenoxy) -3- 3-sodiumsulfophenylcarbamyl)phenylcarbamyl]-benzene sodium sulfonate 5-[4-(2,4 di-tert-amylphenoxy)-3-(phenylcarbamyl)- phenylcarbamyl]-1,3-benzene sodium disulfonate 5-[4-(2,4 di-tert-amylphenoxy)-3-(2-hydroxy-3,5-dichloro 4 methylphenylcarbamyl)phenylcarbamylmethyleneoxy]-1,3-benzene sodium dicarboxylate 5-[4-(2,4-di-tert-amylphenoxy) 3 (4-{l -hydroxy-4- chloro Z-naphthyl}carbamylethyl)phenylcarbamyll-1,31 benzene soduim disulfonate '3-[4-(2,4-di-tert-amylphenoxy) 3 (2-hydroxy-3,5-dichloro 4 methylphenylcarbamyl)phenylcarbamyl] -'benzene sodiumsulfonate. 'Ihe alkali metal. or amine salts of sulfonated naphthalene-formaldehyde condensates such as sold under the trade name Tamol P by the Rohm and Haas Company and under the trade nameDaXad ll by the Dewey and Almy Chemical "Co, and also useful as mordants in our process.
Stage 4 simulates the appearance of the receiving sheet after transfer thereto of the dye image from the element of Stage 3, according to which layer 15 is the support, such as paper, carrying a thin hydrophilic organic colloid coating 16, such as gelatin, containing the mordant and soluble silver salt and to which .the dye image 17 has transferred by imbibition.
Repeated transfers can be made from the same element containing the silver halide image by merely washing the element with dilute acid to remove the soluble silver salt and again treating with the basic dye solution in the presence of soluble iodide salt followed by transferring the dye'to a mordanted receiving sheet in the presence of soluble silver salt.
The amount of dye adsorbed by the silver halide image is so high that the amount of dye needed for maximum density in a final image can be transferred from a silver halide image which had an optical density of about 1.0
' as'a silver image.
for example, by exposing under a color transparency to Q the red, green and blue primary regions of the spectrum and developing the records to low contrast. Good definition in the process is maintained by utilizing thin, well hardened colloid layers both for the silver halide color separation films and the receiving sheet.
, Example I Color-separation images meprepared on a suitable emulsion (forexa-mple, a fine-grained sound recording or' duplicating negative film), and developing to a gamma of 'abont- 0.5. After normal fixing and washing, these images are converted to silver iodide by bathing for two minutes at 7 F. in'a solution of 20 g. K3Fe(CN)s and 20 g. KI in 1.0 liter of water. The film is then washed in running water for five minutes. image is dyed for 1% minutes in a bath of cc. glacial acetic acid, 0.30 g. KI and 5.0 g. Malachite Green or Rhoduline Blue 66A in 1.0 liter -of 'water. It is then washed in at least two changes of a solution of 10 g.
acetic acid per liter of water, to remove dye and iodide J g from the gelatin. A typical receiving sheet may contain 20 g. of the sodium salt of phosphotungstic acid per 100 g. of deashed gelatin, coated at 0.42 g. gelatin per square foot. This sheet is soaked for three minutes in a solution "of '10 g. acetic acid and 17 g. silver nitrate per liter of water and the excess removed. The cyan dyed image is rolled into contact with the receiving sheet; transfer is complete in three minutes or less. The red separation image is then removed and washed in three change s-of acetic acid '10 g. per liter, to remove silver nitrate, before dyeing again. The receiving sheet is re.-
conditioned by soaking againin the acid solution of silver nitrate. Y
The green'separation negative is dyed and transferred like the red, except that Astraphloxine FF is used instead of. Malachite Green. The receiving sheet and separation image are-washed and reconditioned as before. The blue separation imageis transferred in the same way except Acrifl'avine'is used asthe dye. Finally, the receiving sheet with the complete image is washed thoroughly in The red separation .1:
dilute acid to remove excess silver salt, and dried. The transfer should be carried out under light from which ultraviolet and violet have been removed although white light can be used momentarily to. judge color balance.
An alternative method for removing soluble silver salts from the separation images after transfer is to bathe in one or more changes of a solution of 20 g. sodium sulfite in 1.0 liter of water, followed by washing in water. The image can then be dyed as described above.
Example II A receiving sheet is prepared as follows:
13.0 g. 5-[4-(2,4-di-tert-amylphenoxy)-3-(2-hydroxy- 3,5 -dichloro 4 -methylphenylcarbamyl) phenylcarbamyl] 1,3-benzene disulfonyl chloride was hydrolyzed by boiling 5 minutes in a solution of cc. of sodium hydroxide and cc. of ethyl alcohol.
The solution for coating was prepared by adding the above to a solution of 40 g. gelatin, 0.6 g. saponin (spreading agent), 0.3 g. mucochloric acid (hardening agent),
and 690 g. water.
The final solution was coated on a film base of cellulose acetate at 1 lb. dry gelatin per 600 sq. ft.
A silver image in gelatin on film base was bleached 2 minutes in 1% potassium iodide-l% potassium ferricyanide solution in water to produce a silver iodide image. After washing in running water 2 minutes, the sample was bathed 2 minutes in a water solution containing 0.25% Malachite Green, 1 acetic acid, 12% ethanol, and 0.05% potassium iodide. A 3-minute wash in running water followed, leaving an image consisting of dye adsorbed to silver iodide.
The receiving sheet (mordanted blank prepared above)" was conditioned by treating first 2 minutes in a hardening bath consisting of 0.5 g. sodium hexametaphosphate, 5.0 g. sodium bisulfite, 5.0 g. sodium carbonate monohydrate, 1.0 g. potassium bromide, g. sodium sulfate and 20 cc. formalin (40%) made up to one liter with water. This was followed by a l-minute water wash and a 3-minute bath in 0.1 N silver nitrate in 1% acetic acid. 7
The wet imagesample was rolled into contact with the wet, treated receiving sheet and after 2 minutes removed. The receiving sheet, containing the transferred image was washed in running water 1 minute and dried.
It was observed that all the dye had transferred and that the final image had appreciably better definition than images obtained similarly using other classes of non-difiusing acid mordants in the receiving sheet.
Whatwe claim is:
l. A photographic reproduction process which comprises oxidizing a silver image contained in a developed and fixed silver halide emulsion layer, to a silver halide image, dyeing the silver halid image with a basic dye in the presence of a water'soluble halide salt, washing excess dye and halide salt from the emulsion layer, pressing the emulsion layer'while moist into contact with a moist mordanted receiving sheet in the presence of a water-soluble silver salt to transfer the dye image-wise I from the silver halide image to the receiving sheet by imbibition.
2. A photographic reproduction process which comprises oxidizing a silver image contained in a developed and fixed silver halide emulsion layer, to a silver iodide V image, dyeing the silver iodide image with a basic dye in the presence of an alkali metal iodide, washing excess dye and alkali metal iodide from the emulsion layer, pressing the'emulsion layer while moist into contact with a moist mordanted receiving sheet in the presence of silver nitrate to transfer the dyeimagewise from the silver iodide image to the receiving sheet by imbibition. I
3. A photographic reproduction process which comprises preparing a set of silver color-separation records 'in fixed-out silver halide emulsion layers on separate supports, oxidizing each silver color-separation record to 5. The process of claim 1 wherein the water-soluble silver halide, dyeing the silver halide records thus formed halide salt is an alkali metal chloride. respectively with subgractively colored basic dyes in the 6. The process of claim 1 wherein the water-soluble presence of an alkaliimetal iodide, washing excess dye halide salt is an alkali metal bromide. and alkali metal iodide from each dyed silver halide 5 7. The process of claim 1 wherein the water-soluble record, pressing the inoist dyed and washed records halide salt is an alkali metal iodide. successively into contact with a moist mordanted receiving sheet in the presence of a soluble silver salt to form Refefellus Cited 11! file of this Bale!!! a snbtractively colored picture on the receiving sheet. UNITED STATES PATENTS 4. The process of claim 3 wherein red, green and blue 10 color separation records of silver, after oxidizing each Taulelgne 1913 to silver halide, are': dyed with Rhoduline Blue 66A, Astraphloxine FF, and Acriflavine dyes respectively.
Claims (1)
1. A PHOTOGRAPHIC REPRODUCTION PROCESS WHICH COMPRISES OXIDIZING A SILVER IMAGE CONTAINED IN A DEVELOPED AND FIXED SILVER HALIDE EMULSION LAYER, TO A SILVER HALIDE IMAGE, DYEING THE SILVER HALID IMAGE WITH A BASIC DYE IN THE PRESENCE OF A WATER-SOLUBLE HALIDE SALT, WASHING EXCESS DYE AND HALIDE SALT FROM THE EMULSION LAYER, PRESSING THE EMULSION LAYER WHILE MOIST INTO CONTACT WITH A MOIST MORDANTED RECEIVING SHEET IN THE PRESENCE OF A WATER-SOLUBLE SILVER SALT TO TRANSFER THE DYE IMAGE-WISE FROM THE SILVER HALIDE IMAGE TO THE RECEIVING SHEET BY IMBIBITION.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE535053D BE535053A (en) | 1954-01-21 | ||
| US405342A US2713305A (en) | 1954-01-21 | 1954-01-21 | Photographic dye transfer process |
| FR1125410D FR1125410A (en) | 1954-01-21 | 1955-01-21 | Photographic reproduction process |
| GB1941/55A GB763797A (en) | 1954-01-21 | 1955-01-21 | Improvements in dye transfer processes particularly for colour photography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US405342A US2713305A (en) | 1954-01-21 | 1954-01-21 | Photographic dye transfer process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2713305A true US2713305A (en) | 1955-07-19 |
Family
ID=23603301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US405342A Expired - Lifetime US2713305A (en) | 1954-01-21 | 1954-01-21 | Photographic dye transfer process |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2713305A (en) |
| BE (1) | BE535053A (en) |
| FR (1) | FR1125410A (en) |
| GB (1) | GB763797A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940849A (en) * | 1957-07-10 | 1960-06-14 | Eastman Kodak Co | Planographic dye transfer process |
| US3486450A (en) * | 1964-02-27 | 1969-12-30 | Eastman Kodak Co | Color proofing system |
| US3505956A (en) * | 1964-10-01 | 1970-04-14 | Philip A Pizzi | Dye imbibition transfer blank |
| US3620738A (en) * | 1968-03-14 | 1971-11-16 | Itek Corp | Dye transfer color photography |
| US4278749A (en) * | 1979-03-09 | 1981-07-14 | Ciba-Geigy Ag | Receiving elements containing graft gelatin polymers as dye mordants |
| EP0346072A3 (en) * | 1988-06-08 | 1990-09-12 | Eastman Kodak Company (A New Jersey Corporation) | Improved inbibition dye printing blank |
| US5654202A (en) * | 1992-03-24 | 1997-08-05 | Eastman Kodak Company | Stabilization of a patterned planarizing layer for solid state imagers prior to color filter pattern formation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1059917A (en) * | 1910-03-23 | 1913-04-22 | Auguste Jean Baptiste Tauleigne | Process of photography in colors. |
-
0
- BE BE535053D patent/BE535053A/xx unknown
-
1954
- 1954-01-21 US US405342A patent/US2713305A/en not_active Expired - Lifetime
-
1955
- 1955-01-21 FR FR1125410D patent/FR1125410A/en not_active Expired
- 1955-01-21 GB GB1941/55A patent/GB763797A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1059917A (en) * | 1910-03-23 | 1913-04-22 | Auguste Jean Baptiste Tauleigne | Process of photography in colors. |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940849A (en) * | 1957-07-10 | 1960-06-14 | Eastman Kodak Co | Planographic dye transfer process |
| US3486450A (en) * | 1964-02-27 | 1969-12-30 | Eastman Kodak Co | Color proofing system |
| US3505956A (en) * | 1964-10-01 | 1970-04-14 | Philip A Pizzi | Dye imbibition transfer blank |
| US3620738A (en) * | 1968-03-14 | 1971-11-16 | Itek Corp | Dye transfer color photography |
| US4278749A (en) * | 1979-03-09 | 1981-07-14 | Ciba-Geigy Ag | Receiving elements containing graft gelatin polymers as dye mordants |
| EP0346072A3 (en) * | 1988-06-08 | 1990-09-12 | Eastman Kodak Company (A New Jersey Corporation) | Improved inbibition dye printing blank |
| US5654202A (en) * | 1992-03-24 | 1997-08-05 | Eastman Kodak Company | Stabilization of a patterned planarizing layer for solid state imagers prior to color filter pattern formation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB763797A (en) | 1956-12-19 |
| FR1125410A (en) | 1956-10-30 |
| BE535053A (en) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2774668A (en) | Process and product for forming color images from complete dyes | |
| US2756142A (en) | Photographic color reproduction process | |
| US2559643A (en) | Photographic product and process | |
| US2713305A (en) | Photographic dye transfer process | |
| GB470074A (en) | Production of coloured photographic images by development | |
| US3877938A (en) | Etch-bleaching method | |
| US3087817A (en) | Process and product for forming color images from complete dyes | |
| US3414411A (en) | Dye bleach process | |
| US2386167A (en) | Photographic article of manufacture | |
| US2518686A (en) | Aldehyde antistain baths for developed color photographic material | |
| US2366439A (en) | Photographic materials | |
| US2498418A (en) | Production of azo dyestuff images from n-acyl-n-aryl hydrazine developers | |
| US3445228A (en) | Dye diffusion transfer process and element | |
| GB519790A (en) | Colour photographic process | |
| US2034220A (en) | Light-sensitive layer and method of producing colored pictures | |
| US3592645A (en) | Color prints of improved brightness | |
| US3012885A (en) | Pressure image transfer process | |
| US2940849A (en) | Planographic dye transfer process | |
| US1966330A (en) | Process for making two-color subtractive photographic prints on double-coated film | |
| US2563469A (en) | Light sensitive elements for color photography | |
| US2241519A (en) | Photographic material | |
| US2231685A (en) | Photographic color process and film for use therein | |
| GB442522A (en) | Improved process for the production of multi-colour photographic pictures, and photographic material therefor | |
| US3726682A (en) | Photographic materials with alkalisoluble antihalation layer | |
| US3251689A (en) | Masking film |