US2756142A - Photographic color reproduction process - Google Patents
Photographic color reproduction process Download PDFInfo
- Publication number
- US2756142A US2756142A US332728A US33272853A US2756142A US 2756142 A US2756142 A US 2756142A US 332728 A US332728 A US 332728A US 33272853 A US33272853 A US 33272853A US 2756142 A US2756142 A US 2756142A
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- US
- United States
- Prior art keywords
- color
- silver halide
- layers
- dye
- coupler
- Prior art date
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- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 27
- 239000000839 emulsion Substances 0.000 claims description 70
- -1 SILVER HALIDE Chemical class 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 229910052709 silver Inorganic materials 0.000 claims description 35
- 239000004332 silver Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002250 absorbent Substances 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000001429 visible spectrum Methods 0.000 claims description 6
- 230000001131 transforming effect Effects 0.000 claims description 2
- 101000740162 Homo sapiens Sodium- and chloride-dependent transporter XTRP3 Proteins 0.000 claims 1
- 102100037189 Sodium- and chloride-dependent transporter XTRP3 Human genes 0.000 claims 1
- 239000000975 dye Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 38
- 108010010803 Gelatin Proteins 0.000 description 15
- 229920000159 gelatin Polymers 0.000 description 15
- 239000008273 gelatin Substances 0.000 description 15
- 235000019322 gelatine Nutrition 0.000 description 15
- 235000011852 gelatine desserts Nutrition 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 230000033458 reproduction Effects 0.000 description 15
- 238000004040 coloring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 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 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 5
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 5
- 229930182490 saponin Natural products 0.000 description 5
- 150000007949 saponins Chemical class 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000001841 imino group Chemical class [H]N=* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 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 description 4
- 238000003756 stirring Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 150000003931 anilides Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- PWORFEDVDWBHSJ-UHFFFAOYSA-N 2-methylbenzotriazole Chemical compound C1=CC=CC2=NN(C)N=C21 PWORFEDVDWBHSJ-UHFFFAOYSA-N 0.000 description 1
- KJGKVKNUHXSXOH-UHFFFAOYSA-N 3-heptyl-1-phenyl-2-sulfanylideneimidazolidin-4-one Chemical compound S=C1N(CCCCCCC)C(=O)CN1C1=CC=CC=C1 KJGKVKNUHXSXOH-UHFFFAOYSA-N 0.000 description 1
- MVWQCFNJWMLYDF-UHFFFAOYSA-N 4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2,6-disulfonic acid Chemical compound O=C1C2=C(N)C=C(S(O)(=O)=O)C(O)=C2C(=O)C2=C1C(O)=C(S(O)(=O)=O)C=C2N MVWQCFNJWMLYDF-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical class [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 238000003527 Peterson olefination reaction Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- YHFXJKYHUWPWSJ-UHFFFAOYSA-L [Na+].[Na+].OS([O-])=O.OS([O-])=O Chemical compound [Na+].[Na+].OS([O-])=O.OS([O-])=O YHFXJKYHUWPWSJ-UHFFFAOYSA-L 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009792 diffusion process Methods 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
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- IPCKADOBKNUJMU-UHFFFAOYSA-N n-[2-(4-aminoanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCNC1=CC=C(N)C=C1 IPCKADOBKNUJMU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
Definitions
- This invention relates to a process in color photography wherein colored reproductions are made by image-wise imbibition transfer of coloring materials from multilayer photographic elements.
- Processes for preparing a positive photographic reproduction of an original have been known for a long time, according to which a silver halide emulsion layer is exposed to the original subject, developed to a negative, and a positive image transferred to a receiving sheet by placing the receiving layer in close contact with the emulsion layer under suitable conditions.
- Several of these procedures depend upon development of a negative image in the silver halide emulsion layer, using up silver halide or developing agents in the areas of the negative image, transferring to the receiving sheet the residual silver halide or developing agent as a positive image, the silver halide being reduced or the developing agent being used to form a visible density by reducing silver halide, heavy metal salts, or by forming a dye.
- a recent process of that type produces a colored positive image by transferring unused color developer and color coupler from the sensitive layer to the receiving sheet where they are later caused to form a dye by treatment with an oxidizing agent.
- a plurality of receiving sheets, each containing a color separation dye image are superimposed or successive registered transfers are made to a receiving sheet from several negative elements. So far as I am aware, none of these processes can be manipulated so as to yield a multicolor image by transfer of color-yielding substances from a single photographic element.
- One object of my invention is to provide a process which utilizes a single light-sensitive photographic element for recording several negative color-separation aspects of a colored subject and directly utilizing certain color-yielding materials in all regions of the element not occupied by the negative records of the subject, for producing a positive multicolor reproduction of the subject.
- Another object is to provide a means by which a plurality of color reproductions can be made from the coloring materials in a single light-sensitive photographic element.
- the objects are accomplished by exposing to a colored subject a photographic element containing at least tWo silver halide emulsions sensitized to different regions of the visible spectrum and each emulsion having intimately associated with it a potentially diifusible coloring material which is nonwandering during coating and development, developing the exposed photographic element with a solution of a silver halide developing agent which renders said coloring material non-difiusible only in the regions of exposure and development of the emulsions, rendering the coloring material only in the unexposed regions of the emulsions difiusible and placing the emulsions in intimate contact with an absorbent surface to simultaneously cause the 2,756,142 Patented July 24,,
- difiusible coloring material in the emulsions to diffuse imagewise into the absorbent surface.
- the blue-, greenand red-sensitive layers normally contain, respectively, yellow, magenta and cyan dyes or color formers. These dyes or color formers must be such as to be non-Wandering during the coating opera tions and usually during at least the early stages of negative development.
- dyes or color formers are selected such that they will not diffuse from layer to layer during coating or negative development, with the additional characteristic that by an appropriate step in the processing they can be made to diffuse easily so that after a negative development the release mechanism can be called into operation so that unaltered dye or color former can thereupon diffuse readily to a receiving sheet which has been placed in contact with the emulsion layers. It is also necessary that the dyes or color formers be rendered non-diffusible or non-Wandering as a function of the negative development, as by coupling according to one mechanism or another, to form a larger molecule.
- the coupler formers rendered incapable of forming a dye as a function of the formation of negative silver images in the emulsion layers. It will be noted that it is important that the particular dye or color former be so associated with the appropriately sensitized silver halide system that the dye or color former can be made insoluble or non-diffusing at the site of negative development of the silver halide, being released to wander by the secondary mechanism only after it has been immobilized at the negative silver image. If dyes or couplers are used which difi'use at too early a stage, i. e., during coating or development, then the association between the appropriate dye and silver halide is lost and color separation will not be obtained.
- the dyes or color formers may be rendered non-wandering during coating by many tech-. niques which would include mordanting, precipitation with metallic ions, and the like. Similarly, dyes or color.
- any oxidized developer capable of combining with the dye or color former may be used regardless of the color of the reaction product in the negative image, since the color to be formed in the transferred image by diffusion of the dye or color former can be obtained by other means. Therefore, the choiceof developing agent will depend upon other factors not necessarily important in choosing developing agents for conventional color processes and restrictions imposed in,
- developing agents can be not only p-phenylenediarnine" or its derivatives but any other developing agent having oxidation products reactive with the dye or color former in question.
- conventional tanning developers such as derivatives of hydroquinone, catechol or pyrogallol may react with dye or coupler formers containing amino groups to cause image differentiation as a re sult of the coupling action.
- colorless coupler-type color formers are used in the respective layers, then they should be of such type that they are non-diffusing during coating and development but released by a definite mechanism to allow transfer later to a receiving sheet where they could be coupled withan oxidized p-phenylenediamine or possibly with a diazonium salt to give an appropriately colored image.
- the receiving sheet in this case should contain, possibly a mordant, but also either an oxidizing agent provide the oxidized form of the p-phenylenediamine developer if that is used during negative development, or at least a suitable agent for converting the color former after diifusion to a suitable dye image.
- coupler systems which can be employed in the sensitive elements employed in my invention are to be found in the Peterson U. S. Patents 2,353,754, July 18, 1944, and 2,296,306, September 22, 1942, and particularly in the Weissberger et al. U. S. Patent 2,412,700, December 17, 1946.
- These couplers are capable of forming a dye with the oxidation products of a primary aromatic amino silver halide developing agent.
- the couplers of the two former patents have attached to their molecules a heavy metal salt, for ex ample, a silver salt, of a heterocyclic compound having an inzn'no or mercapto group. Examples of these couplers are:
- Couplers of the latter patent have attached to their reactive coupler molecules, heavy metal-containing thioglycolyl groups such as the couplers of the following examples and 1-phenyl-3-( thioglycolylamino) -5-pyrazolone w-benzoylacetamino-p-thioglycolic anilide 2-hydroxy-4-methyl-S-chlorothioglycolic anilide 5- (thioacetylamino) -1-naphthol Accordingly, the above potentially difiusible couplers have attached to their molecules the heavy metal-substituted mercapto or imino groups. These couplers form conventional negative color images in the original photosensitive layer, can be released to wander by treatment with hypo, io
- a developing agent may be incorporated into one or more layers of the sensitive. negative element containing such coupler compounds.
- the emulsion layers of the multilayer sensitive elements can contain different developing agents which allow for greater latitude in choice of dyes and color formers in the respective layers.
- my invention can be carried out with sensitive elements containing superposed emulsions containing potentially ditfusible coloring materials or by means of one or more sensitive layers of the mixed grain or mixed packet type such as disclosed in the Godowsl y U. S. patent application Serial No. 156,066, filed April 15, 1950, now U. S. Patent,2,698,794, granted January 4, 1955, or in Godowsky U.'S. Patent 2,548,526, granted April 10, 1951.
- the sensitive elements have the potentially diffusible coloring materials in intimate association with the silver halide particles and after exposure and development to insolubilize the coloring materials, the coloring materials remaining in the unexposed regions are liberated and transferred simultaneously image-wise to a receiving sheet.
- a single transfer of the coloring materials to a receiving sheet does not deplete the negative element, further transfers to separate receiving sheets can be made in the same manner.
- EXAMPLE 1 This example illustrates the use of the mentioned coupler compounds containing metallic salts of heterocyclic compounds having mercapto groups, in a 3-layer photographic element sensitized in the natural order.
- Red-sensitive emulsion A fine-grain silver chloride dispersion was prepared by adding simultaneously and at a moderate rate a mixed solution of 70.0 cc. of a 1 N KCl solution and 25.0 cc. of a .2 N KBr solution diluted to a total volume of 125 cc. and cc. of a 1 N AgNOs, also diluted to a total volume of cc. to a well agitated solution of 250.0 g. of a 10% de-ashed gelatin solution and 500 cc. of water.
- The. total weight of the silver chloride dispersion was 1000 g.
- a fast bromo-iodide gelatin emulsion sensitized to red light with 5-[(ethyl-2(3)-wnaphthoxazolylidene)-ethylidene]-3-n-heptyl-1-phenyl-2-thiohydantoin is then provided and 112 grams of it combined with 194 grams of the coupler dispersion prepared as above, together with suitable quantities of mucochloric acid hardening agent, antifoggant and saponin spreading agent.
- the couplercontaining emulsion is then coated on a film support at a rate of 11.3 cc. per square foot.
- sion layer is then coated with 10 cc. per square foot of the following gelatin solution:
- Green-sensitive emulsion A mixture of 5.5 g. of p-acetylthioglycolylamino-wcyanoacetophenone, 40.0 cc. of ethyl alcohol, and 8.0 cc. of a 20% aqueous NaOH solution was heated to -140 F. and maintained at that temperature for 10 minutes. The solution was intermittently hand-stirred during this period. To the clear solution was added 35 .0 cc. of water and the whole then added slowly with very good stirring to 400.0 g. of AgCl dispersion described above. Total weight 480.0 g.
- Blue-sensitive emulsion A mixture of 2.2 g. of w-benzoyl-4-(p-acetylmercaptoethanesulfonamido)acetanilide, 16.0 cc. of ethyl alcohol, and 1.54 cc. of a 20% aqueous sodium hydroxide solution was heated with intermittent hand stirring to 125-130 F and maintained at that temperature for 10 minutes. After the addition of 5.0 cc. of distilled water, the clear solution was poured slowly into 100.0 g. of a Well-stirred silver chloride dispersion prepared in the manner described above. The total weight of the dispersion was 140.0 g.
- a blue-sensitive silver halide emulsion 140 grams of the silver salt of the yellow coupler thus obtained are combined with 91 grams of a blue-sensitive silver halide emulsion together with suitable quantities of antifoggant, saponin spreading agent and mucochloric acid hardening agent.
- the resulting emulsion is then coated over the yellow filter layer of the above film to provide the element shown in Fig. 1 of the accompanying drawings.
- the support 10 is shown as carrying the red, green and blue-sensitive emulsion layers 11, 13 and 15, separated by the gelatin layer 12 and the yellow filter layer 14, the emulsions containing the potentially diifusible couplers for forming substractively colored dye images of color complementary to the sensitivity of the respective emulsion layers containing the couplers.
- stage A shows the blue, green and red-sensitive emulsion layers being exposed in regions 16, 17 and 18 respectively by light of those colors reflected from or transmitted by a colored subject.
- the exposed photographic element of this example and shown in stage A can be processed as follows to yield a positive color reproduction:
- the film is developed for minutes in the following color developer composition:
- the result of fixation in addition to removing unused silver halide from the film, is to remove silver from the unused couplers in the unexposed regions of the film and to render them diffusible in the presence of alkali.
- the film may then be washed for about 1 minute and appears substantially as shown in stage B of the drawings wherein areas 19, 20 and 21 contain the non-diflusible yellow, magenta and cyan dye images obtained by color development of the exposed regions of the fihn and in the remaining areas of the layers 11, 13 and are present the water-insoluble couplers which are difiusible in the presence of alkali.
- the washed film, while still moist, is then placed with its emulsion surface in intimate contact with an absorbent surface, for example, an alkaline receiving sheet 22 having an absorbent surface or layer 23, such as a barytacoated paper which has been soaked in a 10 percent solution of trisodium phosphate.
- an absorbent surface for example, an alkaline receiving sheet 22 having an absorbent surface or layer 23, such as a barytacoated paper which has been soaked in a 10 percent solution of trisodium phosphate.
- an absorbent surface for example, an alkaline receiving sheet 22 having an absorbent surface or layer 23, such as a barytacoated paper which has been soaked in a 10 percent solution of trisodium phosphate.
- an absorbent surface for example, an alkaline receiving sheet 22 having an absorbent surface or layer 23, such as a barytacoated paper which has been soaked in a 10 percent solution of trisodium phosphate.
- the receiving sheet 22 is then treated with a solution of a primary aromatic amino silver halide developing agent, such as the formula above, for 1 minute, and then with a solution of an oxidizing agent for the color developing agent.
- a 2 percent solution of potassium ferricyanide is satisfactory.
- the oxidation products of the color developing agent then couple immediately with the couplers which have transferred to sheet 22 to form dye images substantially as shown in stage D.
- one or more other reproductions can be made from the element of stage C by repeating the transfer step using a fresh receiving sheet followed by treatment of the transferred coupler images as described.
- the initial de-' velopment of the exposed element of stage A is not especially critical in the respect that either color developing agents or well-known colloid tanning silver halide developing agents can be used to immobilize the coupler compounds in the exposed regions.
- the light-sensitive emulsions prepared as above can contain other metal salt couplers as disclosed in the Peterson and Weissberger et al. inventions.
- the process outlined above employs a film containing only one or two superposed emulsion layers, the final reproduction is in either a single color or essentially 2-color.
- Other Wellknown color developing agents such as disclosed in the above Weissberger U. S. Patent 2,193,015 and others well known in the art are suitable for use in the initial development step or for use in the treatment of the transferred coupler images on the receiving sheet.
- Example 2 This example illustrates the use of water-insoluble salts of acid dyes as the potentially difiusible coloring materials for the light-sensitive element.
- a green-sensitive gelatino silver halide emulsion is then prepared in a similar manner using the barium salt of the magneta dye -aminod-hydroxy2-p-sulfophenylazonaphthalene-3-sulfonic acid. This emulsion is then coated over the gelatin layer of the element immediately above. If desired to produce a 3-color system, a yellow gelatin filter layer such as that above and a blue-sensitive emulsion layer containnig a potentially diffusible metal salt of a suitable yellow dye can be coatedover the green-sensitive emulsion layer. After exposure to the colored subject, development is carried out for 3 minutes in a gelatin-tanning silver halide developing solution of the composition:
- Solution B Grams Sodium carbonate monohydrate 216 Quadrafos 10 Water to make 1000 cc.
- Glycerin 100 Acetic acid (glacial) 4 Ammonium hydroxide (conc.) 13 Formaldehyde (40%) Water 800
- a baryta-coated receiving sheet is provided containing an acid dye mordant such as a polymerized quaternized vinyl-substituted azine dye-mordant, for example, quatcrnized polyvinyl pyridine as described in Sprague et al. U. S. Patent 2,484,430.
- the receiving sheet which has previously been soaked for at least minutes in the above acidic Working solution .is then squeegeed against the moist emulsion layers with the result that the solubilizcd dyes in the emulsion layer transfer image-wise to the receiving sheet and are mordanted therein.
- the green-sensitive emulsion layer may contain phenosafranine as the potentially ditfusible magneta coloring material.
- Development of the exposed emulsion layers with the above doveloper is believed to yield in this layer a product which facilitates insolubilization of the dye in the exposed region.
- an efficaciousadditional mordant for the receiving sheet is silver halide.
- the image-wise tanning of the gelatin appears to be an incidental feature of the developer.
- a more important feature appears to reside in the reaction of the oxidized developing agent with free amino groups of the dyes to form non-diffusible compounds.
- the efiective potentially diffusible dyes contain free amino groups, dyes free of amino groups or containing only alkylamino groups are not useful in the process.
- representative dyes useful in the process are anthraquinone, azo and safranine dyes containing primary amino groups.
- the process of this example can be used for making monochrome or 2-color transfers by utilizing any one or two of the above emulsion layers for the negative element, insolubilizing the dye salt locally and transferring the residual dye as described.
- a photographic color reproduction process which comprises exposing to a colored subject a photographic element having at least two superposed silver halide emulsion layers sensitized to different regions of the visible spectrum and each containing a coupler compound capable of forming a dye with the development products of a primary aromatic amino silver halide developing agent and having attached to the coupler molecule a group of the class consisting of heavy metal-substituted imino and mercapto groups, developing the exposed emulsion layers with a solution of said developing agent to form non-diffusible dye images only in the exposed regions of the emulsion layers, transforming the coupler compounds in the unexposed regions of the emulsion layers to ditfusible couplers, placing the emulsion layers in intimate contact with an absorbent surface to simultaneously cause the dilfusible coupler compounds in the emulsion layers to diffuse image-wise into the absorbent surface, and reacting the diffused couplers in the absorbent surface with the oxidation products of a primary aromatic amino silver
- a photographic color reproduction process which comprises exposing to a colored subject a photographic element having at least two superposed silver halide emulsion layers sensitized to different regions of the visible spectrum and each containing a coupler compound capable of forming a dye with the development products of a primary aromatic amino silver halide developing agent and having attached to the coupler molecule a group of the class consisting of silver-substituted imino and mercapto groups, developing the exposed emulsion layers with a solution of said developing agent to form nonditfusiblc dye images only in the exposed regions of the emulsion layers, treating the developed emulsion layers with an acid fixing solution to form ditfusible coupler compounds in the unexposed regions of the emulsion layers, placing the emulsion layers in intimate contact with.
- an alkaline absorbent surface to simultaneously cause the diffusible coupler compounds in the emulsion layers to diffuse image-Wise into the alkaline absorbent surface, and reacting the diffused couplers in the alkaline absorbent surface with the oxidation products of a primary aromatic amino silver halide developing agent to form dye images.
- a photographic color reproduction process which comprises exposing to a colored subject a photographic element having at least two superposed silver halide emulsion layers sensitized to different regions of the visible spectrum and each containing a coupler compound capable of forming a dye with the development products of a primary aromatic amino silver halide developing agent and having attached to the coupler molecule a group of the class consisting of heavy metal-substituted imino and mercapto groups, developing the exposed emulsion layers with a solution of said developing agent to form non-diffusible dye images only in the exposed regions of the emulsion layers, placing the emulsion layers in intimate contact with an absorbent surface containing an alkaline fixing solution to render the coupler compounds diffusible in the unexposed regions of the emulsion layers and to cause them to diffuse image-wise into the absorbent surface, and reacting the diffused couplers in the absorbent surface with the oxidation products of a primary aromatic amino silver halide developing agent to form dye images.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Color Printing (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE525871D BE525871A (xx) | 1953-01-22 | ||
US332728A US2756142A (en) | 1953-01-22 | 1953-01-22 | Photographic color reproduction process |
DEE8407A DE964203C (de) | 1953-01-22 | 1954-01-13 | Photographisches Kontaktverfahren zur Erzeugung mehrfarbiger Bilder |
FR1103424D FR1103424A (fr) | 1953-01-22 | 1954-01-19 | Procédé d'obtention d'images photographiques en couleurs et images obtenues par ce procédé |
GB1786/54A GB746686A (en) | 1953-01-22 | 1954-01-21 | Photographic colour reproduction process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US332728A US2756142A (en) | 1953-01-22 | 1953-01-22 | Photographic color reproduction process |
Publications (1)
Publication Number | Publication Date |
---|---|
US2756142A true US2756142A (en) | 1956-07-24 |
Family
ID=23299608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US332728A Expired - Lifetime US2756142A (en) | 1953-01-22 | 1953-01-22 | Photographic color reproduction process |
Country Status (5)
Country | Link |
---|---|
US (1) | US2756142A (xx) |
BE (1) | BE525871A (xx) |
DE (1) | DE964203C (xx) |
FR (1) | FR1103424A (xx) |
GB (1) | GB746686A (xx) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2940849A (en) * | 1957-07-10 | 1960-06-14 | Eastman Kodak Co | Planographic dye transfer process |
US2968554A (en) * | 1954-08-09 | 1961-01-17 | Polaroid Corp | Photographic transfer processes for forming multicolor dye images and photographic products for carrying out the same |
US2983606A (en) * | 1958-07-14 | 1961-05-09 | Polaroid Corp | Processes and products for forming photographic images in color |
US3001873A (en) * | 1956-03-22 | 1961-09-26 | Ncr Co | Photo-printing process and material |
US3019124A (en) * | 1956-04-12 | 1962-01-30 | Polaroid Corp | Multicolor photosensitive film and process of making the same |
US3039869A (en) * | 1957-04-24 | 1962-06-19 | Polaroid Corp | Photographic color processes and compositions |
US3065074A (en) * | 1958-08-20 | 1962-11-20 | Polaroid Corp | 1,4-benzoquinone oxidizing agents for color transfer processes |
US3077400A (en) * | 1962-04-26 | 1963-02-12 | Polaroid Corp | Color diffusion transfer using gelatinsilver halide emulsions containing cellulose ethers |
US3087817A (en) * | 1956-10-03 | 1963-04-30 | Polaroid Corp | Process and product for forming color images from complete dyes |
US3185567A (en) * | 1959-07-06 | 1965-05-25 | Polaroid Corp | Photographic color process and product |
US3188209A (en) * | 1959-12-01 | 1965-06-08 | Polaroid Corp | Diffusion transfer color processes |
US3227551A (en) * | 1959-04-06 | 1966-01-04 | Eastman Kodak Co | Photographic color reproduction process and element |
US3227552A (en) * | 1960-05-13 | 1966-01-04 | Eastman Kodak Co | Preparation of photographic direct positive color images |
US3230084A (en) * | 1959-05-18 | 1966-01-18 | Polaroid Corp | Novel photographic products and processes |
US3230083A (en) * | 1959-04-02 | 1966-01-18 | Polaroid Corp | Photographic processes and products |
US3230082A (en) * | 1962-05-14 | 1966-01-18 | Polaroid Corp | Color processes and products |
US3245791A (en) * | 1964-09-21 | 1966-04-12 | Polaroid Corp | Photographic transfer process and composition |
US3295973A (en) * | 1965-11-03 | 1967-01-03 | Polaroid Corp | Novel photographic products and processes |
US3301772A (en) * | 1961-02-27 | 1967-01-31 | Gen Aniline & Film Corp | Electrolytic color development |
US3320062A (en) * | 1963-07-30 | 1967-05-16 | Polaroid Corp | Photographic processes comprising stepwise control of dye developer diffusibility in alkali |
US3345163A (en) * | 1956-02-13 | 1967-10-03 | Polaroid Corp | Photographic diffusion transfer color processes |
US5051343A (en) * | 1989-06-16 | 1991-09-24 | Eastman Kodak Company | Photographic elements containing removable couplers |
US5118594A (en) * | 1989-06-16 | 1992-06-02 | Eastman Kodak Company | Photographic elements containing removable couplers |
US6054257A (en) * | 1998-01-29 | 2000-04-25 | Eastman Kodak Company | Photographic element containing particular coupler and inhibitor releasing coupler |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1191034A (en) * | 1914-08-31 | 1916-07-11 | Julius Rheinberg | Color photography and color-printing. |
US2456955A (en) * | 1944-06-02 | 1948-12-21 | Eastman Kodak Co | Photographic processes and lightsensitive elements therefor |
US2464798A (en) * | 1944-05-03 | 1949-03-22 | Gen Aniline & Film Corp | Color correction of multicolor negative film by integral masking images |
US2559643A (en) * | 1948-02-19 | 1951-07-10 | Polaroid Corp | Photographic product and process |
US2647049A (en) * | 1947-02-25 | 1953-07-28 | Polaroid Corp | Photographic element for color photography and a process of producing multicolor pictures |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL60753C (xx) * | 1942-12-05 |
-
0
- BE BE525871D patent/BE525871A/xx unknown
-
1953
- 1953-01-22 US US332728A patent/US2756142A/en not_active Expired - Lifetime
-
1954
- 1954-01-13 DE DEE8407A patent/DE964203C/de not_active Expired
- 1954-01-19 FR FR1103424D patent/FR1103424A/fr not_active Expired
- 1954-01-21 GB GB1786/54A patent/GB746686A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1191034A (en) * | 1914-08-31 | 1916-07-11 | Julius Rheinberg | Color photography and color-printing. |
US2464798A (en) * | 1944-05-03 | 1949-03-22 | Gen Aniline & Film Corp | Color correction of multicolor negative film by integral masking images |
US2456955A (en) * | 1944-06-02 | 1948-12-21 | Eastman Kodak Co | Photographic processes and lightsensitive elements therefor |
US2647049A (en) * | 1947-02-25 | 1953-07-28 | Polaroid Corp | Photographic element for color photography and a process of producing multicolor pictures |
US2559643A (en) * | 1948-02-19 | 1951-07-10 | Polaroid Corp | Photographic product and process |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2968554A (en) * | 1954-08-09 | 1961-01-17 | Polaroid Corp | Photographic transfer processes for forming multicolor dye images and photographic products for carrying out the same |
US3345163A (en) * | 1956-02-13 | 1967-10-03 | Polaroid Corp | Photographic diffusion transfer color processes |
US3001873A (en) * | 1956-03-22 | 1961-09-26 | Ncr Co | Photo-printing process and material |
US3019124A (en) * | 1956-04-12 | 1962-01-30 | Polaroid Corp | Multicolor photosensitive film and process of making the same |
US3087817A (en) * | 1956-10-03 | 1963-04-30 | Polaroid Corp | Process and product for forming color images from complete dyes |
US3039869A (en) * | 1957-04-24 | 1962-06-19 | Polaroid Corp | Photographic color processes and compositions |
US2940849A (en) * | 1957-07-10 | 1960-06-14 | Eastman Kodak Co | Planographic dye transfer process |
US2983606A (en) * | 1958-07-14 | 1961-05-09 | Polaroid Corp | Processes and products for forming photographic images in color |
US3065074A (en) * | 1958-08-20 | 1962-11-20 | Polaroid Corp | 1,4-benzoquinone oxidizing agents for color transfer processes |
US3230083A (en) * | 1959-04-02 | 1966-01-18 | Polaroid Corp | Photographic processes and products |
US3227551A (en) * | 1959-04-06 | 1966-01-04 | Eastman Kodak Co | Photographic color reproduction process and element |
US3230084A (en) * | 1959-05-18 | 1966-01-18 | Polaroid Corp | Novel photographic products and processes |
US3185567A (en) * | 1959-07-06 | 1965-05-25 | Polaroid Corp | Photographic color process and product |
US3188209A (en) * | 1959-12-01 | 1965-06-08 | Polaroid Corp | Diffusion transfer color processes |
US3227552A (en) * | 1960-05-13 | 1966-01-04 | Eastman Kodak Co | Preparation of photographic direct positive color images |
US3301772A (en) * | 1961-02-27 | 1967-01-31 | Gen Aniline & Film Corp | Electrolytic color development |
US3077400A (en) * | 1962-04-26 | 1963-02-12 | Polaroid Corp | Color diffusion transfer using gelatinsilver halide emulsions containing cellulose ethers |
US3230082A (en) * | 1962-05-14 | 1966-01-18 | Polaroid Corp | Color processes and products |
US3320062A (en) * | 1963-07-30 | 1967-05-16 | Polaroid Corp | Photographic processes comprising stepwise control of dye developer diffusibility in alkali |
US3245791A (en) * | 1964-09-21 | 1966-04-12 | Polaroid Corp | Photographic transfer process and composition |
US3295973A (en) * | 1965-11-03 | 1967-01-03 | Polaroid Corp | Novel photographic products and processes |
US5051343A (en) * | 1989-06-16 | 1991-09-24 | Eastman Kodak Company | Photographic elements containing removable couplers |
US5118594A (en) * | 1989-06-16 | 1992-06-02 | Eastman Kodak Company | Photographic elements containing removable couplers |
US6054257A (en) * | 1998-01-29 | 2000-04-25 | Eastman Kodak Company | Photographic element containing particular coupler and inhibitor releasing coupler |
Also Published As
Publication number | Publication date |
---|---|
DE964203C (de) | 1957-05-16 |
GB746686A (en) | 1956-03-21 |
FR1103424A (fr) | 1955-11-03 |
BE525871A (xx) |
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