US2609292A - Light-sensitive photographic element and process using it - Google Patents
Light-sensitive photographic element and process using it Download PDFInfo
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- US2609292A US2609292A US682300A US68230046A US2609292A US 2609292 A US2609292 A US 2609292A US 682300 A US682300 A US 682300A US 68230046 A US68230046 A US 68230046A US 2609292 A US2609292 A US 2609292A
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- silver
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- photographic
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- 238000000034 method Methods 0.000 title description 13
- 229910052709 silver Inorganic materials 0.000 claims description 92
- 239000004332 silver Substances 0.000 claims description 92
- -1 SILVER HALIDE Chemical class 0.000 claims description 52
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 43
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical compound [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 claims description 41
- 239000000084 colloidal system Substances 0.000 claims description 36
- 239000000839 emulsion Substances 0.000 claims description 35
- 229940100890 silver compound Drugs 0.000 claims description 14
- 150000003379 silver compounds Chemical class 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- ORWQBKPSGDRPPA-UHFFFAOYSA-N 3-[2-[ethyl(methyl)amino]ethyl]-1h-indol-4-ol Chemical compound C1=CC(O)=C2C(CCN(C)CC)=CNC2=C1 ORWQBKPSGDRPPA-UHFFFAOYSA-N 0.000 claims 1
- 229920000159 gelatin Polymers 0.000 description 17
- 235000019322 gelatine Nutrition 0.000 description 17
- 108010010803 Gelatin Proteins 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 150000003378 silver Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012505 colouration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000004060 quinone imines Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CZLPCLANGIXFIE-UHFFFAOYSA-N 1-amino-3-prop-2-enylthiourea Chemical compound NNC(=S)NCC=C CZLPCLANGIXFIE-UHFFFAOYSA-N 0.000 description 1
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 1
- CJLSDBRIXZFCKV-UHFFFAOYSA-N 4-chloro-3-oxo-n-phenylbutanamide Chemical compound ClCC(=O)CC(=O)NC1=CC=CC=C1 CJLSDBRIXZFCKV-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 241000784714 Cupido osiris Species 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MCIURFJELJKSNV-UHFFFAOYSA-N benzene-1,4-diamine;hydron;chloride Chemical compound Cl.NC1=CC=C(N)C=C1 MCIURFJELJKSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000001013 indophenol dye Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- 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 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/8255—Silver or silver compounds therefor
Definitions
- the colloid layer becomes coloured to a yellow to' red or brown hue.
- the substantially colourless colloid layer containing silver sulphide nuclei also contains a silver compound as a source of silver ions, or is coated adjacent to a second colloid layer which contains a silver compound as a source of silver ions, and the treatment with the reducing agent is effected in the presence of a solvent for the silver compound, e. g. sodium thiosulphate or thiocyanate.
- a solvent for the silver compound e. g. sodium thiosulphate or thiocyanate.
- a useful way of forming the coloured colloid layer is to coat in super-position on a support a colloid layer containing silver sulphide nuclei and a colloid layer containing silver halide, and to treat the combination with a reducing agent, e. g. a photographic developer, containing a silver halide solvent.
- a reducing agent e. g. a photographic developer, containing a silver halide solvent.
- a proportion of silver halide may be included in the colloid layer containing the silver sulphide nuclei and the layer treated with a photographic developer containing a Vsilver halide solvent.
- Colloid layers containing silver sulphide nuclei may be prepared by various methods.
- the mere addition of silver nitrate followed by a short heating, e. g. at 120 F., may be suflicient to cause formation of suilicient silver sulphide nuclei by reaction between the silver nitrate and the sulphur compounds naturally present in gelatin.
- a small quantity of a silver halide preferably in the form of a photographic emulsion, may be employed.
- Suitable sulphur compounds which may be thus employed are thiourea, allyl thiourea, thiosulphates, thiosemicarbazide and allyl thiosemicarbazide.
- the formation of the silver sulphide nuclei is best eiected by heating the gelatin containing the silver compound and the sulphur compound for a short period. Temperatures of the order of F. are Vsuitable and the duration of the heating may be from 5 to 60 minutes or more, though the shorterfperiods of treating are usually adequate. It is perferable that the pH of the solution should be above about 5.8.
- Colloid layers thus prepared are substantially colourless .since the silver sulphide nuclei impart no appreciable colour or opacity to the colloid ⁇
- the coloured colloid layers .of this invention are of particular value as lter-A layers inmultilayer photographic elements for usev in .colour photography, and according to a further feature of this invention, therefore, a photographic element comprising a plurality of photographic emulsion layers carried on a support also includes a layer or layers of a substantially colourless colloid containing silver sulphide nuclei, such layer or layers containing a silver compound as a source of silver ions or being coated adjacent to a silver halide emulsion layer.
- a photographic element which comprises the following layers:
- Such a photographic element exposed to record v a coloured object, the rays 'beingjncident on layer emulsion layers.
- the layers b and d may be transposed and their processing correspondingly varied.
- the layers c :and-fe may be adapted "to yield ⁇ rector".red-brown images and the ⁇ colour of the exposing "light used Y for re-exposing the layers correspondingly adjusted to a wavelength, or band of wavelengths,
- the intensity of the developed colour depends ⁇ onthe particularfconditions prevailing, i. e. on
- the nature-of the layers cand ve and on the development conditions A- veryv intense colouration is'usually obtained by including a/source of silver ions in the layers c and 'e themselvesfor example by including' a smallproportion of silver halide.
- the added silver halide can usefully be a line grain emulsionsincethisis not only of high transparency but, presumably by termeson of vthe liinenerss of grain of the silver halide, is very reactiveas a'source of silver ions.
- the nature and quantity of the silver halide added' should not be suclnho'wever, that any substantial 'light-sensitivity-'is imparted to layers c ande since these should not give any Vappreciable black silver image on development.
- the ⁇ emulsion layers of the photographic ele- 'ment :obtained by the procedure outlined above can be :further selectively processed to colour by making use of the coloured layers c and e Yas light-barrier layers.
- the element may be exposed to blue light through the support and then developed in a solution containing :an aromatic Yprimary .amino developing agent and a colourl-former .which combines With the oxidation .products of such developing agent, formed during development, to form a bluegreen azomethineor quinone-imine dyeimage in situ with the developed positive record in layer b.
- the .element ⁇ may then beexposed to blue 'lightincident on layer f and that layer similarly processed ⁇ to 'form a positive yellow image in layer j. Neither of these treatments affect layer d since the blue exposing light is absorbed by the yellow layers c and e.
- Layer d may then be rendered developable either by exposure to very bright light, Yadequate to penetrate 'layer c or e or by X-rays or by chemical treatment, e. g. With a 5% aqueous solution of sodium arsenite or hydrogen peroxide or with guanidine thiocyanate. This layer .may .be similarly developed to form in it a positive magenta image.
- V16k-photographic multi-layer element was prepared consisting of the ⁇ following layers in superposition inthe order stated. l
- the element was then exposed toviolet light passing through the support a and then developed in a developer of the following composition:
- the process described above and'exemplied in the foregoing example may be modiiied'in various ways.
- the-'exposedV positive silver halide records may be processed to colour by methods other than colour-development, e. g. by dye toning or chemical toning. f
- one or more'ofthe emulsion layers may contain colour-immers;- the following isan example of such a process: 4
- Example A photographic multi-layer element wasf'prepared consisting of the following layers in superposition in the order stated as illustrated in the accompanying drawing:
- a photographic element which comprises a support Vcarrying at least three superimposed layers, the outer ones of which are colloid silver halide photographic emulsion layers and the middle one of which is a layer of substantially colourless colloid containing silver sluphide nuclei, of such particle size and quantity that they impart no colour to the layer, the said colourless colloid' containing a quantity of silver compound insuiliciently sensitive to light Vto produce any appreciable image in the-saidcolourless colloid layer on photographic development, but suiiicient in quantity to producegwith'thei aid 'of said silver sulphide nuclei, alayer of silversubstantially opaque to blue light on photographic development.
- a photographic element which comprises v(a) a transparent Vsubstantially colourless sup-- port and in superimposition thereon, in order, (b) asilver halide emulsion layer sensitive to red light, (c) a layer ofA a colourless colloid containing silver sulphide nuclei of suchparticle size and quantity that they 'impart no colourl to the layer, and a quantity 'of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but suiiicient in quantity to produce, with the aid of said silver sulphide nuclei,'a4 layer of silver ⁇ substantially opaque to blue light on photographic'develop* ment (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart nocolou'rrto the layer, and a quantity of a silver compound
- a photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon, in order, (b) a silver halide emulsion layer sensitive'to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart ⁇ no colour ⁇ to the layer, and a quantity of silver rhalide insuf'- flciently sensitive to light tofyield any ⁇ appreciable l, image on photographic development but suflicient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of.
- a silver halide emulsionlayer sensitive to green light (d) a silver halide emulsionlayer sensitive to green light, (e) a layer of colourless Acolloid containing silversulphide nuclei of such'lpfflrticle size and quantity that they impart no colour to the layer, and a quantity of silver halide insufently sensitive to light to Vyield any appreciable image on photographic development but Asuicient in quantity to produce, with theaid of said silver sulphide nuclei, a layer of 'silvensubsta'ntially opaque to blue lighten photographic development, and a removable yellow colouring'material, and (f) a silver halide emulsion' sensitive only to blue light.
- a photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon,.in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layenand a quantity of an emulsion of silver halide insufficiently sensitive to light to yield any appreciable image on photographic development but sufcient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, (d) a silver halide emullof'sanv emulsion, of.
- silver ⁇ halide insuiiiciently sensitive to light to ,yield any1;altlpreciable ⁇ image en .photographic development but suicient in .quantity to,.produce, withthe.aid of said's'ilver sulphide :nuclei, a layer of lsilver substantially opaque. toblue light on photographic ⁇ development, and-fa removable yellow colouring material, and (f) afsilver halide emulsionsensitiveponly to blue light.
- a photographic element which comprises (a) Aa'transparent substantially colourless support and' in superimposition thereon, in order, 1(1))A a silverhalide emulsion layersensitive to red light, ⁇ (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer, and a quantity of an emulsion of silver halide insuiiiciently sensitive to light to yield any appreciable image on photographic development but sulcient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer, and a quantity of an emulsion of silver halide insuiciently sensitive to light to yield any appreciable image on photographic development but sufficient in
- a process of colour photography which includes the step of treating an exposed photographic element which comprises (a) a transparent substantially colourless support and in super-imposition thereon, in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to lblue light on photographic development, (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any
- a process of colour photography which comprises treating an exposed photographic element which comprises (a) .a transparent substantially colourless support and in superimposition thereon, in order, (b) a silver halide emul- 10 sion layer sensitive j to redl light;V (c) a layer y.of a colourless :colloid .zcontaining silver.- sulphide nuclei of such particlesize and quantity :that they impartv no.
- a process of colour photography which comprises treating an exposed photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon. in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid layer containing silver sulphide nuclei of such particle size and quantity that they impart no colourv to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufciently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development.
- a silver halide emulsion layer sensitive to green light (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and a removable yellow colouring material, and (f) a silver halide emulsion sensitive only to blue light by the following operations; develop in a non-colour-forming developer, bleach out the developed records in layers bl, d and f, develop in adeveloper containing a silver halide solvent.
Description
Sept. 2, 1952 c. WALLER ET AL 2,609,292
LIGHT-'SENSITIVE PHOTOGRAPHIC ELEMENT AND PROCESS USING IT Filed July 9, 194e i E\\\\\\IIIIIIIIIIIIIIIIIIIIIIIIII Bl. UE GREEN RED STAGE .Z
:a FMF/vr Arme @rPaw/ef olv f To camera aJf-cr, mvo .sz Ac/r -WH/ rf off/a aP/wf/vr HPPERH/VCEOFFLFMFNT BY nunununumm BLUE @eff/v .een 'ec fuller and,
.Harold wezz ic'iIlSolz @Y m@ www Patented Sept. 2, 1952 LIGHT-SENSITIVE PHOTOGRAPHIC ELE- MENT AND PROCESS USING IT Cecil Wallerand Harold Owen Dickinson, Ilford, England, assignors to Ilford Limited, Ilford, England, a British company Application July 9, 1946, Serial No. 682,300 In Great Britain July 10, 1945 This invention relates to the production of coloured colloid layers and more particularly to the production of multilayer materials for colour photography and to the processing of such may terials.
the colloid layer becomes coloured to a yellow to' red or brown hue.
More particularly according to the invention the substantially colourless colloid layer containing silver sulphide nuclei also contains a silver compound as a source of silver ions, or is coated adjacent to a second colloid layer which contains a silver compound as a source of silver ions, and the treatment with the reducing agent is effected in the presence of a solvent for the silver compound, e. g. sodium thiosulphate or thiocyanate.
' A useful way of forming the coloured colloid layer is to coat in super-position on a support a colloid layer containing silver sulphide nuclei and a colloid layer containing silver halide, and to treat the combination with a reducing agent, e. g. a photographic developer, containing a silver halide solvent.
Alternatively a proportion of silver halide may be included in the colloid layer containing the silver sulphide nuclei and the layer treated with a photographic developer containing a Vsilver halide solvent.
Colloid layers containing silver sulphide nuclei may be prepared by various methods. When the colloid is gelatin the mere addition of silver nitrate followed by a short heating, e. g. at 120 F., may be suflicient to cause formation of suilicient silver sulphide nuclei by reaction between the silver nitrate and the sulphur compounds naturally present in gelatin. Alternatively, instead of using silver nitrate or other soluble silver salt, a small quantity of a silver halide, preferably in the form of a photographic emulsion, may be employed. When using gelatin containing little or no sulphur compounds, or when using other colloids free from sulphur compounds, it is necessary to add to the colloid a quantity of a sulphur 87Claims. (Cl. 95-2) compound which will react with the silver nitrate or silver halide to form suflicient silver sulphide. Suitable sulphur compounds which may be thus employed are thiourea, allyl thiourea, thiosulphates, thiosemicarbazide and allyl thiosemicarbazide. Generally speaking, for a gelatin containing little or no sulphur compounds (a so-called inert gelatin) quantities of the order of 5 cc.r of M/lOO silver nitrate and 2.5 cc. of M/ thiourea per 100 cc. of a 5% solution of the gelatin are found to be suitable,
The formation of the silver sulphide nuclei is best eiected by heating the gelatin containing the silver compound and the sulphur compound for a short period. Temperatures of the order of F. are Vsuitable and the duration of the heating may be from 5 to 60 minutes or more, though the shorterfperiods of treating are usually adequate. It is perferable that the pH of the solution should be above about 5.8.
Colloid layers thus prepared are substantially colourless .since the silver sulphide nuclei impart no appreciable colour or opacity to the colloid` As already indicated, the coloured colloid layers .of this invention are of particular value as lter-A layers inmultilayer photographic elements for usev in .colour photography, and according to a further feature of this invention, therefore, a photographic element comprising a plurality of photographic emulsion layers carried on a support also includes a layer or layers of a substantially colourless colloid containing silver sulphide nuclei, such layer or layers containing a silver compound as a source of silver ions or being coated adjacent to a silver halide emulsion layer.
When such a photographic element is developed with a photographie developer containing a silver halide solvent, the said colloid layer containing silver sulphide nuclei is developed to a yellow-to red or brown hue.
In particular, according to this invention, there is provided a photographic element which comprises the following layers:
(a) A transparent, substantially colourless support.
(b) A silver'halide emulsion layer sensitive to red light.
(c) A layerl of colourless colloid containing silver sulphide nuclei which, on development with and an outer colioid layer to actasan'anti-abrasion layer or ultra-violet ray absorbing layer. f
Such a photographic element, exposed to record v a coloured object, the rays 'beingjncident on layer emulsion layers.
vOn treating the iinal product with Farmers reducer all the silver and silver salts are removed, and the colour of layers c and e is also removed, leaving a true colour record of the originalobiect.
Many variations may be made in this procedure Without departing from the essential features of this invention. For example the layers b and d may be transposed and their processing correspondingly varied.. lFurther the layers c :and-fe may be adapted "to yield `rector".red-brown images and the `colour of the exposing "light used Y for re-exposing the layers correspondingly adjusted to a wavelength, or band of wavelengths,
-. :which .areabsorbed by such layers c and c. V1t .fis sometimes considered desirable when using a photographic element of the general character' referred'to above to remove the firstgraphic developer, these are converted to silver image colour separation negative records andthe fugitive dyestui is removed. If the photographic Adeveloper contains a silver solvent, or if the elel- Vineni'gis subsequently treated with a'photographic developer containing a silver solvent, layersV yc and e become coloured.V The fugitive dyestuf in layer e 'may be replaced by colloidal silver which im partsa yellow colour'to the layer. y
` The intensity of the developed colour depends `onthe particularfconditions prevailing, i. e. on
:the nature-of the layers cand ve and on the development conditions. A- veryv intense colouration is'usually obtained by including a/source of silver ions in the layers c and 'e themselvesfor example by including' a smallproportion of silver halide.Y lnv order to keep-the 4transparency of such layers,v before vdevelopment to colour, as high-asy possible, the added silver halide can usefully be a line grain emulsionsincethisis not only of high transparency but, presumably by vreason of vthe liinenerss of grain of the silver halide, is very reactiveas a'source of silver ions. The nature and quantity of the silver halide added' should not be suclnho'wever, that any substantial 'light-sensitivity-'is imparted to layers c ande since these should not give any Vappreciable black silver image on development.
The `emulsion layers of the photographic ele- 'ment :obtained by the procedure outlined above can be :further selectively processed to colour by making use of the coloured layers c and e Yas light-barrier layers. For example the element may be exposed to blue light through the support and then developed in a solution containing :an aromatic Yprimary .amino developing agent and a colourl-former .which combines With the oxidation .products of such developing agent, formed during development, to form a bluegreen azomethineor quinone-imine dyeimage in situ with the developed positive record in layer b. The .element `may then beexposed to blue 'lightincident on layer f and that layer similarly processed `to 'form a positive yellow image in layer j. Neither of these treatments affect layer d since the blue exposing light is absorbed by the yellow layers c and e. Layer d may then be rendered developable either by exposure to very bright light, Yadequate to penetrate 'layer c or e or by X-rays or by chemical treatment, e. g. With a 5% aqueous solution of sodium arsenite or hydrogen peroxide or with guanidine thiocyanate. This layer .may .be similarly developed to form in it a positive magenta image.
g halide records developable.
formed;1neg'ative" .silver records before re-exposing'to'render the complementary positive silver With the types of light-barrier layer which have been prepared in the past, e. g. dyestuis or black metallic silver layers (formed from .pre-fogged silver halide layers as described A'in British Patent No. 505,099), the removal of the negative *silver images has 'been impractical-ble since the treatment, usually With acid dichromate or acidpermanganate, has also removed theY dyestuis or metallic silver from the barrier layer.
`It `has lbeen found, however, that with fthe light-barrier Vlayers of the present vinvention the removalof the original negative silver image before exposure is `possible since the silver sulphide nuclei are .substantially unaffected bythe usual aciddichromate :bleach 'baths and a re-develop- Ament of the element with a developer containing a silver halide solvent results in colouration of the layers. V ,Accordingly an "important eature of the pres- .ent .invention consists inthe processing of an element of the general character of that set out above by the following steps:
:1. 'Develop to form original negative in'l'ayersb; d and T2. .Bleach `out the records 'formed in 1 by an acid dichroinate lbleach bath'. At this stage the dye in layer e has been bleached out by `the treatments .specied and if colloidal silver is used instead of dye'this lalso is removed.
3. 'Develop in 'a :developer containing a silver halide solvent. y 4. Ete-expose through'the' support a with light absorbed Aby the layer c and colour develop to form a positive blue-green azomethine or quinone-imine dyeiniagein b.
Syrie-expose with light falling on Ilayer `j and absorbed by layer e and colourdevelop to'form a positive yellow azomethine' or quinone-imine dye image in j.
i6. Treat' the assembly to render the silver halide in Alayer developable and colour develop to form a positive magenta azomethine or quirione-"iminedye imagein d.
7. Remove silver, silver salts and the colour in layers -c and 'e with Farmers reducer.
Appropriate variations would be made in this process lwere the layers b and d reversed. The following example will vserve toillustrate the production -rof la coloured colloidA layer and of a photographic 'element and its processing, according tothe invention.
y y Example Y V16k-photographic multi-layer element was prepared consisting of the `following layers in superposition inthe order stated. l
(a) Transparent colourless fllmsupport.
' (b) Gelatino silver iodobromide emulsion, sensitised to the red'reg'ion of the spectrum by means of 2.2'.8triethyl4.4' dichloroethiacarbocyanine bromide. (c) Gelatin layer containing rsilver` sulphide nuclei'and silver halide (prepared as described below). L
(d) Gelatine silver iodobromide emulsion, sensitised to the green region of the spectrum by means of 2.2'-diethyl-pseudocyanine iodide.
(e) Gelatin layer containing silver sulphide nuclei and silver halide (prepared asdescribed below)- and containing the dyestu l-pf-sulphophenyl-S-methyl Vl 'cinnamylidene-pyrazoleone. A y v (f) Gelatino silver iodobromide emulsion having anatural sensitivity inthe blue region of the spectrum and substantially insensitive to the green and red regions of the spectrum.. -l The layers c and e were prepared by adding to a 5% solution of gelatin, 5 cc. of AM/100fsilver nitrate solution and 2.5 cc. of` M/100l thiourea solution per 100 cc. of gelatin solution, digesting at 120 F. for 60 minutes, and adding 10 cc. of fine grain silver iodobromide emulsion (containing 250 mgm. of silver) per 100 cc. of gelatin soluf tion. In the case of layer ea quantity of the stated dye equal to 5% on the weight of the gelatin was addedy y 'Ihe element thus prepared was exposed to` a coloured object, the light being incident on layer f and developed for 3 minutes in a metol-hy- Water and re-developed for 8 minutesintafdeveloper consisting of:
An1id0'l V f 7.5 Sodium sulphite (anhyd.) 30 Sodium carbonate (anhyd.) y.40 Potassium thiocyanate 1;.0 Potassium'bromide i `1`.0
Water up to 1000 cc.
At this stage the `originally developed silver images `had been removed (by the dichromate bath), the dye in layer e had been removed (on the original development) anda yellow-red colour had been formed in layers c and e (by the amidol development).
The element was then exposed toviolet light passing through the support a and then developed in a developer of the following composition:
N.Ndiethy1 p-phenyiene diamine hydrochloride gm 0.4 Ethyl alcohol cc 40 Sodium carbonate (Na2CO3.10I-I2O) 20%A` solution cc 160 Sodium sulphite (NazSOs.7H2O) r20% solution Cc 25 2.4-dichlor-a-naphtho1 gm 0.4 Potassium bromide gm' 0 .1
Water to make 400 cc.`
This treatment resulted in the formation of a positive silver plus vblue-green indophenol dye image in layer b. The element was then re- 62 washed andV exposed ltof=violetl lightfalling-'on layer f. It'was then redeveloped in afdeveloper of "the: formula vgiven above' butcontaining '2+ chloracetoacetanilide "(0.4 gm.) instead of4 2.4- dichlorea-naphthol. By. this means a positive silver plusl yellowv azomethine dye image was formedin layer f.y -t j A n n The element was lthen-re-.washed andv exposed to X-rays, rendering f, thefresidual silver rhalide inlayer d developable.' It was then developed in a developer as above but containing iep-nitro.-l phenyl-3-methyl 5epyrazolone (0.4 gm.) :instead of the 2.4-dichlor-a-naphthol. This resulted in the formation of a positive silver plus magenta yazomethine dye image in layer d.
The element Was'then re-Washed and bathed in Farmers reducer, vwhich removed all the silver and silver salts and also the colour from layers c and e, leaving a fullcolour image of the original object. The line grain emulsionincluded in layersc and e' was too slow to record; an' imagejduring the various exposure operations. j
The process described above and'exemplied in the foregoing example may be modiiied'in various ways. For example, the-'exposedV positive silver halide records may be processed to colour by methods other than colour-development, e. g. by dye toning or chemical toning. f
'Moreover, one or more'ofthe emulsion layers may contain colour-immers;- the following isan example of such a process: 4
Example A photographic multi-layer element wasf'prepared consisting of the following layers in superposition in the order stated as illustrated in the accompanying drawing:
(a) Transparent colourless lm support.V '(b) Gelatino silver iodobromide 'emulsionsenf sitised to the red region by means of 2:2"8-'triethyl-4*:4dichlorwo thiacarbocyanine bromide and containing 2 parts v`olfl-hydroxy-Z-naphthoyl stearylamide-lfsulphonic acid yper` parts of emulsion. A I Y (c) Gelatin layer containing silver sulphide nuclei and silverhalide (prepared as'described below). f
(d) Gelatino silver iodobromide emulsion, sensitised to the green region f -the spectrum by means of 2.2f-diethyl-pseudocyanineiodide.V
(e) Gelatin layer containing silver sulphide nuclei and silver halide and yellow colloidal Esilver as lter medium. Thelatter isprepared by the reduction of an aqueous solution of silver nitrate in thepresence of gelatin by glycine. l (f) Gelatino silver iodobromide emulsionihaving a natural sensitivity in the blue region of the spectrum and substantiallyl -insensitive to th green and red regions of the spectrum. I The layers c ande were preparedas for the previous example. A r n The element thus prepared was exposed to a coloured object, the light being incident Aon layer f. It was then developed .for-B'minutes', in
a developer of the following formula:
Gms. Metol Q 3 Sodium sulphite (anhydrous) Hydroquinone 16V Sodium carbonate (anhydrous) 37.5 Sodium thiocyanate '2 Eotassium bromide 2 Water to 1 litre.
This produced negative yrecords in -silver in layersb.. d andi corresponding to the blue, green and red aspects of'the object-and, in addition, produceda uniform yellow-brown silver deposit in. layers c ande. The element was then washed in -runningfwater for 20 minutes yielding the product identified as stage l in the accompany,- ing drawing, and then processed Vto givef afull colour image in the following stages: i
. 1. Exposed to the top layer JJt'o .blue light, the exposure being confined to this layer by the barrierilayer e. s f
2. This layer colour-developed'4 in `a yellow colour developer ofthe following composition:
N.Ndiethyl p-phenylene diamine hydro- Water to make 400 cc..
3. Washed for l minutes. The element was then at stage 2 shown in the drawing.
4. rThe bottom layer b exposed to blue light, exposure being confined to this layer by means of the barrier layer c.
5. "Colour-developed in a developer of the following composition:
mN-diethyi p-phenylene diamine hydrochloride gm 0.4 Ethyl alcohol cc 40 Sodium carbonate (NazCO3-l0I-I2O) 20% solution cc 160 Sodium sulphite (NazSO3-7H2O) 20% soluy tion cc 25 Potassium bromide gm-- 0.1
Water-5to make 10D-cc.
6. Washed for l0 minutes.' Theelement lwas then at stage 3 shown in the drawing.
7. The middle layer d exposedirom both sides to white light. White light will penetrate' the barrier layers. "'v Y y `8. This layer colour-developed in a magenta colour developer of the following composition:
chloride ',i g m. 0.4 Ethyl alcohol cc 40 Sodium carbonate (NazCOalO'I-IzO) 20% solution f cc 160 Sodium sulphite (Na2SOs-7HzO) .20% solution i cc l-p nitrophenyl 3 methyl 5 pyrazo- Alone gm 0.8
9. Washed for minutes. The element was then at stage 4 shownin the drawing. y
10. 'Fixed and bleached in Farmers reducer.
1l. Washed for 20 minutes. `The elementwas then at 'stage 5 shown in the drawing. The full colour image of the originalobjectwas thereby obtained.
What we claim is: K
,1. A photographic element which comprises a support Vcarrying at least three superimposed layers, the outer ones of which are colloid silver halide photographic emulsion layers and the middle one of which is a layer of substantially colourless colloid containing silver sluphide nuclei, of such particle size and quantity that they impart no colour to the layer, the said colourless colloid' containing a quantity of silver compound insuiliciently sensitive to light Vto produce any appreciable image in the-saidcolourless colloid layer on photographic development, but suiiicient in quantity to producegwith'thei aid 'of said silver sulphide nuclei, alayer of silversubstantially opaque to blue light on photographic development.
2. A photographic element which comprises v(a) a transparent Vsubstantially colourless sup-- port and in superimposition thereon, in order, (b) asilver halide emulsion layer sensitive to red light, (c) a layer ofA a colourless colloid containing silver sulphide nuclei of suchparticle size and quantity that they 'impart no colourl to the layer, and a quantity 'of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but suiiicient in quantity to produce, with the aid of said silver sulphide nuclei,'a4 layer of silver `substantially opaque to blue light on photographic'develop* ment (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart nocolou'rrto the layer, and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but suiiicient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and a removable yellow colouring material, and (f) a silver halide emulsion sensitive only to bluelight.
`3. A photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon, in order, (b) a silver halide emulsion layer sensitive'to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart `no colour` to the layer, and a quantity of silver rhalide insuf'- flciently sensitive to light tofyield any` appreciable l, image on photographic development but suflicient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of. silver.` substantially opaque to blue light on photographic development, (d) a silver halide emulsionlayer sensitive to green light, (e) a layer of colourless Acolloid containing silversulphide nuclei of such'lpfflrticle size and quantity that they impart no colour to the layer, and a quantity of silver halide insufently sensitive to light to Vyield any appreciable image on photographic development but Asuicient in quantity to produce, with theaid of said silver sulphide nuclei, a layer of 'silvensubsta'ntially opaque to blue lighten photographic development, and a removable yellow colouring'material, and (f) a silver halide emulsion' sensitive only to blue light.
4. A photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon,.in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layenand a quantity of an emulsion of silver halide insufficiently sensitive to light to yield any appreciable image on photographic development but sufcient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, (d) a silver halide emullof'sanv emulsion, of. silver` halide insuiiiciently sensitive to light to ,yield any1;altlpreciable` image en .photographic development but suicient in .quantity to,.produce, withthe.aid of said's'ilver sulphide :nuclei, a layer of lsilver substantially opaque. toblue light on photographic `development, and-fa removable yellow colouring material, and (f) afsilver halide emulsionsensitiveponly to blue light.
5. A photographic element which comprises (a) Aa'transparent substantially colourless support and' in superimposition thereon, in order, 1(1))A a silverhalide emulsion layersensitive to red light,` (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer, and a quantity of an emulsion of silver halide insuiiiciently sensitive to light to yield any appreciable image on photographic development but sulcient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer, and a quantity of an emulsion of silver halide insuiciently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and yellow colloidal silver, and (f) a silver halide emulsion sensitive only to blue light.
6. A process of colour photography which includes the step of treating an exposed photographic element which comprises (a) a transparent substantially colourless support and in super-imposition thereon, in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to lblue light on photographic development, (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but suicient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and a removable yellow colouring material, and (f) a silver halide emulsion sensitive only to blue light with a photographic developer containing a solvent for silver halide.
7. A process of colour photography which comprises treating an exposed photographic element which comprises (a) .a transparent substantially colourless support and in superimposition thereon, in order, (b) a silver halide emul- 10 sion layer sensitive j to redl light;V (c) a layer y.of a colourless :colloid .zcontaining silver.- sulphide nuclei of such particlesize and quantity :that they impartv no. 'colourrtd the-` layer land; a quantity' of a vsilver lcompound:soluble'.in-.-alkalithiosulphate insuiciently sensitiveto ,lightltof yield any appreciable ,i1nage;;l 0.11 photographic development but sufjcientin ,quantity to produca-.with the aid of said silver-sulphi nuclei, a; layerof silver substantially opaquetox-'bluelight on photographicdevelopmentgKd), a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloidl. containing silver sulphide nuclei of such particle size and quantity that. they impart no colour to the layer anda quantity of a silver compound soluble in alkali- 'thiosulphate insuiciently sensitive toy light to yield any appreciable image on photographic development .but suilicient in quantity to; produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and a removable yellow colouring material, and (f) a silver halide emulsion sensitive only to blue light by the following operations: develop in a non-colour-forming developer containing a solvent for silver halide, expose layer b to blue light passing through layer a and re-develop layer b in an aromatic primary amino colour-developing solution containing a blue-green colour-former, expose layer f to blue light incident on that layer and re-develop layer f in an aromatic primary amino colour-developing solution containing a yellow colour-former, render layer d re-developable and re-develop in an aromatic primary amino colour-developing solution containingA a magenta colour-former, and treat the final product with Farmers reducer to remove all silver and silver salts and all colouration from layers c and e.
8. A process of colour photography which comprises treating an exposed photographic element which comprises (a) a transparent substantially colourless support and in superimposition thereon. in order, (b) a silver halide emulsion layer sensitive to red light, (c) a layer of a colourless colloid layer containing silver sulphide nuclei of such particle size and quantity that they impart no colourv to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufciently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development. (d) a silver halide emulsion layer sensitive to green light, (e) a layer of colourless colloid containing silver sulphide nuclei of such particle size and quantity that they impart no colour to the layer and a quantity of a silver compound soluble in alkali thiosulphate insufficiently sensitive to light to yield any appreciable image on photographic development but sufficient in quantity to produce, with the aid of said silver sulphide nuclei, a layer of silver substantially opaque to blue light on photographic development, and a removable yellow colouring material, and (f) a silver halide emulsion sensitive only to blue light by the following operations; develop in a non-colour-forming developer, bleach out the developed records in layers bl, d and f, develop in adeveloper containing a silver halide solvent. expose layer b to blue light passing through layer a and re-develop layer b in an aromatic primary amino colour-developing solution containing a blue-green colour-former, .expose layer f to blue light 'incident ou that layer Yarid re-develop layer f in an aromatic primary amino colour-developing solution containing a yellow colour-former, render layer d, re-developable and re-develop nlan aromatic primary amino colourdeveloping solution containinga magenta colourformer, and treat the nal product vwith Farmers reducer toremove all silver and silver salts and all colouration from layers candf e.
CECIL WALLER.
HAROLD OWENDICKINSON.
REFERENCES CITED The `following references are of record in' the le of this patent:
UNITED STATES PATENTS Name Date- Number I5 Number Name Date Wendt 4-- Feb. 21, v1933 Knocher July 27, 1937 Eggert et a1. Apr. 11, 1939 Schnzel Sept. 5, 1939 Seaseret al Feb. 27, 1940 Sease et al.V Nov. 11, 419,41 Schinzel- Sept. 8, 1942 Eggert et a1., June 1,1943 Carroll Aug. 24, 19.43 Rott June 20, 1944 Staud May 15, 1945 FOREIGN PATENTS Country Date Great Britain Aug. 24, 1939 France Dec. 10, `19,42 France Sept. 25, 1944
Claims (1)
1. A PHOTOGRAPHIC ELEMENT WHICH COMPRISES A SUPPORT CARRYING AT LEAST THREE SUPERIMPOSED LAYERS, THE OUTER ONES OF WHICH ARE COLLOID SILVER HALIDE PHOTOGRAPHIC EMULSION LAYERS AND THE MIDDLE ONE OF WHICH IS A LAYER OF SUBSTANTIALLY COLOURLESS COLLOID CONTAINING SILVER SLUPHIDE NUCLEI, OF SUCH PARTICLE SIZE AND QUANTITY THAT THEY IMPART NO COLOUR TO THE LAYER, THE SAID COLOURLESS COLLOID CONTAINING A QUANTITY OF SILVER COMPOUND INSUFFICIENTLY SENSITIVE TO LIGHT TO PRODUCE ANY APPRECIABLE IMAGE IN THE SAID COLOURLESS COLLOID LAYER ON PHOTOGRAPHIC DEVELOPMENT, BUT SUFFICIENT IN QUANTITY TO PRODUCE, WITH THE AID OF SAID SILVER SULPHIDE NUCLEI, A LAYER SILVER SUB-
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB17544/45A GB595582A (en) | 1945-07-10 | 1945-07-10 | Improvements in or relating to coloured colloid layers |
| GB1754446 | 1946-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2609292A true US2609292A (en) | 1952-09-02 |
Family
ID=32232443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US682300A Expired - Lifetime US2609292A (en) | 1945-07-10 | 1946-07-09 | Light-sensitive photographic element and process using it |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2609292A (en) |
| DE (1) | DE874705C (en) |
| FR (1) | FR959749A (en) |
| GB (1) | GB595582A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362470A (en) * | 1991-05-30 | 1994-11-08 | Konica Corporation | Ultrafine gold and/or silver chalcogenide and production thereof |
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| US2262055A (en) * | 1940-01-25 | 1941-11-11 | Du Pont Film Mfg Corp | Method of color photography |
| FR879995A (en) * | 1941-01-24 | 1943-03-10 | Ig Farbenindustrie Ag | Process for the constitution of positive photographic images |
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| US2376202A (en) * | 1943-05-27 | 1945-05-15 | Eastman Kodak Co | Retarding diffusion of sensitizing dyes |
| FR900266A (en) * | 1942-12-05 | 1945-06-25 | Gevaert Photo Prod Nv | Process for the production of corrected partial photographic images |
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| US1279276A (en) * | 1917-01-25 | 1918-09-17 | Eastman Kodak Co | Tinting process and product thereof. |
| US1898512A (en) * | 1927-01-07 | 1933-02-21 | Agfa Ansco Corp | Process of manufacturing photographic silver salt emulsions and lightsensitive material |
| US2088523A (en) * | 1934-02-14 | 1937-07-27 | Belz Gaspar | Multicolor photographic material |
| US2153617A (en) * | 1935-06-22 | 1939-04-11 | Agfa Ansco Corp | Manufacture of colored photographic pictures |
| US2320418A (en) * | 1935-06-22 | 1943-06-01 | Gen Aniline & Film Corp | Color photographs |
| US2295013A (en) * | 1936-05-09 | 1942-09-08 | Eastman Kodak Co | Method of developing multilayer photographic color films |
| US2172262A (en) * | 1936-05-09 | 1939-09-05 | Eastman Kodak Co | Ultraviolet filter in multilayer film |
| US2191502A (en) * | 1937-01-22 | 1940-02-27 | Pont Film Mfg Company Du | Multicolor film and process |
| GB511800A (en) * | 1938-02-25 | 1939-08-24 | Kodak Ltd | Filter-layers for colour photography |
| US2262055A (en) * | 1940-01-25 | 1941-11-11 | Du Pont Film Mfg Corp | Method of color photography |
| FR879995A (en) * | 1941-01-24 | 1943-03-10 | Ig Farbenindustrie Ag | Process for the constitution of positive photographic images |
| US2327764A (en) * | 1941-05-09 | 1943-08-24 | Eastman Kodak Co | Ultraviolet filter |
| US2352014A (en) * | 1941-07-21 | 1944-06-20 | Rott Andre | Photomechanical printing process and printing material for carrying out the same |
| FR900266A (en) * | 1942-12-05 | 1945-06-25 | Gevaert Photo Prod Nv | Process for the production of corrected partial photographic images |
| US2376202A (en) * | 1943-05-27 | 1945-05-15 | Eastman Kodak Co | Retarding diffusion of sensitizing dyes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362470A (en) * | 1991-05-30 | 1994-11-08 | Konica Corporation | Ultrafine gold and/or silver chalcogenide and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB595582A (en) | 1947-12-09 |
| FR959749A (en) | 1950-04-04 |
| DE874705C (en) | 1953-04-27 |
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