US2509232A - Color photography - Google Patents

Color photography Download PDF

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Publication number
US2509232A
US2509232A US712245A US71224546A US2509232A US 2509232 A US2509232 A US 2509232A US 712245 A US712245 A US 712245A US 71224546 A US71224546 A US 71224546A US 2509232 A US2509232 A US 2509232A
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United States
Prior art keywords
colour
emulsion
images
silver
silver halide
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Expired - Lifetime
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US712245A
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English (en)
Inventor
Coote Jack Howard
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British Tricolour Processes Ltd
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British Tricolour Processes Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to the production of coloured photographic images and more particularly to the production of motion pictures in colour.
  • a multi-layer sensitive material usually consisting of three distinct emulsion layers with interposed filter layers, is printed by a single exposure from a multicoloured image.
  • This method requires the provision of multi-layer material having colour sensitive emulsions and dyed filter layers and requires extreme consistency in the coating of the very thin layers of which it is composed. If the processing of the material is to be in any way comparable with ordinary black and white material appropriate colour-forming materials must also be incorporated in the colour sensitive emulsions; the introduction of these is in addition to that of the necessary sensitizers. Such additions add greatl to the complexity and cost of manufacture of the colour film.
  • the second general method depends upon the successive production of the colour images by means of the transfer of dye images or the successive production of developed silver images which are in turn toned to the appropriate colour images.
  • This general method involves a considerable departure from the technique of black and white work and requires a set of colour separation negatives with which to work. Nevertheless it has many features and advantages which render it of considerable value.
  • a second form of the second general method is described in British Patent 585,477 in which there is disclosed a method of producing a threecolour image which is especially suitable for cinetamographic work when three-colour separation negatives are available.
  • a multi-coloured photographic image is produced by printing a silver halide emulsion layer from a first colour separation record, developing and colouring to produce the required positive colour record, coating the layer containing the first formed colour record with a composition containing silver halide and the same emulsion colloid as that of the emulsion layer so as to produce, on drying, a second silver halide emulsion layer directly superposed upon the image-containing layer and having a substantially normal weight of silver halide and a colloid/silver ratio (based on the silver nitrate used in its production) of not more than 1.5 to 1, printing from a second colour separation record, developing and colouring to produce the required positive colour record, the sequence of formation of the colour images being chosen with respect to the chemical and image-wise desens
  • ing of the film can be achieved in a minimum of time.
  • the present invention seeks to provide amodi- .fication ofthis prior process lin whi'ch certainoi :the, processin stages are eliminated.
  • Thecolour developmentstage may be carried developer 'to;givethe desired colour images. ca-result. it is-not necessary to develop-each latent image as. it isprinted. Instead the additional with the said coupler subtractive images of correct hue are obtained, printing from the third colour separation negative of said three-colour set, simultaneously developing the three successively produced latent images and coupling with a coupler to simultaneously produce the three icolour images.
  • the applied emulsion layers may have a colloid/silver .ratio (based on the silver nitrate used in their ,production) of not more than 1.5:1 and, preferably, 'of approximately 1:1.
  • The. present invention is similar to that described'in BritishPatent 585,477 in that it proceeds by thebuilding up of 9, multi-layer material each layer of which contains one of the component images. of'th'e'multi-colour image but differs therefrom in that the colour formers which are present in the emulsion layers are so chosen that they can all be developed with the same colour .As
  • alow developing potential it is preferred first todevelop the three latent images in an ordinary black-and white developer such as one-based upon metol and-hydroquinone or-amidol, to convert .the 'resulting imagesiinto silver halideyfor examplaby treatment with a solution .of potassiumzferricyanide and'potassium bromide, to reexpose andthen redevelop-with the colour developer after-which the: silver. images -may beremoved by farmerstreduccr;
  • an ordinary black-and white developer such as one-based upon metol and-hydroquinone or-amidol
  • the colourfonners usedaccording to the present invention should be substantially non-mobile.
  • colour formers containing alkyl sub- :stituents having at least five and preferably from twelve to eighteen carbon atoms or the colour 'former may have been combined by chemical reaction with a suitable residue such as that of a high molecular weight water-permeable but water-insoluble natural or synthetic resin, that of a sterol, that of a substance of the cyclic methane series, that of a, polypeptide, that of a, highly polymeric carboxylic acid, that of a polymeric material of which a carboxylic acid is a component or that of a carbohydrate.
  • the colour formers are so chosen that upon coupling with the selected colour developer colour images of the correct tone are obtained. Since all the images are developed simultaneously it follows that, in general, any desired order of printing the images may be adopted since such considerations as desensitization and degradation of an already formed colour image do not arise in the present process.
  • the process can be conveniently carried out using gelatine emulsions of normal characteristics having incorporated therein the said colour formers but preferably the emulsions employed are the emulsions of reduced gelatin silver ratio described in British Patent 585,477.
  • the use of these emulsions not only enables the three distinct images to be accommodated within a minimum of depth but avoids any tendency for reticulation and frilling to occur due to swelling during processing as described in that application and also to be carried out in a minimum of time due to the reduced overall thickness of the multi-layer emulsion being treated.
  • the process of the present invention utilizes as starting material a film base material (e. g. pyroxylin or cellulose acetate strip material) to which is first applied a conventional primer. After removing the volatile solvent of the primer composition, a silver halide photographic emulsion composition, preferably having a gelatine/silver ratio of about 1:1 and containing a suitable concentration of a substantially nonmobile yellow colour former is applied.
  • a film base material e. g. pyroxylin or cellulose acetate strip material
  • Suitable yellow colour formers are terephthalolyl bis-acetanilide, benzoyl acetanilide, 5 (4 stearyl amidobenzoylacetamido) isophthalic acid and 4-methoxybenzoy1acetd l-(2- methylstearylamino 4' carboxyphenol) amide.
  • the layer is preferably coated at such a thickness as to produce, on drying, a substantially normal coating weight of silver halide.
  • substantially normal coating weights of silver halide are meant those containing from 40 to 80 milligrams, and preferably 50 to 60 milligrams, of silver per square decimeter of coating. After drying this layer is printed from the blue record separation negative.
  • magenta colour formers are 1-(4-stearylamino-phenyl)- S-methyl-B-pyrazolone, l-(4'-phenoxy 3 sulphophenyl) -3-heptadecyl 5 pyrazolone, 1- (3- sulphophenyl 3 (4" stearyl-amido-phenyl) 5- pyrazolone and 4(1S-stearyl-fi-carboxypropionamido)-benzoylacetonitrile.
  • This layer is also preferably coated at such a thickness as to produce an emulsion layer containing a substantially normal coating weight of silver halide. After setting and drying this layer is printed, in register, from the green record separation negative. The multi-layer material, now containing two latent images is coated a third time. The third coating is with a silver halide emulsion composition having emulsion characteristics similar to those of the first and second applied compositions but containing a substantially non-mobile bluegreen colour former.
  • bluegreen colour formers are di-(2.8-dihydroxy-3- naphthoic acid) benzidide, naphthalene-l-hydroxy-z-stearyl carbonamido 4 sulphonic acid, naphthalene-l-hydroxy 2 N (dodecylcarbonamido) -4 sulphonic acid, naphthalene 1 hydroxy 2(2m'ethyl stearylamino 5 sulphophenyl) carbonamido and naphthalene l-hydroxy 2 carbon (N stearyl N -i.sophthaly1) amide.
  • This layer is also preferably coated at such a thickness as to produce an emulsion containing a substantially normal coating weight of silver halide.
  • the multi-layer material after setting and drying, is printed, in register, from the red colour separation negative and is ready for development.
  • development may be by either of two methods.
  • development of all three images may be carried out with a bath containing para-diethyIl-aminoaniline as colour developer.
  • This colour developer is used in the present case since with all the above named colour components it gives dye images of the correct hue.
  • Other paradialkyl aminoanilines may be used.
  • the development bath is preferably kept in a state of thorough agitation but free from aeration throughout the development.
  • the silver images are simultaneously developed with a conventional metol-hydroquinone developer. This is controlled so as to prevent development being carried too far in view of the intention to subsequently redevelop.
  • the developed material is then treated with a bath containing potassium ferricyanide and potassium bromide to reconvert the developed material to silver bromide.
  • the image is then re-eXp-osed and developed again in the colour developer.
  • a fugitive dyestufi' such as tartrazine may be incorporated in the second and any subsequently applied emulsion compositions.
  • An alternative is to print the emulsion layers using ultra-violet light or to print the emulsion layers containing a fugitive dyestufi using ultra-violet light. Fugitive dyestuifs such as tartrazine are readily eliminated durin the subsequent processing especially when the applied layers are of reduced colloid/silver ratio.
  • a silver halide emulsion may be prepared as follows. A solution containing the following is prepared and brought to 70 (3.:
  • the starting material is a-base material, shown at A on the flow sheet such as a nitrocellulose or cellulose acetate.
  • This is first coated with a primer andthen-with a silverhalide-emulsion containing the selected colour former.
  • the emulsion employed is one having agelatine/silver ratio of not more than 1.5 to 1 and advantageously about 1 to l.
  • the emulsion is printed'from-the appropriate colour. separation. negative.
  • the selected colourformer incorporated into the emulsion is a yellow colour former (as shown at B on-the flow sheet)
  • the colour separation nega-- tive from which it-is printed is the blue record separation negative (as at C 0n the flowsheet).
  • the printedemulsion is coated with a second emulsion which preferably has been prepared in a similar manner to the first emulsionbut contains a colour former from which an appropriately coloured image can be obtained when coupled 'with the same coupler as the first colour.
  • the second emulsion may have the same gelatine/silver ratio as the first emulsion or it may differ therefrom.- In order to avoid reticulation and frilling in the developing stages it is preferred to use an emulsion having a gelatine/silver ratio of not more than 1.5 to 1 and preferably about 1 to 1.
  • the second, emulsion may have incorporated therein aiugitive dyestulT; such as tartrazine, which restricts the action of the printing light to the emulsion. Alternatively the second image may lie-printed using ultra-violet light.
  • the second emulsion may contain the'magentacolour 'former (D on the flow sheet) and, in that case; it is printed from the green record separation negative, as shown at E on theflow sheet.
  • theemulsion has thesame gelatine/silverratioasthe second emulsion; This: emulsion alsolmay haveincorporated therein a fugitive dyestuff; such as tartrazine; which restricts theactionof the-print-' ing.
  • the order of printing thesimagesneed not necessarily be that outlined.
  • Thecessential point is to obtain three emulsion layers each of which contains anappropriate colour former and has beenprinted froma colour separation record which is complementary to the positive colour record'which will be obtained ondeveloping- (or redeveloping) withthe coupler.
  • A-bath is made up contain- Para-diethylaminoaniline sulphate gms 3 Sodium sulphite gms 2 Potassium carbonate -1 gms 75 7 Potassium bromide gms 2.5 Water to make; litre 1 Potassium ferricyanide gms l0 Ammonia 28% ccs 10 Water to make litre 1 after whichthefilmis again rinsed (I on the flow sheet) and'then treated with'a strong aqueous solution (about. 20%) of-"sodium thiosulphate (-G-f on; theflovr sheet). 7
  • More than one colour component may be incorporated into any one of the applied emulsions so long as upon colour development an image of the correct hue is obtained.
  • a mixture of 5-(4'-stearylamidobenzoylacetamido) isophthalic acid and e-methoxybenzoylacet-N-(2'-methylstearylamino-'-carboxyphenyl) amide may be used together as the colour components for the yellow image when the developer is a paradialkylaminoaniline such as paradiethylaminoaniline.
  • the process is applicable also to the formation of colour positives from the negatives of a two-colour process.
  • Such process may be operated in the same general way as that described using the appropriate colour components.
  • a suitable colour component from which to produce a yellowish-red positive colour record, when using diethylaminoaniline as the colour developer, is 1 (5-sulpho-3' -stearylaminophenyl) -3-methyl-5-pyrazolone.
  • the blue-green colour components previously exemplified may be used in the emulsion for the second image.
  • a protective outer supercoating of emulsion or of a lacquer may be applied to the film to preserve it from damage by abrasion.
  • a gelatine emulsion may be employed or a transparent lacquer having a basis of a film-forming material which will adhere to gelatine, such as a polyvinyl alcohol lacquer.
  • the invention can also be used for the production of images in which two or four images are produced on a single side of a base material and also when three or more images are produced by coating both sides of the base material.
  • the general procedure is exactly as outlined, a suitable choice of colour components for coupling with a single coupler being made depending upon the colours desired in the positive records to be produced.
  • a process for the production of a multicoloured photographic image which comprises coating a photographic base material with a first composition containing a silver halide and a colour former which is substantially non-diffusing under the process conditions dispersed in a photographic emulsion colloid, printing from a first colour separation record, coating the printed emulsion with a second composition containing a silver halide and a colour former of said nondifiusing type but adapted to produce a different coloured image, dispersed in the same photographic emulsion colloid as that of said first composition so as to produce, on drying, a second silver halide emulsion layer directly superposed on said printed emulsion, printin in register from a second colour separation record, simultaneously developing the successsively produced latent images with a developer capable of forming dyes from said colour formers and removing developed silver from the images.
  • a process according to claim 1 in which the concentration of the ingredients of the second applied composition is such as to produce a silver halide emulsion layer having a colloid/silver ratio based on the silver nitrate used in its production of not more than 1.5:1.
  • a process for the production of a multicoloured photographic image' which comprises coating a photographic base material with a first composition containing a silver halide and a colour rormer which is substantially non-difiusing under the process conditions dispersed in a photographic emulsion colloid, printing from a first colour separation record, coating the printed emulsion with a second composition containing a silver halide and a colour former of said nondiffusing type but adapted to produce a different coloured image, dispersed in the same photographic emulsion colloid as that of said first composition so as to produce, on drying, a second silver halide emulsion layer directly superposed on said printed emulsion, printing in register from a second colour separation record, simultaneously developing the successively produced latent images with a developer incapable of forming dyes from said colour formers, removing unused silver halide, reconverting the developed silver images into silver halide, reexposing and developing with a developer capable of forming dyes from said colour formers and removing developed
  • a process according to claim 5 in which the concentration of the ingredients of the second applied composition is such as to produce a silver halide emulsion layer having a colloid/silver ratio based on the silver nitrate used in its production of not more than 1.5:1.
  • a process for the production of a threecoloured subtractive photographic image which comprises coating a photographic base material with a first composition containing a silver halide and a colour former which is substantially nondiiiusing under the process conditions dispersed in a photographic emulsion colloid so as to produce, on drying, an emulsion layer containing a substantially normal coating weight of silver halide, printing from the first colour separating negative of a three colour set, coating the printed emulsion with a second composition containing silver halide and a second colour former of said non-diffusing type dispersed in the same emulsion colloid as that of said first applied composition so as to produce, on drying, a second emulsion layer, superposed upon the first printed emulsion and containing a substantially normal coating weight of silver halide, printing in register from the second colour separation negative of said three colour set, coating the second printed emulsion with a third composition containing silver halide and a third colour former of said non-diffusing type dispersed in
  • a process forrthe production of a threecoloured' subtractive photographic image which cQmprises coatingwa photographic base material with a first composition containing a silverhalide and a -colour former whichis substantially non diffusing under the process conditions dispersed in -a photographic emulsion colloid so as to produce, on dr ying, an emulsion layer containing a substantially normal coating weight of silver halide, printingfrom thefirst colour separating negative of a three colour set, coating the printed emulsion with a second composition containing 3 silver halide and?

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US712245A 1945-11-28 1946-11-26 Color photography Expired - Lifetime US2509232A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB32117/45A GB608507A (en) 1945-11-28 1945-11-28 Improvements in colour photography
GB36297/46A GB626897A (en) 1945-11-28 1946-12-09 Improvements in colour photography

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US792094A Expired - Lifetime US2592864A (en) 1945-11-28 1947-12-16 Color photography

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US (2) US2509232A (fi)
BE (2) BE479269A (fi)
FR (2) FR936362A (fi)
GB (2) GB608507A (fi)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2886435A (en) * 1953-08-21 1959-05-12 Panacolor Inc Photographic iron-silver color process
US2927020A (en) * 1954-08-16 1960-03-01 David A Zilli Photographic process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1187421A (en) * 1913-12-17 1916-06-13 Kinemacolor Company Of America Photographic process.
US1256675A (en) * 1917-01-13 1918-02-19 Natural Color Picture Company Inc Production of colored pictures.
US1435283A (en) * 1919-07-17 1922-11-14 Procoudine-Gorsky Serge De Production of colored diapositives
US2179234A (en) * 1935-10-03 1939-11-07 Agfa Ansco Corp Manufacture of multicolor photographs
US2200018A (en) * 1937-07-09 1940-05-07 Bertrand Jean Pierre Process of polychrome photography
US2415626A (en) * 1941-11-14 1947-02-11 British Tricolor Processes Ltd Production of three-colour subtractive photographic images
US2443909A (en) * 1946-06-28 1948-06-22 Eastman Kodak Co Process of producting multicolor photographic images in a single emulsion layer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1260324A (en) * 1915-09-01 1918-03-26 Eastman Kodak Co Making multiple photograph exposures.
BE416147A (fi) * 1935-06-22
BE416898A (fi) * 1935-08-07
GB470074A (en) * 1936-02-06 1937-08-06 Humphrey Desmond Murray Production of coloured photographic images by development
BE427106A (fi) * 1937-03-30
GB520076A (en) * 1938-08-12 1940-04-15 Kodak Ltd Improvements in multi-layer colour photography

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1187421A (en) * 1913-12-17 1916-06-13 Kinemacolor Company Of America Photographic process.
US1256675A (en) * 1917-01-13 1918-02-19 Natural Color Picture Company Inc Production of colored pictures.
US1435283A (en) * 1919-07-17 1922-11-14 Procoudine-Gorsky Serge De Production of colored diapositives
US2179234A (en) * 1935-10-03 1939-11-07 Agfa Ansco Corp Manufacture of multicolor photographs
US2200018A (en) * 1937-07-09 1940-05-07 Bertrand Jean Pierre Process of polychrome photography
US2415626A (en) * 1941-11-14 1947-02-11 British Tricolor Processes Ltd Production of three-colour subtractive photographic images
US2443909A (en) * 1946-06-28 1948-06-22 Eastman Kodak Co Process of producting multicolor photographic images in a single emulsion layer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2886435A (en) * 1953-08-21 1959-05-12 Panacolor Inc Photographic iron-silver color process
US2927020A (en) * 1954-08-16 1960-03-01 David A Zilli Photographic process

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Publication number Publication date
GB608507A (en) 1948-09-16
GB626897A (en) 1949-07-22
US2592864A (en) 1952-04-15
BE479270A (fi)
BE479269A (fi)
FR936362A (fr) 1948-07-19
FR58155E (fr) 1953-09-29

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