US2304939A - Multilayer photographic material containing color formers - Google Patents

Multilayer photographic material containing color formers Download PDF

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Publication number
US2304939A
US2304939A US314688A US31468840A US2304939A US 2304939 A US2304939 A US 2304939A US 314688 A US314688 A US 314688A US 31468840 A US31468840 A US 31468840A US 2304939 A US2304939 A US 2304939A
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layers
layer
emulsion
sensitive
photographic
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US314688A
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English (en)
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Leopold D Mannes
Jr Leopold Godowsky
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex

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  • This invention relates to colorqphotography and particularly to a multi-layer photographic material containing color formers.
  • a process of this type which is widely used commercially involves the coupling of a color forming compound with a primary aromatic aminoideveloping agent to form a colored image.
  • the coupling compounds used in this process are those having a reactive methylene group or a reactive phenolic group which couples with the oxidation product of the primary aromatic amino developing agent on photographic development. Suggestions have been made for incorporating these coupling compounds either in the developing solution or in the sensitive layer before exposure.
  • the coupling compounds When the coupling compounds are incorporated in the developing solution, it is desirable that they be as soluble as possible in the developing solution'so that upon photographic development they will penetrate the gelatin or other colloidal material of the sensitive layer and thereby permit the formation of a dye image in any exposed portion of the layer.
  • the coupling compounds when the coupling compounds are to be incorporated in the sensitive layer prior to exposure they should not diffuse out of the layer during coating of a multi layer material or during photographic development. Methods have been proposed for keeping the coupler compounds in the photographic layer most of these involving the use of large molecules of coupler to prevent diffusion.
  • Fischer describes a multi-color process using coupler compounds incorporated in the photographic layers. It has since been found that the coupling compounds known to Fischer could not be kept in the respective layers of a multi-layer material by merely mixing them with the gelatin of the emulsion. All of the coupling compounds disclosed by .Fischer diffuse from the layer and no color separation can be obtained in Fischers process.
  • coloring materials such as coupling compounds in a photographic layer or layers so that they do not diffuse from the layer or layers but may be made to react with the oxidation productof an aromatic amino developing agent to form a colored image or colored images on photographic development.
  • Our method consists in mixing the coupling compound with an emulsion of collodion or other cellulosic material which is separated from another emulsion in a multi-layer coating by an I inter-layer of gelatin Or other water-susceptible colloid, such as albumin or agar.
  • an emulsion of collodion or other cellulosic material which is separated from another emulsion in a multi-layer coating by an I inter-layer of gelatin Or other water-susceptible colloid, such as albumin or agar.
  • coupler does not diffuse from the collod'ion emulsion past the collodion-gelatin interface. This is true even when the coupler is quite alkali-soluble and for this reason couplers can be employed which have hitherto been regarded as unsuitable for incorporation in photographic layers either*because of the readiness with which they diffuse or because of the diffusion of dyes formed from them upon photographic development.
  • a photographic element having a plurality of diilerentially color-sensitive cellulosic emulsions on a single support at least one of which emulsion containing a coupling compound.
  • the element may have a plurality of layers of differentially color-sensitive emulsions on'a single support each of which contains a coupler, the emulsion layers being separated by gelatin interlayers.
  • the photographic element may consist of a support of transparent material such as-cellulose nitrate or cellulose acetate or opaque material such as paper having thereon an emulsion of silver halide-collodion, the collodion having distributed therein finely dispersed particles of the coupler compound.
  • the coupler might be in true solution in the cellulosic compound.
  • a plurality of layers may be coated in this way each containing in the collodion emulsion a coupling compound yielding a dye corresponding in a suitable manner to the sensitivity of the emulsion.
  • a red sensitive photographic emulsion would be chosen containing ablue-green coupling compound, a green-sensitive emulsion containing a magenta couplingcompound and a blue-sensitive emulsion containing a yellow coupling compound.
  • the coupling compounds are those which produce dyes on development in an aromatic amino developing agent and by blue-green coupling compound etc., we refer to a coupling compound which produces a blue-green dye on development in this way.
  • collodion emulsions As used in the preferred embodiment of our invention, it is to be understood that emulsions of other cellulosic materials such as cellulose acetate or'mixed organic acid esters of cellulose such as cellulose acetate phthalate may be used. These emulsions should be sufliciently permeable to photographic processing baths to enable them to be processed in the usual way. Cellulosic emulsions of this type are described, for example, in Salo U. S. Patent 2,110,491, granted March 8, 1938', and Sheppard and Houck U. S. Patent 2,127,573, granted August 23, 1938.
  • the two emulsion layers are made in a similar manner except that different couplers are used.
  • the coupler in the case of the red-sensitive emulsion l-hydroxy-Z-N-methyl naphthanilide can be used as the coupler and in the case of the green-sensitive emulsion a coupler mixture yielding an orange-red dye upon development such as n-propyl-p-benzoyl acetamino benzene sulfonate and 2 cyanoacetyl-naphthalene sulfone N methyl anilide.
  • couplers are used in the amount of about 5 grams each and produce an orangered dye upon development in a coupling developer.
  • the gelatin inter-layer may contain a yellow filter such as tartrazine or the film may contain throughout-the emulsions a yellow dye which is removable during processing.
  • a yellow filter such as tartrazine
  • the film may contain throughout-the emulsions a yellow dye which is removable during processing.
  • Example 2 A three-layer sensitive material is made as follows: A suitable support is coated with a redsensitive collodion silver halide emulsion to which has been added a solution of 5-phenoxy acetamino-l-naphthol to serve as a blue-green coupler made as described in Example 1. Over this there is coated a gelatin inter-layer followed in succession by a green sensitive collodion silver halide layer, a second gelatin inter-layer and a blue-sensitive collodion halide emulsion layer.
  • the green-sensitive collodion silver halide emulsion contains as a magenta coupler 2-cyanoacetylnaphthalene-sulfon-N-methylaniline.
  • the blue-sensitive collodion silver halide emulsion contains as a yellow coupler a-benzoyl acetochloranilide, all of these emulsions containing the coupler prepared as in Example 1.
  • the amount of coupler used in the emulsions may vary over wide limits depending upon the dye density to be produced, the thickness of the layers, and other factors. In general, the coupler concentration ranges from about 2 grams to about 15 grams of coupler per liter of emulsion.
  • a. support ill of any suitable material such as cellulose nitrate or cellulose acetate synthetic resin or paper is coated with an emulsion layer ll of suitable cellulosic material containing red-sensitive silver halide particles 12 and particles of a blue-green-dye-generating coupler l 3. Over this is coated agelatin layer It and a layer
  • a support I0 is coated in succession with collodion emulsion layers I 8, I9 and 20 containing respectively silver halide nartigenerating coupler particles 26.
  • the emulsion layers l8 and I! are separated by a gelatin interlayer 21 and the emulsion layers 18 and 20 are separated by a gelatin inter-layer 28.
  • the couplers used in our process may consist of any compounds having a reactive methylene group or a reactive phenolic group which couples with the oxidation product of a primary aromatic developing agent on photographic development to form a dye, and which, although capable of diffusing through gelatin, will not wander out of the collodion emulsion into an adjacent sensitive layer. Couplers of this type are described in the copending application of Vittum and Weissberger, Serial No. 314,679 filed January 19, 1940.
  • Couplers suitable for thus purpose are the following: 7
  • Couplers producing cyan images 2,2-dihydroxy-5,5'-dibromostilbene p,p' -Di- (Z-hydroxybenzamido) -diphenylmethane Sebacic acid di-(2-hydroxyanilide) 8 hydroxy 1-a-naphthoyl-1,2,3,4-tetrahydroquinoline l-naphthol--sulfo-cyclohexylamide 1-naphthol-2-carboxylic-a-naphthalide 5 [N (p toluenesulionyl)l [N' s-hydroxyethyllamino-l-naphthol I 5-diphenylethersulfonamido-l-naphthol 5-phenoxyacetamino-1-naphthol 5 [N benzoyl N-p-hydroxyethyl]-amino-1- naphthol 5-amyldiphenylethersulfona
  • a multi-layer photographic element comprising a plurality of collodion-silver halide emulsions, each containing alkali-soluble color-formers having'a solubility between about 0.01 gram per liter and about 0.05 gram per liter at C. in an aqueous solution having a pH value of 8.5 to 11.0, dispersed therein, the layers being separated by gelatin layers, the color formers being incapable of diffusing past the gelatin layers.
  • a multi-layer photographic element comprising a plurality of collodion-silver halide emulsions, each containing difierent alkali-soluble color-formers having a solubility between about 0.01 gram per liter and about 0.05 gram per liter 20 at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0, dispersed therein, the layers being separated by gelatin layers, the color formers being incapable of diflusing past the gelatin layers.
  • a multi-layer photographic element comprising a plurality of collodion-silver halide emulsions, each sensitive to a different region of the spectrum and containing different alkali-soluble color-formers having a solubility between about 0.01 gram per liter and about 0.05 gram per liter at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0,,dispersed therein, the layers being separated by gelatin layers, the colorformers being incapable of diffusing past the gelatin layers.
  • a multi-layer photographic element comprising three collodion-silver halide emulsions sensitive respectively to the blue, green and red regions of the spectrum and having dispersed therein alkali-soluble color-forming compounds having a solubility between about 0.01 gram per 40 liter and about 0.05 gram per liter at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0, capable of reacting with a primary aromatic amino developing agent on photographic development to produce respectively yellow, magenta, and blue-green images, the layers beingseparated by gelatin layers; the color formers being incapable of diffusing past the gelatin layers.
  • a multi-layer photographic element comprising a plurality of cellulose ester-silver-halide emulsions each sensitive to a different region of the spectrum, at least one of which contains an alkali-soluble color-former having a solubility between about 0.01 gram per liter and about. 0.05 gram per liter at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0 dispersed therein,
  • a multi-layer photographic film comprising a plurality of silver halide emulsion layers each sensitive to a different region of the spectrum, at least one of which layers is a cellulose ester layer containing an alkali-soluble color-former having a solubility between about 0.01 gram per liter and about 0.05 gram per liter at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0, and is separated from the remaining layers by a water- 7 susceptible colloidal material into which the 'color-former does not diffuse.
  • a multi-layer photographic element comprising a plurality of silver-halide emulsion layers each sensitive to a different region of the spectrum, at least one of which layers is a cellulose ester layer containing an alkali-soluble colorformer having a solubility between about 0.01 gram per liter and about 0.05 gram per liter at 20 C. in an aqueous solution having a pH value of 8.5 to 11.0, and is separated from the remaining layers by gelatin into which the color former does not diffuse.
  • the method of forming a colored image in a photographic element comprising a plurality of collodion-silver halide emulsions, which, comprises dispersing in the emulsions dumblerent alkalisoluble color forming compounds having a solubility between about 0.01 gram per liter and about 0.05 gram per liter at 20C. in an aqueou solution having a pH value of 8.5 to 11.0, capable of reacting with a primary aromatic amino developing agent on photographic development, the layers being separated by gelatin layers into which the color formers do not diiiuse, exposing the element to light, and developing theexposed emulsion in a primary aromatic amino developing agent.
  • a multi-layer photographic element comprising a plurality of collodion silver halide emulsionseach sensitive to a diiferent region of the spectrum,v and containing porosity modifiers and dverent alkali-soluble color formers having a I
  • a photographic element comprising a plurality of 10 collodion silver halide emulsions which comprises mixing porosity modifiers with the collodion of the emulsions and dispersing in the emulsions different alkali-soluble color forming compounds having a solubility between about 0.01 gram per liter and about 0.05 gram per liter at 20 C.
  • aqueous solution having a pH value of -8.5 to 11.0, capable of reacting with a primary aromatic amino developing agent on photographic development, layers being separated by gelatin layers into which the color formers do not diiiuse, exposing the element to light and developing the exposed emulsion in a primary aromatic amino developing agent.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US314688A 1939-01-23 1940-01-19 Multilayer photographic material containing color formers Expired - Lifetime US2304939A (en)

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GB2265/39A GB524154A (en) 1939-01-23 1939-01-23 Improvements in colour photographic materials

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2454043A (en) * 1944-04-04 1948-11-16 Ilford Ltd Gelatino-silver halide photographic elements containing higher fatty alcohols
US2478400A (en) * 1945-08-17 1949-08-09 Eastman Kodak Co Silver halide photographic emulsion with developer and color coupler dispersed therein
US2567750A (en) * 1945-10-25 1951-09-11 Du Pont Light sensitive elements for color photography
US2588765A (en) * 1944-03-21 1952-03-11 Gevaert Photo Prod Nv Lubricated photographic element containing a mixture of higher fatty alcohols and higher fatty acids
US2639233A (en) * 1944-06-09 1953-05-19 Polaroid Corp Photographic product for forming a transfer image
US2884325A (en) * 1954-03-05 1959-04-28 Agfa Ag Process for the production of a yellow mask image in magenta-colored photographic images
US3033680A (en) * 1958-01-13 1962-05-08 Eastman Kodak Co Plasticized gelating compositions
DE1130286B (de) * 1961-02-07 1962-05-24 Agfa Ag Verfahren zur Herabsetzung der Viskositaet von farbstoffkomponentenhaltigen photographischen Halogensilber-Gelatineemulsionen
EP0124795A2 (fr) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Emulsion photographique aux halogénures d'argent
EP0136924B1 (fr) * 1983-10-05 1987-09-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0320939A2 (fr) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent
EP0452984A1 (fr) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique à l'halogénure d'argent pour un emploi photographique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE528163A (fr) * 1953-04-17
US4973535A (en) * 1987-09-21 1990-11-27 Eastman Kodak Company Photographic recording material comprising a dye image-forming coupler compound

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2588765A (en) * 1944-03-21 1952-03-11 Gevaert Photo Prod Nv Lubricated photographic element containing a mixture of higher fatty alcohols and higher fatty acids
US2454043A (en) * 1944-04-04 1948-11-16 Ilford Ltd Gelatino-silver halide photographic elements containing higher fatty alcohols
US2639233A (en) * 1944-06-09 1953-05-19 Polaroid Corp Photographic product for forming a transfer image
US2478400A (en) * 1945-08-17 1949-08-09 Eastman Kodak Co Silver halide photographic emulsion with developer and color coupler dispersed therein
US2567750A (en) * 1945-10-25 1951-09-11 Du Pont Light sensitive elements for color photography
US2884325A (en) * 1954-03-05 1959-04-28 Agfa Ag Process for the production of a yellow mask image in magenta-colored photographic images
US3033680A (en) * 1958-01-13 1962-05-08 Eastman Kodak Co Plasticized gelating compositions
DE1130286B (de) * 1961-02-07 1962-05-24 Agfa Ag Verfahren zur Herabsetzung der Viskositaet von farbstoffkomponentenhaltigen photographischen Halogensilber-Gelatineemulsionen
EP0124795A2 (fr) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Emulsion photographique aux halogénures d'argent
EP0136924B1 (fr) * 1983-10-05 1987-09-23 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0452984A1 (fr) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique à l'halogénure d'argent pour un emploi photographique
EP0320939A2 (fr) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent

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GB524554A (en) 1940-08-08
GB524555A (en) 1940-08-08
GB524154A (en) 1940-07-31
FR867331A (fr) 1941-10-13

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