Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
• • 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
  • G03C1/83—Organic dyestuffs therefor
  • G03C1/832—Methine or polymethine dyes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J13/00—Discharge tubes with liquid-pool cathodes, e.g. metal-vapour rectifying tubes
  • H01J13/02—Details
  • H01J13/48—Circuit arrangements not adapted to a particular application of the tube and not otherwise provided for
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J2893/00—Discharge tubes and lamps
  • H01J2893/0072—Disassembly or repair of discharge tubes
  • H01J2893/0073—Discharge tubes with liquid poolcathodes; constructional details

Definitions

• This invention relates to colour photography and more particularly to a simplified multilayer material for use in colour photography.
• a yellow filter layer is usually employed between the uppermost (blue sensitive) layer and the other sensitive layers, which in addition to being sensitised to other parts of the spectrum are also sensitive to blue light.
• the yellow filter layer absorbs the blue light and prevents it striking these lower sensitive layers.
• the coating of the yellow filter layer itself provides an undesirable complication of the process of manufacture of .the photographic film or paper and when colloidal silver is used in theyellow filter layer, as is usual in commercial processes, further complications are-- introduced by the necessity of coating separationlayers between. the filter layer and the light sensitivelayers to avoid fogging. of the sensitive emulsions by the colloidal silver.
• a photographic material adapted for use in colour photography which comprisesthree differently sensitisedv gelatinoesilver halide .emulsion layers containin yellow, magenta and cyan colour formers superimposed on a support, characterised in that one of the outermost sensitive layers is sensitive to blue light and is adjacent to, and; not separated by a filter layer from the middle sensitive layer which middle sensitive layer contains a yellow styryl dyestuif as hereinafter defined.
• the yellow styryl dyestuffs used in; the process of the present invention which function both as a yellow filter 'dyestuff and as amagenta colour former arethe water'soluble dyestuffs which carry a substituent rendering the dyestuff' non-diffusible, for example a substituent containing an alkyl chain of at least 5 carbon atoms, and which are obtainable by condensing a reactive methylene compound with an anil of a Water-soluble or alkali-soluble aldehyde of the formula and wherein at least one of the radicals R1 and.
• R2 is an alkyl radical substituted with for exam-. ple, CN, COOAlkyl, NO2 carboxyl or sulphonic acid groups, and, when only one. of the radicals R1 and R2 is an alkyl radical so substituted, the other radical isa substituted or unsubstituted hydrocarbon radical.
• Suitable styryl'dyestufis may be obtained by condensing an anil of a p-substituted-aminobenzaldehyde with a reactive methylene compound of the kind used for forming magenta dyestuffs in colour photography by reaction with colour developers.
• reactive methylene compounds may be for example, compounds of the pyrazolone series or of the cyanoacetylseries.
• p-substituted-amino-benzaldehydes there may be mentioned for example p-(N- methyl N sulphoethyl amino) -benzaldehyde, p-(N :N 5:5 disulphodiethylamino) -benzaldehyde, 4-(NzN' 6:18 disulphodiethylamino)-2- methyl benzaldehyde, p-(N-methyl-N-carboxyethylamino)-benzaldehyde, p-(N:N-;9:;8.' dicarboxydiethylamino) -benzaldehyde, p-N :N-di(carboxymethyD-amino benzaldehyde, p-(N-B-sulphoethylamino) benzaldehyde, 4 (N:N 6:5- dichlorodiethylamino)
• p-NzN-di-(carboxymethyl) -amino benzaldehyde may be made by introducing the aldehyde group into di-(ethylcarboxymethyl) -aniline by the method of Vilsmeier and Haaok (Berichte, volume 60, page 119) and hydrolysing the diester so obtained.
• Ihe other monoor di-(carboxyalkyl) derivatives may be made by hydrolysis of the appropriate cyanoalkyl compounds which may be made by treating the corresponding hydroxyalkyl or dihydroxydialkyl anilines with phosphorus pentabromide, treating the corresponding bromoalkyl or dibromodialkyl compounds so obtained with potassium cyanide, and introducing the aldehyde group by reaction with phosphorus oxychloride and N-methylformanilide and subsequent hydrolysis, that is to say by the methods of Vilsmeier and Haack (Berichte, volume 60, page 119).
• the monoand di-(sulphoalkyl) derivatives may be made by the action of sodium sulphite on the corresponding chloroalkyl compounds.
• top layer is blue sensitive, the material will be exposed in the normal way to light, but if the bottom layer is blue sensitive, the material will be exposed to light through the support.
• the photographic material in which the photographic material is especially valuable for use in the production of colour positive transparencies and prints, there are 3 sensitive layers superimposed on the support, the top layer being blue sensitive (that is not spectrally sensitised) and containing a yellow colour former, the middle layer containing a styryl dyestuff as hereinbefore defined, which serves both as a yellow filter dyestufi and as a magenta colour former and the bottom layer containing a cyan colour former, either the middle layer or the bottom layer being red sensitive and the other being green sensitive.
• the top layer being blue sensitive (that is not spectrally sensitised) and containing a yellow colour former
• the middle layer containing a styryl dyestuff as hereinbefore defined, which serves both as a yellow filter dyestufi and as a magenta colour former and the bottom layer containing a cyan colour former, either the middle layer or the bottom layer being red sensitive and the other being green sensitive.
• Such a photographic material may be exposed and processed by known means when the filter dyestuff is largely discharged in the developing process.
• the material may, if desired, be treated after the development step with hydrazine hydrate which may if desired be added to the fixing bath.
• magenta dyestuiT obtained from the yellow styryl dyestuff is not entirely suitable for a positive print or transparency, then some modification is possible by the addition to the yellow styryl dyestuff of a small proportion of a colourless colour former yielding a suitable magenta dyestuil.
• a second embodiment of our invention in which the photographic material is especially valuable for the production of negative transparencies, there are 3 sensitive layers superimposed on a support, the top layer being blue sensitive (that is not spectrally sensitised) and containing a yellow colour former, the middle layer containing a mixture of a yellow styryl dyestufi as hereinbefore defined and a yellow styryl dyestuff derived from a reactive methylene compound and a water-insoluble and alkali-insoluble p-N-substituted amino-benzaldehyde, and the bottom layer containing a cyan colour former, either the middle layer or the bottom layer being red sensitive and the other being green sensitive.
• Suitable water-insoluble and alkali-insoluble p-N-substituted amino-benzaldehyde are p- (N-methyl-N-fi-hydroxyethylamino) benzaldehyde, p-(N-ethylN B hydroxyethylamino) -benzaldehyde, p- (,3 c-dihydroxydiethylamino) -benzaldehyde, p- (N-methyl-N-methoxyethylamino) -benzaldehyde, p- (N-ethyl-N-methoxyethylamino) -benzaldehyde, p- (N-butyl-N-fi hydroxyethylamino) -benzaldehyde, p- (N-methyl-N-e-chloroethylamino) -benzaldehyde, p-(N- ethyl
• Such a photographic material may be exposed and developed, bleached and fixed by known means and then treated with formaldehyde or sodium nitrite when a yellow colour correction mask is formed in the middle layer. It is su gested as a possible explanation of this process that both styryl dyestuifs function as filter dyestuffs and colour formers and that in the development with an aromatic amine as developer, magenta images are formed in the exposed parts of the middle layer by the action of the oxidation product of the developer on the styryl dyestuffs and the rest of the styryl dyestuffs are decomposed by the developer to give the parent reactive methylene compounds and also anils formed from the parent aldehydes by reaction with the developer.
• the anil from the soluble aldehyde is washed out from the photographic material during the processing steps.
• the insoluble aldehyde is liberated from the corresponding anil by the action of formaldehyde or sodium nitrite and it then reacts with the reactive methylene compound to re-form the yellow styryl dyestuiT. Since the concentration of residual reactive methylene compound Will be much higher in the counter-imagewise parts of the layer than in the imagewise parts (where it has been used for forming magenta dyestuffs) then the intensity of yellow styryl dyestuff formed will be higher in the counter-imagewise parts and accordingly the, styryl dyestuiT will form a colour correction masking image.
• the strength of the masking image can be controlled by adjusting the proportions of the two styryl dyestuffs in the layer.
• Example 1 A multilayer light sensitive photographic paper is made up as follows:
• a red sensitive gelatino-silver halide emulsion layer containing 10 grams per litre of the sodium salt of the cyan colour forming component l-hydroxyl-sulpho- 2 naphthoyloctadecylamide is coated on a paper support and on this layer there is coated a gelatin separation layer and subsequently a green sensitive gelatino-silver halide emulsion layer containing 15 grams per litre of the sodium salt of the yellow styryl dyestuff 1- (4'-phenoxy-3'-sulphophenyl) -3-heptadecyl 4 p N:N- di (carboxyethyl) aminobenzylidene-S-pyrazolone, to act both as the magenta colour forming component and also as the yellow filter dyestuff.
• a gelatin separation layer is then coated and finally as the top layer there is coated a blue sensitive gelatino-silver halide emulsion containing 10 grams per litre of p-stearylamino-benzoylacetanilide-p'-carboxylic acid sodium salt, the yellow colour forming component described in Example 3 of British specification No. 486,848.
• the paper is exposed to the light transmitted by a subtractively coloured negative transparency and then developed in a solution of the following composition:
• the paper is further washed andltreatedulna fixing and dyestuff-discharee solutionof the following composition:
• the paper is finally washed and dried when a positive paper print is obtained.
• This layer serves as a yellow filter layer, and provides the magenta colour forming components and also the yellow masking dyestufi.
• a blue sensitive gelatino-silver halide emulsion containing 10 grams per litre of p-stearylamino-benzoy1acetanilide 3p carboxylic acid sodium salt (the yellow colour forming component described in Example 3 of British specification No. 486,848)
• the film is exposed to the light from a coloured object and developed in a developer solution of the following composition:
• Parts 3 1 p-N N diethylaminoaniline hydrochloride- Sodium sulphite, anhydrous Sodium carbonate, anhydrous 60 Potassium bromide 2 Water to make up to 1000 6 ofthe developer solution has been-removedr duing the processing" and washing steps.
• the processed material contains in the first layer a cyan dyestuif.,negative image, in the second layer a magenta dyestufi negative image and a yellow styryl dyestufi positive image and in the etopzlayer:a;yellowz:dyestuff :negative' image.
• Example 4 In addition to the yellow styryl dyestuff of Example 3 there may be added 3 grams of the colourless colour former 1-(4-phenoxy-3'-sulphophenyl) 3 heptadecyl-S-pyrazolone(sodium salt).
• a photographic material adapted for use in colour photography which comprises three superimposed differently sensitized gelatino-silver halide emulsion layers, the layers comprising a middle sensitive layer between two outermost sensitive layers, said layers containing colour formers which couple with the oxidation product of a primary aromatic amino developer to form the color image and are adapted to yield, upon exposure and development, yellow, cyan and magenta coloured images in separate layers, said material being characterized in that one of the outermost sensitive layers is sensitive to blue light and is adjacent to, and not separated by a filter layer from, the middle sensitive layer, which middle sensitive layer contains a water-soluble yellow styryl dyestuff carrying a substituent which renders the dyestufi non-difiusible and obtainable by condensing a reactive methylene compound selected from the group consisting of compounds of the pyrazolone and cyanoaeetyl series, with an anil of an aldehyde selected from the group consisting of water-soluble and alkal
• R is selected from the group consisting of an unsubstituted monocyclic aryl radical and a sulphonic acid substituted monocyclic aryl radical, at least one of the radicals R1 and R2 is a substituted alkyl, said substituent being selected from the group consisting of cyano, carboxy alkyl, nitro, chloro, carboxyl and sulphonic acid groups, and when only one of the radicals R1 and R2 is said substituted alkyl, the other radical is a hydrocarbon radical wherein one of R, R1 and R2 in all cases contains a member from the group consisting of carboxyl and sulphonic acid groups in the case of R1 and R2 and-a sulphonic acid group in the case of R.
• top layer is blue sensitive and contains a colour former adapted to yield a yellow coloured image upon exposure and development and the bottom layer contains a colour former adapted to yield a cyan coloured image upon exposure and development, one of the layers other than the top layer being red sensitive and the other layer being green sensitive.
• top layer is blue sensitive and contains a colour former adapted to yield a yellow coloured image upon exposure and development
• bottom layer contains a colour former adapted to yield a cyan coloured image upon exposure and development
• middle layer contains a mixture of said yellow styryl dyestufi and a yellow styryl dyestufi which is the condensation product of a reactive methylene compound and a water-insoluble and alkaliinsoluble p-N-substituted amino-benzaldehyde, the substituent on the p-N atom being selected from the group consisting of alkyl, chloroalkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl, and alkyl carboxyalkyl groups, one of the layers other than the top layer being red sensitive and the other layer being green sensitive.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (6)

Citations (5)

• 0
  • BE BE507221D patent/BE507221A/xx unknown
• 1950
  • 1950-11-20 GB GB28301/50A patent/GB698047A/en not_active Expired
• 1951
  • 1951-11-13 US US256127A patent/US2688541A/en not_active Expired - Lifetime
  • 1951-11-20 FR FR1050450D patent/FR1050450A/fr not_active Expired
  • 1951-11-20 CH CH302939D patent/CH302939A/de unknown

Patent Citations (5)

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