US2747996A - Photographic element protected against action of ultraviolet radiation - Google Patents

Photographic element protected against action of ultraviolet radiation Download PDF

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US2747996A
US2747996A US318096A US31809652A US2747996A US 2747996 A US2747996 A US 2747996A US 318096 A US318096 A US 318096A US 31809652 A US31809652 A US 31809652A US 2747996 A US2747996 A US 2747996A
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ultraviolet
fading
gelatin
photographic element
group
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Richard O Edgerton
Cyril J Staud
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to GB30020/53A priority patent/GB748189A/en
Priority to FR1104767D priority patent/FR1104767A/fr
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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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/08—Varnishing, e.g. application of protective layers on finished photographic prints
    • G03C11/10—Varnishing, e.g. application of protective layers on finished photographic prints for protection from ultraviolet light
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/132—Anti-ultraviolet fading

Definitions

  • This invention relates to a method of protecting multilayer photographic elements against the action of ultraviolet radiation and to multilayer elements containing ultraviolet filtering materials.
  • an object of the present invention to provide a simple method for protecting finished, multilayer photographic materials against the action of ultraviolet radiation.
  • a further object is to provide finished,- multilayer color materials, such as color print materials, in which the color image is not appreciably subject to fading or discoloration by the action of ultraviolet radiation.
  • ultraviolet absorbing agents such as those described in the Richardson Patent 2,160,907 mentioned above, are quite useful for short periods of time, they fail in providing prolonged protection, clue to actual deterioration of the ultraviolet absorbing agent itself upon prolonged exposure to light.
  • the valuable ultraviolet absorbing properties of ultraviolet absorbing agents such as those shown in the Richardson patent, for example
  • other ultraviolet absorbing agents such as those described in Salniinen and Allen application 91,422, for example
  • the combination of ultraviolet absorbing agents employed in our invention provide prolonged and efiicient protection which has not heretofore been obtainable, the elfect realized being more than a mere additive one;
  • a multilayer photographic element which absorbs ultraviolet radiation of wavelengths between about 300 and 400 millimicrons, but transmits light of wavelength longer than 400 millimicrons.
  • the multilayer photographic elements which are treated according to our invention comprise a support having thereon a plurality (e. g. 2 to 3) of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing at least one (e. g.
  • ultraviolet absorbing compound which absorbs wavelengths of radiation between about 300 and 400 millimicrons (but transmits light of wavelength longer than 400 millimicrons).
  • the ultraviolet absorbing compound in the photographic element is diif erent chemically from that employed in the bathing solution.
  • the combination of dyes exhibits an effect not shared by the compounds individually.
  • the particular combinations of ultraviolet absorbing compounds can be varied, depending on the particular effect desired, although the ultraviolet absorbing compound in the bathing solution must be water-soluble.
  • the ultraviolet absorbing compound in the photographic element may, or may not, be water-soluble, although in the former instance, it" is convenient to employ am'ordant (e. g.
  • R and R1 each represent an alkyl group, such as methyl, ethyl, n-propyl, n-lauryl, etc.
  • R2 represents a hydrogen atom, an alkyl group (such as methyl, ethyl, n-propyl, isopropyl, etc., for example), or an aryl group (such as phenyl, o-, m-, and p-tolyl, m-, and p-chlorophenyl, etc., for example)
  • R3, R4, and Rs each represents an aryl group (such as phenyl, o-, m-, and p-tolyl,
  • R5 represents an alkyl group (such as methyl, ethyl, n-propyl, isopropyl, etc., for example) or an alkoxyl group (such as methoxyl, ethoxyl, etc., for example)
  • Q represents a divalent, nonmetallic atom (e. g. oxygen, sulfur, etc., for example) or radical (e. g.
  • X represents an anion, such as chloride, bromide, iodide, perchlorate, thiocyanate, etc.
  • Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, e. g.
  • those of the benzoxazole series such as benzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, 6-ethoxybenzoxazole, etc.
  • those of the thiazole series such as thiazole, 4,5-diphenylthiazole, 4-phenylthiazole, 5phenylthiazole, etc.
  • those of the thiazoline series such as thiazoline, 4phenylthiazoline, etc.
  • those of the benzothiazole series such as benzothiazole, S-methylbenzothiazole, S-phenylberrzothiazole, etc.
  • D represents the non-metallic atoms necessary to com plete a fluoranthene nucleus.
  • the gelatin layer containing at least one of the above ultraviolet absorbing compounds can be the outermost layer of the photographic element, or such layer can be an interlayer, lying between two photographic emulsion layers, one of which is subject to image degradation due to fading of the coupled-dye image.
  • the gelatin layer containing one of the ultraviolet absorbing compoundsselected from those represented by Formulas I-VIII above is used as an interlayer, its position in the photographic element will depend on which particular emulsion layer containing a coupled-dye image is subject to fading.
  • Patent 2,112,139 issued March 22, 1938; for example, 1-acetylmethylene-Z-methylbenzothiazoline, 1 methyl 2 propionylmethylene fi naphthothiazoline, 1-trichloroacetylmethylene-2-ethylbenzothiazoline, Z-ethyl-1lauroylmethylenebenzoth'iazoline, etc.
  • Typical ultraviolet absorbing compounds represented by Formula I above comprise, for example 3,3'-diethyloxacyanine iodide, 3,3-di-n-lauryloxacyanine perchlorate, 3-ethyl-3-n-lauryloxathiazolinocyanine iodide, 3-met'hyl- 3,4-diphenylthiazolinothiazolocyan ine perchlorate, 3,3- diethyl 5,5 diphenyloxacyanine chloride, 3 carboxymethyl-3-ethylthiacyanine iodide, 3,3-diethylthiacyaninep-toluenesulfonate, etc.
  • Typical ultraviolet absorbing compounds selected from those represented by Formula III above comprise, for example, 7,10-diethyl-8,9-dihydrofluoranthene dicarboxylic anhydride, 7,10-diphenyl- 8,9-dihydrofluoranthene dicarboxylic anhydride, etc.
  • Typical ultraviolet absorbing compounds represented by Formula VI above comprise, for example, 5-benzal-2- phenylimino-4-thiazolidone, 5-benzal-3-ethyl-2-phenylimino 4 thiazolidone, 5 anisal 3 phenyl 2 phenylimino-4-thiazolidone, 5-benZal-2,4-dithiothiazoledione, 5- o-chlorobenzal 2,4 dithiothiazoledione, 5 o methoxybenzal-2,4-dithiothiazoledione, S-p-rnethyl enzal-2,4- dithiothiazoledione, 5 o-hydroxybenzal 3 phenyl 7.- phenylimino-4-thiazolidone, 3phenyl-2-phenylimino-5-osulfobenzal-4-thiazolidone, 5o-carboxybcnzal-3-phenyl- 2-phenylimino-4-thiazolidone, 5-cumal
  • Typical ultraviolet absorbing compounds represented by Formula VII above comprise, for example, 9-ben2alfluorene, 9-p-anisalfluorene, etc.
  • Photographic emulsions containing such agents are described in Sawdey application Serial No. 317,865, filed on even date herewith, now U. S. Patent 2,685,512, issued August 3, 1954.
  • Typical ultraviolet absorbing compounds represented by Formula VIII above comprise for example, 4-benzoyl 2 methylresorcinol, 4 o carboxybcnzoyl 2- methylresorcinol, 4 p sulfobenzoyl 2 methylresorc'inol, 4 [3 (3 chlorosulfonylbenzamido)benzoyll 6- n-hexylresorcinol, etc.
  • Such compounds can advantageously be prepared as described in application Serial art sts No. 317,904, filed on even date herewith, now U. S. Patent 2,719,086, issued September 27, 1955.
  • the water-soluble organic compounds which are employed for treating the photographic element containing different ultraviolet absorbing compounds selected from those of Formulas I-VIII in one of the gelatin layers, comprise compounds selected from those represented by the following formulas, for example:
  • D1 represents a mononuclear aromatic group of the benzene series, such as phenyl, p-hydroxyphenyl, p-tolyl, etc., It represents a positive integer of from 1 to 3
  • Y represents a member selected from the group consisting of a s-triazinyl and an acyl group of a mom onuclear aromatic carboxylic acid, such as benzoyl, and its hydroxyl, alkyl, alkoxyl, etc., derivatives, the watersoluble cyanine dyes selected from those of Formula 1 above, the water-soluble compounds of Formulas VI-- VIII (e. g. those compounds wherein R3,- R4 or Rs represents an aryl group containing a solubilizing group, such as hydroxyl, carboxyl, sulfo, etc.).
  • the above water-soluble ultraviolet absorbing materials have a high ultraviolet absorption in the regions between about 300 and 400 millimicrons, but relatively little absorption in the visible region of the spectrum at wavelength longer than 400 millimicrons.
  • aqueous solutions of the above water-soluble ultraviolet absorbing materials to a multilayer photographic element, such as those described in U. S. Patent 2,304,940 issued December 15, 1942, U. S. Patent 2,322,027, issued June 15, 1943, or U. S.
  • Patent 2,160,907 issued June 6, 1939, by bathing or coating from a simple aqueous solution after the multilayer ele menthas been developed and fixed.
  • the solution of the ultraviolet absorber can be used as the final stage of the processing of the material described in the U. S. Patents 2,160,907; 2,304,940; or 2,322,027, that is, after the final wash but before drying.
  • the ultraviolet absorber may be applied after drying and the photograph rinsedand dried.
  • Patents 2,160,907, 2,304,940 and 2,322,027 we refer to multilayer color materials containing in addition to the emulsion layers containing the dye couplers, a gelatin layer containing at least one ultraviolet absorbing compound, such as one of those selected from Formulas I to VIII above.
  • the following example illustrates a method of applying the water-soluble organic compound, such as those selected from Formulas IX to XII to the multilayer photo graphic element containing at least one, different ultraviolet absorbing compound, such as those selected from Formulas I to VIII.
  • the ultraviolet absorbing compound applied to the photographic element by means of an aqueous solution is usually dispersed in varying degrees of concentration throughout the entire photographic element, however, there is generally a higher concentration in the gelatin overcoat layer than in the other layers.
  • the ultraviolet absorbing compounds such as those represented hy Formulas I to VIlI
  • the water-soluble organic compound such as those selected from Formulas IX to XII will be present primarily in the same layer.
  • the ultraviolet absorbing compounds such as those of Formulas I to VIII
  • the water-soluble compounds such as those of Formulas IX to XII will be present in one of the other layers, primarily the gelatin overcoat layer.
  • a mordant for these compounds can be employed in the gelatin layer.
  • Polyvinylpyridine methyl p-toluenesulfonate, phenol-formaldehyde ion exchange resins, etc. have proven particularly useful as a mordant for the various water-soluble compounds of Formulas IX to XII.
  • mordants bind the water-soluble absorber more firmly to the gelatin layer and permit a washing operation after application of the absorber.
  • the absorber may be introduced at some stage of the process before the final washing, thus obviating the necessity for the aforesaid butfer treatment mentioned above.
  • Styrene-maleamic acid resins (U. S. Patent 2,313,565) have been found to be useful mordants for certain ultraviolet absorbing compounds, such as the cyanine dyes of Formula I. See Fierke application Serial No. 317,896, filed on even date herewith, now U. S. Patent 2,691,579, issued October 12, 1954.
  • the above enumerated compounds are representative of those which can be employed in our invention.
  • Other ultraviolet absorbing compounds can be used to advantage, for example, compounds of Formula VHI where R5 is a hydrogen atom and R5 is an aryl group containing a solubilizing group (e. g. hydroxyl, carboxyl, sulfo, etc.) can advantageously be employed in the after bath treatment.
  • the optimum combinations of ultraviolet absorbers can be determined in accordance with the method described in the above example.
  • the advantages of our invention are especially marked when the ultraviolet absorbing compounds present in the processed photographic element (before treating with the water-soluble ultraviolet absorbing compound) provide protection against ultraviolet radiation but undergo decomposition due to absorption of the ultraviolet radiation. The presence of the water-soluble ultraviolet absorbing compound prevents this unwanted effect.
  • Example 1 --Methyl Nn-laurylanthranilate -(OH2)1iCH3
  • a mixture of 15 g. of methyl anthranilate (Eastman Organic Chemical 159), 25 g. of n-lauryl bromide (Eastman Organic Chemical 896), and 7.6 g. of anhydrous potassium carbonate was heated at ISO-190 C. for 18 hours.
  • the cooled mixture was poured into 40 cc. of water, the oil separated and the aqueous layer extracted twice with 10 cc. portions of ether.
  • the oil and extracts were combined, the ether was distilled, and the residue fractionated in vacuo.
  • the methyl N-lauryl-anthranilate can be crystallized, is desired, from an acetone-methanol mixture by cooling the solution in ice. It then melts at 3940 C.
  • Example 2.--Disalicylbenzidide sodium sulfonate SO NS. S O Ntt A solution of 40 g. of benzidine, 10 g. of phenyl salicylate and 500 g. of a-chloronaphthalene was heated in a 1-liter flask attached to a 12-inch Vigreux column so that the phenol distilled (180200 C.). When no more phenol distilled, the reaction mixture was heated strongly until the temperature of the distilling vapours was between 235-240" C., at which point the reaction was considered to be complete. On cooling to room temperature, the product separated. It was collected by filtration and washed with dioxane and then acetone. The
  • Benzidine (4.6 g.; 0.025 mole) was suspended in 150 ml. of acetic acid, and 5 g. of anhydrous sodium acetate was added. Then 13 g. of m chlorosulfonylbenzoyl chloride was added all at once with good stirring. An immediate precipitate was formed. Stirring was continued for one and a half hours. The yellow precipitate was filtered and dried at 80 C. overnight. Yield 17 g.; theory 14.1 g. p
  • Example 4.'-7,10-diethyl-8,9 dihydrofluoranthenedicarbo'xylic anhydride 36 parts (0.3 mol) of acenaphthenequinone, 50 ml. of di-n-propyl ketone and 300 ml. of methanol were rapidly stirred While 50 ml. of 20 percent methanolic potassium hydroxide were slowly added. Reaction began immediately, the acenaphthenequinone went into solution and 2,5 diethyl-3,4-(l,8-naphthylene)cyclopentadienone (as carbinol) separated as white needles. The reaction mixture was allowed to stand for 4 hours at room temperature, 300 ml.
  • the sodium salt of 4,4'-disulfo p-terphenyl can be prepared as described in Example 5 on page 2 of U. S. Patent 2,004,546.
  • Compound 3 above was prepared by replacing the benzidine of Example 3 above by a molecularly equivalent amount of o dianisidine.
  • the 3,3'-di-n-lauryloxacyanine perchlorate can be prepared as described in Jones, Reed and Kuniskis U. S. application S. N. 291,802, filed June 4, 1952.
  • the Water-soluble compounds of Formulas IX to XII can advantageously be employed in the form of their alkali metal (e. g. sodium, potassium, etc.), ammonium or amine salts, as shown above and in application Serial No. 91,422, mentioned above.
  • the compounds of Formulas VI-VIII which contain a sulfo or carboxyl group can be employed in the form of their alkali metal (e. g. sodium, potassium, etc.), ammonium, or amine salts.
  • Such salts are particularly advantageous when it is desired to apply the ultraviolet absorbing compound to the photographic element by a bathing treatment, such as is described above.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupleddye image subject to fading lying between said support and a gelatin layer containing at least one ultraviolet absorbing compound selected from those represented by the following general formula:
  • R and R1 each represents an alkyl group
  • X represents an anion
  • Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series, and adsorbed to said gelatin outer layer a watersoluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • n represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • 11 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons 3.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • 12 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • 11 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic g'elatino-ernulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • )1 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon three superposed, developed and fixed photographic gelatino-emulsion layers each containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet absorbing compound of the following formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • n represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said adsorbed sulfonic acid salt compound being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing an ultraviolet light absorbing compound selected from those represented by the following formulas:
  • R and R1 each represents an alkyl group
  • - R2 represents amember selected from the group consisting of a hydrogen atom, and alkyl group of l to 3 carbon atoms, and a monocyc'lic aryl group
  • R3, R4 and Rs each represents a monocyclic aryl group
  • R5 represents a member selected from the group consisting of an alkyl group and an alkoxyl group
  • Q represents a member selected from the group consisting of an oxygen atom, a sulfur atom, and an imino group
  • X represents an anion
  • Z and Z1 each represents a non-metallic atom necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series
  • D represents the non-metallic atoms necessary tocomplete
  • N80 38 S O 3N8 wherein D1 represents a monouclear aromatic group of the benzene series, n represents a positive integer of from 1 to 3, and Y represents a member selected from the group consisting of a s-triazinyl group and an acyl group of a i, j, k and I being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:
  • said ultraviolet light absorbing compound affording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic elernent in an aqueous non-colloidal solution of a watersoluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • 11 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:
  • QW-QQWQOH which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • n represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboXylic acid, said sulfonic acid salt being absorbent of ultraviolent light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a paper supmononuclear aromatic carboxylic acid, said compounds port and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:
  • said ultraviolet light absorbing compound aifording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D1 represents a mononuclear aromatic group of the benzene series
  • n represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxlic acid, said sulfonic acid salt being absorbent of ultraviolent light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer containing an ultraviolet light absorbing compound of the following formula:
  • said ultraviolet light absorbing compound aifording temporary protection only against the harmful effects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D represents a mononuclear aromatic group of the benzene series
  • 11 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a method of preventing image degradation in a finished photographic element comprising a paper support and superposed thereon a plurality of developed and fixed photographic emulsion layers containing coupleddye images, at least one of said dye images being subject to fading by the action of ultraviolet light, said emulsion layer containing a coupled-dye image subject to fading lying between said paper support and a gelatin layer con- 16 taining an ultraviolet light absorbing compound of the following formula:
  • said ultraviolet light absorbing compound atfording temporary protection only against the harmful efiects of ultraviolet light due to decomposition on exposure to light, which comprises bathing said photographic element in an aqueous non-colloidal solution of a water-soluble sulfonic acid salt of a compound selected from those represented by the following general formula:
  • D represents a mononuclear aromatic group of the benzene series
  • 11 represents a positive integer of from 1 to 2
  • Y represents an acyl group of a mononuclear aromatic carboxylic acid, said sulfonic acid salt being absorbent of ultraviolet light of wavelength between 300 and 400 millimicrons but transmissive of light of wavelength longer than 400 millimicrons.
  • a finished photographic element comprising a gelatin outer layer and a support having thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupleddye image subject to fading lying between said support and a gelatin layer containing at least one ultraviolet absorbing compound selected from the group consisting of those represented by the following general formulas:
  • R and R1 each represents an alkyl group
  • R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group of from 1 to 3 carbon atoms, and a monocyclic aryl group
  • R3 R4 and Rs each represents a monocyclic aryl group
  • R5 represents a member selected from the group consisting of an alkyl group and an alkoxyl group
  • Q represents a member selected from the group consisting of an oxygen atom, a sulfur atom, and an imino group
  • X represents an anion
  • Z and Z1 each represents a non-metallic atom necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the thiazole series, those of the thiazoline series, and those of the benzothiazole series
  • D represents the non-metallic atoms necessary to complete a fluoranthene nucleus, and adsorbed to said gelatin outer layer a water-

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US318096A 1952-10-31 1952-10-31 Photographic element protected against action of ultraviolet radiation Expired - Lifetime US2747996A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE523923D BE523923A (id) 1952-10-31
US318096A US2747996A (en) 1952-10-31 1952-10-31 Photographic element protected against action of ultraviolet radiation
GB30020/53A GB748189A (en) 1952-10-31 1953-10-30 Method of protecting multilayer colour photographic elements against the action of ultraviolet radiation
FR1104767D FR1104767A (fr) 1952-10-31 1953-10-30 Images photographiques protégées de l'ultraviolet et procédé pour leur obtention

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BE (1) BE523923A (id)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846306A (en) * 1955-06-01 1958-08-05 Ici Ltd Photographic process
US3037863A (en) * 1959-08-14 1962-06-05 Ibm Photosensitive record
US3064260A (en) * 1952-12-26 1962-11-13 Honeywell Regulator Co Recording system
US3069262A (en) * 1958-03-27 1962-12-18 Polaroid Corp Processes for forming dye developer images having stability in sunlight
US3244524A (en) * 1960-03-01 1966-04-05 Gen Aniline & Film Corp U. v. absorbing composition
US3249432A (en) * 1960-08-22 1966-05-03 Polaroid Corp Novel photographic processes
US5110717A (en) * 1990-12-17 1992-05-05 Eastman Kodak Company Stability improvement of amorphous particle dispersions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1152056B (de) * 1960-04-08 1963-07-25 Telefunken Patent Einrichtung zum Sortieren von auf einem Foerderband befoerderten Gegenstaenden unter Verwendung eines synchron mit dem Foerderband mitlaufenden Magnetbandes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB493308A (en) * 1936-04-29 1938-10-06 Ig Farbenindustrie Ag Improvements relating to colour photography
US2241239A (en) * 1939-01-23 1941-05-06 Eastman Kodak Co Ultraviolet light filter
US2295013A (en) * 1936-05-09 1942-09-08 Eastman Kodak Co Method of developing multilayer photographic color films
GB565929A (en) * 1943-03-20 1944-12-05 Kodak Ltd Improvements in the production of coloured photographs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB493308A (en) * 1936-04-29 1938-10-06 Ig Farbenindustrie Ag Improvements relating to colour photography
US2295013A (en) * 1936-05-09 1942-09-08 Eastman Kodak Co Method of developing multilayer photographic color films
US2241239A (en) * 1939-01-23 1941-05-06 Eastman Kodak Co Ultraviolet light filter
GB565929A (en) * 1943-03-20 1944-12-05 Kodak Ltd Improvements in the production of coloured photographs

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3064260A (en) * 1952-12-26 1962-11-13 Honeywell Regulator Co Recording system
US2846306A (en) * 1955-06-01 1958-08-05 Ici Ltd Photographic process
US3069262A (en) * 1958-03-27 1962-12-18 Polaroid Corp Processes for forming dye developer images having stability in sunlight
US3037863A (en) * 1959-08-14 1962-06-05 Ibm Photosensitive record
US3244524A (en) * 1960-03-01 1966-04-05 Gen Aniline & Film Corp U. v. absorbing composition
US3249432A (en) * 1960-08-22 1966-05-03 Polaroid Corp Novel photographic processes
US5110717A (en) * 1990-12-17 1992-05-05 Eastman Kodak Company Stability improvement of amorphous particle dispersions

Also Published As

Publication number Publication date
BE523923A (id)
GB748189A (en) 1956-04-25
FR1104767A (fr) 1955-11-24

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