US3753395A - Photo-thermographic recording process with 5-pyrazolane - Google Patents

Photo-thermographic recording process with 5-pyrazolane Download PDF

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US3753395A
US3753395A US00132585A US3753395DA US3753395A US 3753395 A US3753395 A US 3753395A US 00132585 A US00132585 A US 00132585A US 3753395D A US3753395D A US 3753395DA US 3753395 A US3753395 A US 3753395A
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pyrazolin
group
image
compound
reducing agent
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A Poot
Besauw J Van
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor

Definitions

  • ABSTRACT A photosensitive recording material containing a pyrazolin-S-one reducing agent having at least one hydrogen atom in its 4-position in chemical interreactive relationship with a photoreducible dye capable when exposed to activiating electromagnetic radiation adsorbable by the dye of initiating oxidation of the pyrazolin-S-one reducing agent, whereby imagewise exposure of the material to such radiation causes the reducing properties of said pyrazolin-S-one agent to be substantially eliminated in the exposed areas thereof and an image recording method using the same.
  • the material can also contain a bi-imidazolyl compound.
  • thermographic process a heatsensitive copy sheet is used, which when heated beyond a certain temperature, turns black or dark coloured.
  • the original containing infrared light-absorbing image areas is exposed to infrared radiation while being in heatconductive contact with the copy sheet.
  • the copy sheet reaches a temperature at which a coloured product is formed. So, in this process heat is used, which is accumulated image-wise in the original and transferred therefrom to the copy sheet.
  • the copy paper will remain heatsensitive and the image-containing copy paper will be blackened completely by overall heating. This characteristic and the fact that this process is limited to the copying of originals containing infrared radiationabsorbing image-markings on an infrared radiationreflecting background make that process less attractive.
  • an intermediate photosensitive sheet is used for the information-wise exposure.
  • the intermediate sheet includes a first reactant that becomes transformed with the aid of exposed photoreducible dye into a form that is unreactive for a second reactant contained in a receptor sheet.
  • the photoreducible dye has been characterized by its ability to cause reduction of silver ions in a dilute solution of silver nitrate and triethanolammonium nitrate.
  • a photographic recording and reproduction process based on a photochemical reduction of photoreducible dyes has hitherto been mentioned, e.g., in the U.K. Pat. 903,942 filed July 26, 1960 by Gisela K. Oster and Gerard Oster (corresponding with U.S. Pat. 3,145,104 of Gisela K. Oster and Gerard Oster, issued Aug. 18, 1964).
  • the chemicals being in inter-reactive relationship with the photo-reducible dye are polymers containing sulfhydryl groups. Said groups become oxidized on irradiation of the photoreducible dye and form disulphide groups crosslinking the polymer chains.
  • the first and second reactant are capable of rapidly chemically inter-reacting at a conversion temperature between about 90 C and about 150 C with production of a visibly distinct reaction product.
  • the first and second reactants are characterized by a positive result in a test which conveniently is run as follows.
  • material A being said first reactant is first dissolved in an inert liquid solvent at low concentration.
  • the solvent is selected to be non-reactive with either of the reactant materials, and neither absorbs nor is altered by the actinic radiation employed.
  • the concentration of material A is just sufficient to produce a distinctly visible reaction with material B being the second reactant.
  • a portion of the solution is in a small transparent quartz test tube, is exposed to radiation of 3,0004,200 A. from a B-H6 high pressure mercury arc lamp at 6 inches from the sample for a time up to 45 minutes. A second portion is retained as a control.
  • a small amount of material B is then mixed into each of the irradiated and the non-irradiated portions, with heating on a waterbath to about C, where required, and the two solutions are compared for colour.
  • a system in which the colour of the test solution is widely different or decidedly reduced in intensity from that of the control, is by definition according to the above-mentioned U.S. Pat.
  • 3,094,417 a readily desensitizable system as that term is employed in that document and useful in the practicizing the invention described therein.
  • the B-A6 lamp is marketed by General Electric, U.S.A.; the output of the lamp in the wavelength region of 3,200-4,000 A. is 109.3 Watt (see U.K. Pat. 966,694 filed Aug. 10, 1960 of Minesota Mining and Manufacturing Co.
  • First reactants or reactants A mentioned in connection with properly selected second reactants are 4- methoxy-l-naphthol, dithiooxamide ascorbyl palmitate, l-phenyl-dithiohydrazocarbonamide, N,N'-bis(ptoluenesulphonyl)-N,N-dichloroethylenediamine, tin- (II)sulphate, 2-methyl- 5-hexadecyl-benzoquinone, N- nitroso-diphenylamine and 3,3-dimethoxy-4.4'- diphenylene-bis(3-methyl-3-(sodium methylene carboxylate l -triazene.
  • One aspect of the invention makes use of the discovery that pyrazolin-S-one compounds containing at least one hydrogen atom in the 4-position are capable of reducing a noble metal salt of an organic acid at elevated temperature.
  • a further aspect of the invention is based on the fact that such pyrazoline-S-one compounds are capable of reaction with exposed photosensitive substances which during exposure are converted to a form which exerts an oxidizing function.
  • a particular class of such photosensitive substances are the so-called photo-reducible dyes.
  • the exposed sample containing 4-methoxy-lnaphthol showed already before reaching the temperature of 60 C a substantial lower colour intensity when compared with the unexposed sample.
  • the colour produced at the temperatures of 60-80 and 95 C respectively changed from grey over palebrown to deep brown.
  • the exposure unit used in the test was a so-called photochemical reactor RAYONET TYPE RS" provided with 4 RUL 3500 A. tube like lamps having a total capacity of 800 W and emitting in the wavelength range of 300 to 400 nm.
  • test was carried out with 0.005 by weight solutions of products I and ii in n-propanol.
  • reducible dye being in inter-reactive chemical relationship with a said pyrazolin-S-one compound as a first reactant, the exposure being carried out for a time and with an intensity sufficient to cause a 5 corresponding destruction of reducing capacity of pyrazolin-5-one molecules contained in the exposed portions, and overall heating the recording element under conditions to allow the pyrazolin-S-one compound in the unexposed areas to come into contact, e.g., in situ or by physical transference with a second reactant with which by chemical reaction it forms a physicallyor chemically-detectable change, for example a colour change.
  • a photothermographic recording process comprises using an intermediate recording material containing a transferable pyrazolin-S-one compound being in chemical interreactive relationship with a photoreducible dye which in a first step is information-wise exposed with electromagnetic radiation to activate the dye for the destruction of the reducing power of the pyrazolin-S-one compound in the exposed areas and wherein in a second step heat is applied to transfer unmodified reducing pyrazolin-S-one compound, e.g., by vapourisation or as a result of melting of a binding agent therefor (when present) from the intermediate sheet to a receiving material such as a receptor sheet containing a reducible substance with which the pyrazolin-S-one compound is capable of reacting to form a substance differing in colour from the reactants.
  • R1 1% o o N Rr- -RI
  • R stands for hydrogen, an organic group, e.g., an allphatic or carbocyclic group including said groups in substituted form, e.g., an alkyl group, preferably a C C, alkyl group, a cycloalkyl group, e.g.
  • a cyclohexyl or cyclopentyl group a substituted alkyl group, e.g., a benzyl group, a cyano alkyl group, a halogen substituted alkyl group, an aminosubstituted alkyl group, a dialkyl aminoalkyl group, an aryl group, e.g., a phenyl group including a substituted aryl group, e.g., an aryl group substituted with substitucnts of the group of alkyl, halogen,
  • a substituted alkyl group e.g., a benzyl group, a cyano alkyl group, a halogen substituted alkyl group, an aminosubstituted alkyl group, a dialkyl aminoalkyl group, an aryl group, e.g., a phenyl group including a substituted aryl group, e.g., an aryl group
  • a heterocy- 6o ciic group including a substituted heterocyclic group, e.g., a benzothiazolyi group,
  • R stands for hydrogen, an organic group, e.g., an aliphatic or carbocyclic group including said groups in substituted form, e.g., an alkyl group, preferably a C,-C,, alkyl group, a cyeloalkyl group, e.g., cyclohexyl or cyclopentyl, a substituted alkyl group, e.g., a benzyl group, a carboxy-substituted alkyl group, a halogen-substituted alkyl group, a hydroxyl- 6 substituted alkyl group, an alkoxy-substituted alkyl Q Q group, a hydroxyl group including an etherified hydroxyl group, an ester group, an amino group, a substituted amino group, e.g., an acylamino group, a substituted acylamino group, an ureido group, a 5 J substituted urei
  • G1 with halogen e.g., chlorine or bromine
  • halogen e.g., chlorine or bromine
  • alkoxy group with an alkoxy A carbonyl group or with an anilinocarbonyl group
  • C -C alkyl group or a 4-amino phenylamino Q 'Q' group, at least one of the substituents R or R CH being hydrogen.
  • CH7 N/ H The following is a list of suitable R R R and R a substituents of pyrazolin-S-one compounds applicable GoN(CHa)h C0N(CHa)h Axons).
  • C2Hh in the present invention 40 NHCOCH3, Bl, NHN(C:H5)1.
  • the pyrazolin-S-one compounds can be prepared by condensation of a proper hydrazine with a selected active methylene keto compound such as an acyl acetic ester.
  • a selected active methylene keto compound such as an acyl acetic ester.
  • a solution is prepared in an inert neutral light-stable liquid solvent containing per litre of solution approximately 0.001 mole of silver nitrate, 0.01 mole of triethanolammonium nitrate (prepared, for example, by neutralizing triethanolamine with nitric acid), and 0.0001 mole of the dye.
  • concentrations are not critical but should be of the indicated order of magnitude.
  • Water is apreferred solvent where the dye to be tested is soluble therein; methanol, dioxane, or mixtures of these with water are useful with dyes that are insoluble or partially soluble in water alone. Two ml portions are placed in Pyrex test tubes in a water-bath at 50 C.
  • the two tubes are then visually compared.
  • the control tube is found to contain a visible trace of precipitated silver, ordinarily as a fine black powder.
  • the amount of silver precipitated from the test solution is significantly increased. Large increases may be estimated visually, or the amounts of precipitate may be determined by quantitative analysis. Precipitation of silver under test conditions may occur in the form either of dense black flakes or of a silver mirror on the clean wall of the tube.
  • the silver precipitate may be distinguished from precipitated portions of dye or other materials by its insolubility in excess of organic solvent.
  • Copious precipitation of silver occurs in the justdescribed test when applied to halogen-containing fluorescein dyes, e.g., erythrosin, Rose Bengale, D & C Orange l6, and Aizen Acid Phloxine PB, and to pararosaniline dyes, e.g., Calcozine Violet Ex.Conc.
  • fluorescein dyes e.g., erythrosin, Rose Bengale, D & C Orange l6, and Aizen Acid Phloxine PB
  • pararosaniline dyes e.g., Calcozine Violet Ex.Conc.
  • the dye is a coloured organic compound that absorbs light in the visible wavelength range above about 420 nm, which causes reduction of silver ion and precipitation of metallic silver under the test conditions hereinbefore described, and which reduces under irradiation with visible light the reducing power the pyrazolin-S-ones have at elevated temperatures, e.g., at -1 50 C.
  • Another test that can be used to determine whether an operable dye is at the disposal or not makes use of the photo-oxidation by means of these dyes of a compound containing a sulfhydryl group, e.g., a thiol polymer.
  • Dyes that on irradiation with visible light sensitize the oxidation of the sulfhydryl groups of a thiol polymer are described, e.g., in the UK. Pat. 903,942 mentioned above. These dyes include rose bengal, phloxine, erythrosine, eosin, fluorescein, aeriflavine. thionine, riboflavine, chlorophylls, hematoporphyrin. proflavine, methylene blue, and the like. The dyes thus include mem bers of the fluorescein family, the thiazine family, and
  • the amount of photoreducible dye may be varied over wide ranges in respect of the pyrazolin- -one compound, it is preferred to employ minimal amounts so that the light may readily penetrate the dyed coating and allow a reflux exposure in combination with opaque originals having differentially lightabsorptive image and background areas.
  • the light-sensitive sheets used according to the present invention contain at least one pyrazolin-5-one compound in a ratio of preferably 1 mole to 0.1-0.2 mole of photo-reducible dye(s).
  • the pyrazolin- 5-one compound is applied in an amount of 0.1 to 1.5 g per sq.m., but the amount can be adapted according to the requirements of the copying process and the kind of photoreducible dye(s) and reducible substance in the receptor layer or sheet.
  • the photoreducible dye(s) and the reducing pyrazolin- 5-one compound which is transferable by heat in volatilized or molten state, are applied together from a solution or dispersion preferably in the presence of a filmforming binding agent to a suitable support.
  • binding agent for the photosensitive layer all kinds of natural, modified natural and synthetic resins can be used, e.g., proteins such as gelatin, cellulose derivatives, e.g., a cellulose ether such as ethylcellulose, cellulose esters, carboxymethyl cellulose, alginic acid and derivatives, starch ethers, galactomannan, polyvinyl alcohol, poly-N-vinylpyrrolidone, polymers derived from a,B-ethylenically unsaturated compounds, e.g., homoand co-vinyl polymers such as polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate partially saponified polyvinyl acetate, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, or polyethylene.
  • proteins such as gelatin, cellulose derivatives, e.g., a cellulose ether such as ethylcellulose, cellulose esters
  • the ratio by weight of pyrazolin-S-one compound to binder is e.g., 0.02-0.3.
  • the photosensitive material may consist of a selfsupporting sheet or may comprise a photosensitive layer applied to a support.
  • Suitable supports are, e.g., supports of paper of which glassine paper is preferred, and resin supports known in silver halide photography. It is also possible to apply the photosensitive material to glass or to a support from which it can be stripped off and transferred to a permanent support.
  • a receptor layer or separate material used in conjunction with a photosensitivematerial applied an intermediate sheet contains a substance that is a reactive component in a colour reaction with the reducing pyrazolin-S-one contained in the photosensitive sheet.
  • a practical test that can be used to know whether a particular reducible compound used in a receiving layer or sheet is suited or not to produce a visible colour change with the pyrazolin-S-one compound is to heat the elected reaction partners in one ofthe above binding agents or an inert solvent beyond a temperature of 60 C with a particular reaction partner to be used in the receiving layer or sheet, and to take notice,
  • the pyrazolin-S-compounds have a particularly high reactivity with the photo-exposed photo-reducible dyes, which is important in order to obtain clear copies in the receptor layer or sheet within a suitable exposure and processing time.
  • Reaction partners for the reducing pyrazolin-S one compounds are, e.g.,
  • Noble metal compounds e.g. silver compounds, which under the conditions of the copying process of the present invention are extremely non-light sensitive, e.g., the silver salts of aliphatic carboxylic acids with a thioether group such as described, e.g., in the U.K. Pat. 1,111,492 filed Aug. 13, 1965 by Agfa AG, or silver salts of long chained aliphatic (at least C carboxylic acids such as silver behenate, silver palmitate, silver stearate and others.
  • Diazonium salts that are reactive with the pyrazolin-5-one compound through the active hydrogen atom(s) present in 4-position to the 5-one group. By coupling known from diazotype chemistry the diazonium salts form a dye with said pyrazolones.
  • the layer or sheet in which the image is formed may contain further additives, e.g., toning agents e.g. 1-(2H)-phtha1azinone, and agents which accelerate the reaction for the formation of the image substance, e.g., sterically hindered phenols that on heating become reactive partners in the reduction reaction, e.g., 2,4,6-tritert. butylphenol.
  • Suitable image-receiving layers are known already, e.g., from the U.S. Pat. Nos. 3,094,417 precited, 3,094,619 of Edwin A. Grant Jr., issued June 18, 1963 and 3,094,620 of John L.
  • the spectral sensitivity of the photo-sensitive materials depends on the type of the photo-reducible dye used and the enlargement and/or enhancement of the spectral sensitivity by means of spectral sensitizing dyes.
  • the photoreducible dyes may be used in admixture with photooxidantia such as the bi-imidazolyl compounds described in the U.K. Pat. No. 997,396 filed Mar. 21, 1963 by du Pont de Nemours.
  • the bi-imidazolyl compounds can be spectrally sensitized by means of fluorescing coumarln derivatives having the following general formula W represents hydrogen, an alkyl group including a substituted alkyl group, an aryl group, including a substituted aryl group, e.g. a phenyl group having in the or p-position an alkoxy ordialkylamino group.
  • the coumarin derivative contains a dialkylamino group or alkoxy group in 3 and/or 7 position of the coumarin nucleus.
  • the biimidazolyl compounds are inherently sensitive to ultraviolet light of a wavelength below 300 nm.
  • the biimidazolyl compounds can further be spectrally sensitized advantageously by means of sensitizing dyes known as spectral sensitizing agents in silver halide photography.
  • cyanine dyes Preferably used are cyanine dyes, merocyanines, styryl dyes and rhodacyanines of all sorts, e.g., as described by F.M. Hamer in his book The Cyanine Dyes and Related Compounds, 1964, e.g., as described on pages 90, 100, 433, 502 and 511.
  • sensitizing agents for a photoreducible dye, or a particular biimidazolyl compound can be determined by means of the usual sensitometric tests, without difficulty by those skilled in the art.
  • sensitizing agents not only an increase of sensitivity is reached but also a marked increase of the general sensitivity, which is desirable for obtaining shorter times of copying. Thanks to the possibility of spectral sensitization of recording layers'according to this invention also for the red and green regions of the spectrum it is possible not only to copy coloured originals in an unobjectional way but also to prepare copies in natural colours by a suitable choice of the image-forming systems, which yield dyestuffs in the subtractive selection colours.
  • the information-wise exposure may be carried out-by means of visible light produced, e.g., with an incandescent or fluorescent lamp.
  • the exposure time and intensity are preferably the time and light-intensity required to destroy the ability of the recording material to produce a visible reaction when heated in contact with a silver behenatecontaining receptor sheet.
  • Heat may be applied to the exposed recording material in any way. It has to allow and/or to promote the chemical reaction producing the'visible image.
  • heat may be supplied from heated plates or rollers, from an infrared radiation source, by means of an electric resistance or high-frequency current heating source.
  • the present invention makes it possible to produce by reflex exposure a visible'positive directly legible image on receiving sheets containing an image-forming reactant for the pyrazolimS-one compound transferred from a photosensitive intermediate sheet.
  • the copies need not to be stabilized and have a substantially colourless background.
  • a copy sheet comprising on a thin transparent paper-like backing a thin coating containing a substance that can form a coloured product by reaction with the pyrazolin-S-one compound, but is kept out of direct chemical contact with said compound.
  • Direct chemical contact can be avoided, e.g., by
  • the unitary photo-thermosensitive copy sheet when applied in a reflex exposure technique yields a copy that is directly legible through the rear side-of the transparent support.
  • a pigment such as titanium dioxide and zinc oxide having an average grain size of 5 to l p. allows the penetration on heating of a vaporizable pyrazolin-S-one compound through a binder such as ethylcellulose.
  • the permeable layer may alternatively be replaced by a normally impermeable thin coating of a fusible film-forming material, which melts and becomes compatible (see the UK. Pat. No. 1,184,054 filed Apr. 5, 1966 by Gevaert-Agfa N.V. and the U.S. Pat. 3,223,838 of Shoichiro l-loshino and Akira Kato, issued Dec. 14, 1965 with the underlaying binder medium for the reducible substance.
  • a fusible medium e.g., a fusible waxy or resinous medium. Transfer can be speeded up by using a solvent causing some swelling as described in the U.K. Pat. 1,135,371 filed Jan. 7, 1966 by Agfa AG. Heat transfer of. polymer substrata without solvent swelling is described, e.g., in the Belgian Pat. No. 700,472 flled Dec. 27, 1967 by Gevaert Photo-Producten N.V. corresponding with the UK. Pat. No. 1,195,842 filed June 24, 1966 by Gevaert- Agfa N.V.
  • Example 1 To a map overlay tracing paper the following composition was applied in a ratio of 25 g/sq.m
  • n-(2,5-dichlorophenyl)-3-methyl pyrazolin-S-one 1 g erythrosin 440 mg ethylcellulose 50 g methyl ethylketone up till by coating and drying thereon a continuous thin colourless layer of a ball-milled mixture of silver behenate, phthalazinone as toning agent, 2,6-di-tert.-butyl-4- methylphenol as heat-sensitive reductor, polytert.butyl methacrylate as binding agent (three parts for every parts of silver behenate) and 86 parts of acetone.
  • the dried receptor sheet contained per sq.m an amount of silver behenate equivalent with 0.2 g of silver per sq.m, 400 mg of phthalazinone per sq.m, and 40 mg of 2,6-di-tert.-butyl-4-methylphenol per sq.m.
  • Example 1 was repeated but instead of using the mentioned pyrazolin-S-one, N-(2-chlorophenyl)-3- methyl-pyrazolin-S-one and N-(4-nitrophenyl)-3-methyl-pyrazolin-S-one were used respectively.
  • Example 4 Example 1 was repeated, but the mentioned pyrazolin-S-one was replaced by N-(ph yl)-3,4-dimethylpyrazolin-S-one.
  • An image recording method which comprises imagewise exposing to activating electromagnetic radiation a photosensitive recording layer containing a pyrazolin-S-one reducing agent having at least one'hydrogen atom in its 4-position and in chemically interreactive contact with said agent a photoreducible dye adapted to be activated by said radiation and when activated to initiate oxidation of said reducing agent in the exposed areas of said layer to substantially eliminate the reducing properties of said agent in such areas while such properties in the unexposed areas remain unimpaired.
  • a method according to claim 1, comprising the steps of l. image-wise exposing to activating electromagnetic radiation a photosensitive recording material containing in admixture in a layer of a binder medium a volatilizable pyrazolin-S-one agent and said dye, and

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Cited By (9)

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US4247618A (en) * 1979-05-11 1981-01-27 E. I. Du Pont De Nemours And Company Photoimaging systems with cyclic hydrazides
US5264320A (en) * 1991-09-06 1993-11-23 Eastman Kodak Company Mixture of dyes for black dye donor thermal color proofing
US5922528A (en) * 1998-03-20 1999-07-13 Eastman Kodak Company Thermographic imaging element
US5928856A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5928855A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5994052A (en) * 1998-03-20 1999-11-30 Eastman Kodak Company Thermographic imaging element
US6066445A (en) * 1996-12-19 2000-05-23 Eastman Kodak Company Thermographic imaging composition and element comprising said composition
US6410533B1 (en) * 2000-02-10 2002-06-25 Genzyme Corporation Antibacterial compounds
CN103411908A (zh) * 2013-09-02 2013-11-27 中国科学院合肥物质科学研究院 基于藻红B与Ag+混合水溶液的荧光增强法或比色法检测卤素离子的方法

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US2350380A (en) * 1940-08-01 1944-06-06 Du Pont Photography
US2534050A (en) * 1946-06-11 1950-12-12 Du Pont Process of treating photographic layers containing color formers with metal salt hardening agents
US2940849A (en) * 1957-07-10 1960-06-14 Eastman Kodak Co Planographic dye transfer process
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CA981512A (en) 1976-01-13
GB1338604A (en) 1973-11-28
DE2117053A1 (de) 1971-11-04
BE765402A (nl) 1971-10-07
FR2089285A5 (enrdf_load_stackoverflow) 1972-01-07

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