US3764322A - Photography dry copying process with a merocyanine dye - Google Patents

Photography dry copying process with a merocyanine dye Download PDF

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US3764322A
US3764322A US00174929A US3764322DA US3764322A US 3764322 A US3764322 A US 3764322A US 00174929 A US00174929 A US 00174929A US 3764322D A US3764322D A US 3764322DA US 3764322 A US3764322 A US 3764322A
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image
layer
compounds
image receiving
light sensitive
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H Kampfer
H Ohlschlager
J Gotze
Konig A Von
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • 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

Definitions

  • the present invention relates to a photographic dry copying process and to a light sensitive material for carrying out this process.
  • the photographic materials used are mainly materials which contain layers sensitive to light or to heat. These layers are exposed imagewise to light or heat to initiate a color forming reaction which results in formation of the image.
  • the known light sensitive materials of the type mentioned above which can be used for producing negative copies of images have, however, numerous disadvantages, including the fact that their sensitivity to light is insuflicient, especially in the visible region of the spectrum, so that the copying times required are too long and the reproduction of colored originals is difiicult. Moreover, the produced images are still sensitive to light and generally they can only be stabilized against daylight by a very complicated aftertreatment.
  • the last mentioned process has the disadvantage that the sensitivity of the layers is relatively slight and the keeping quality of the material is limited.
  • R4 (Cae i t
  • R (1) a saturated or unsaturated aliphatic group preferably containing up to 6 carbon atoms which may be substituted, e.g. with halogen such as chlorine, bromine or iodine or with phenyl, hydroxyl, amino, carboxyl, sulfo, sulfamino, sulfamoyl, carbamoyl, carboxyamino, carboxyalkyl, alkoxycarbonyl, sulfate or thiosulfato groups; (2) a cycloalkyl group such as cyclohexyl or (3) aryl, in particular a group of the phenyl series;
  • R and R taken together may represent the ring members required to complete an isocyclic or heterocyclic ketomethylene ring, suitable rings being those commonly found in cyanine chemistry, for example those of the rhodanine series such as 3-ethylrhodanine, 3-allylrhodanine or 3-cyclohexyl rhodanine, those of the 2- thio-2,4-oxazolidinedione series such as 2-ethyl-2-thio- 2,4-oxazolidinedione, those of the thiohydantoin series such as 1,3 dimethyl 2 thio-hydantoin or l-methyl- 3 phenyl 2 thiohydantoin, those of the barbituric acid or thiobarbituric acid series such as 1,3-diethylthiobarbituric acid or 1,3 diphenyl-thio barbituric 3 acid, those of the isoxazolone, oxindole, 2-thio-2
  • R a hydrogen atom, an alkyl group having up to 4 carbon atoms, hydroxyl, alkoxy having up to 4 carbon atoms such as methoxy or ethoxy, or aryl such as phenyl;
  • R (1) a saturated or unsaturated aliphatic group having preferably up to 6 carbon atoms which may be substituted, e.g. with phenyl, hydroxyl, halogen such as chlorine, bromine or iodine, with amino, carboxyl, sulfo or (2) aryl such as phenyl or naphthyl;
  • X oxygen or sulfur
  • n 0, 1, or 2;
  • Q the members required to complete a S-membered or 6-membered heterocyclic group which may contain a condensed benzene or naphthalene ring and further substituents.
  • Suitable heterocyclic groups are those customarily found in cyanine chemistry, for example those of the thiazole series (e.g.
  • thiazole 4 methylthiazole, S-methylthiazole, 4,5 dimethylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4,5-diphenylthiazole, benzothiazole, 4-chlorobenzothiazole S-chlorobenzothiazole, 6- chlorobenzothiazole, 7-chlorobenzothiazole, 6-bromobenzothiazole, 5 iodobenzothiazole, 6-iodobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6- methylbenzothiazole, 5,6 dimethylbenzothiazole, 4- phenylbenzothiazole, 5-pheny1benzothiazo1e, 6-phenylbenzothiazole, S hydroxybenzothiazole, 6 hydroxybenzothiazole, 4 methoxybenzothiazole, 5 methoxybenzothiazole, fi-methoxybenzothiazole, S-ethoxy
  • oxazole 4 methyloxazole, 4 phenyloxazole, 4,5-diphenyloxazole, benzoxazole, 5 chlorobenzoxazole, 6- chlorobenzoxazole, 5,6 dimethylbenzoxazole, 5- phenylbenzoxazole, 5 hydroxybenzoxazole, 5- methoxybenzoxazole, 5 ethoxybenzoxazole, 6 dialkylaminobenzoxazole, 5 carboxybenzoxazole, 5 sul phobenzoxazole, 5 sulphonamidobenzoxazole, 5 )8- carboxyvinylbenzoxazole, naphtho[1,2 d] oxazole, naphtho[2,1 d] oxazole or naphtho [2,3 d]oxazole), those of the imidazole series (e.g.
  • thiazoline 4 methylthiazoline, etc.
  • those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine series those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine series.
  • the heterocyclic rings may carry any substituents, eig they may be substituted with other alkyl groups preferably containing up to 3flcarbon atoms, such as methyl or ethyl, with halogen such as chlorine, iodine or bromine, with trifluoromethyl or hydroxyl or with alkoxy having preferably up to 3 carbon atoms such as methoxy or ethoxy, with hydroxyalkyl, alkylthio or aryl such as phenyl or aralkyl such as benzyl or amino or substituted amino and the like.
  • alkyl groups preferably containing up to 3flcarbon atoms, such as methyl or ethyl, with halogen such as chlorine, iodine or bromine, with trifluoromethyl or hydroxyl or with alkoxy having preferably up to 3 carbon atoms such as methoxy or ethoxy, with hydroxyalkyl, alkylthio or aryl such as pheny
  • the merocyanines according to the invention may be prepared by known methods (see F. M. Hamer The Cyanine Dyes and Related Compounds (1964). Preparation of the open chain cyanothioacetamide merocyanines has been described in British patent specification No. 1,219,330.
  • the image-producing compounds must meet the following conditions:
  • reducing agents for example are particularly suitable image-producing compounds:
  • Phenols and naphthols especially benzene compounds of the naphthalene series containing at least two aromatic hydroxyl groups which may be partly etherified such as 1-hydroxy-4-alkoxy-naphthalenes, or which are substituted with a hydroxyl group and an amino or substituted amino group, substituted being in the paraor ortho-position in the case of benzene derivatives. Examples of such compounds are listed in Table 1 below.
  • image-producing compounds are the aminophenol developers described in German patent specifications 1,159,758, 1,200,679, 1,203,129 and 1,203,- 605.
  • R represents hydrogen, alkyl or aryl which may be substituted for example with lower alkyl or alkoxy groups or with halogen such as chlorine, bromine, or iodine, and
  • R R R and R represent hydrogen, alkyl, aryl or a substituted alkyl or aryl group.
  • the compounds listed above may be prepared by the processes described in British patent specification Nos. 679,677 and 679,678, the phenimines which may be obtained by reacting acrylonitrile derivatives with the corresponding hydrazine compounds being saponified to 3-pyrazolidones.
  • 3-pyrazolidones may also be prepared by the process described in British patent specification No. 703,669, the end products being obtained by direct condensation of esters of acrylic acid or derivatives thereof with hydrazines. This process is particularly suitable for reactions with hydrazine itself.
  • the 3-pyrazolidones obtained in this way which have an oily consistency can be obtained as crystalline compounds by converting them into salts, e.g. hydrochlorides, sulfates, or 1,5-naphthalene disulfonates.
  • salts e.g. hydrochlorides, sulfates, or 1,5-naphthalene disulfonates.
  • the preparation of 4,4-dialkyl-3-pyrazolidones has been described in US. Pat. 2,772,282. In the process described there, 2,2-dialkyl-fl-chloropropionic acid chlorides are reacted with hydrazines.
  • the 3-pyrazolidones may be used as free bases or in the form of their salts.
  • N,N-dialkylphenylenediamine derivatives especially those in which the alkyl groups contain up to 3 carbon atoms and the phenylene nucleus may be substituted with alkyl or alkoxy groups.
  • the free primary amino groups may be blocked, for example in the form of a Schiifs base by reaction with aldehyde, especially benzaldehyde, or with a sulfomethyl group which may be introduced by a Mannich reaction.
  • Phenylenediamine derivatives which have a blocked primary amino group are particularly suitable because stable layers can easily be prepared with such compounds.
  • N,N-diethyl-p-phenylenediaminesulfate N,N'-dibenzylidene-p-phenylenediamine, N,N-diethyl-N'-sulfomethyl-p-phenylenediamine, N,N-dimethyl-N'-sulfomethyl-p-phenylenediamine, 3-methyl-4-sulfomethylamino-N,N-diethylaniline
  • N-benzylidene-N',N'-diethyl-p-phenylenedimaine 3-methoxy-4-sulfomethylamino-N,N-diethylaniline.
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group preferably containing up to 6 carbon atoms which may be substituted, e.g. with phenyl as in the benzyl group, with cyano, with halogen, e.g. fluorine, with amino in which case the amino group may itself be substituted, e.g. alkylated amino groups, especially dialkylamino, the alkyl groups in the alkylamino group preferably containing up to 3 carbon atoms, (3) aryl, especially a group of the phenyl series, the aryl ring being itself optionally substituted, e.g.
  • alkyl or alkoxy preferably containing up to 3 carbon atoms, with nitro, halogen such as fluorine, chlorine or bromine, with amino or substituted amino groups, e.g. alkylated amino groups, (4) a heterocyclic group, e.g. benzothiazolyl or (5) cycloalkyl such as cyclohexyl or cyclopentyl;
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group preferably containing up to 6 carbon atoms, the aliphatic group optionally carrying further substituents, e.g. phenyl as in the case of a benzyl or phenylethyl, halogen such as fluorine, chlorine or bromine, alkoxycarbonyl, hydroxyl or alkoxy, (3) aryl, especially a group of the phenyl series, the aryl ring being optionally itself substituted, e.g.
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having preferably up to 6 carbon atoms which may be substituted, e.g. with phenyl as in the case of benzyl or phenylethyl groups, or With halogen such as chlorine or bromine, nitrile, alkoxy, alkoxycarbonyl or anilinocarbonyl, (3) aryl,
  • 1 1 especially a group of the phenyl series, in which the polyvinyl chloride, copolymers of vinyl chloride and vinyl aryl ring may itself be substituted, e.g. with alkyl or acetate, polyvinyl acetate or completely or partly saponialkoxy having preferably up to 3 carbon atoms, nitro fied polyvinyl acetate or copolymers of vinyl acetate, for or nitrile, (4) amino in which the amino groups may example with olefines such as ethylene or propylene and be substituted, e.g.
  • alkyl having preferably up to copolymers of monomers of acrylic or methacrylic acid 3 carbon atoms, cycloalkyl, phenyl or acyl, especially or derivatives thereof such as esters, amides of nitriles,
  • the light sensitive layers may be used as self-support- (S) alkoxy having preferably up to 3 carbon atoms; ing layers or applied to a support.
  • 13 and 14 may together represent the esters, e.g. cellulose triacetate, polyesters, especially those ring members required to complete a S-membered or 6- based on ethylene f p l glass, em
  • the image receiving materlal advantageously consists of
  • l compounds are listed in the following table an image receiving layer applied to a suitable support.
  • pyrazolin-S-one derivatives are prepared by methfor the light sensitive material are suitable as binding ods known from the literature. Reference may be made agent for the image receiving layer or as the layer supe.g. to the monograph by R. H. Wiley Pyrazolones, port.
  • the light sensitive layers contain at least one of the that the layers will not stick at elevated temperature.
  • These sensitizers in quantities of 10 to 300 mg./m. and one or diificulties are well-known from other transfer more image producing compounds in quantities of 0.02 processes, e.g. the silver salt diffusion process or heat deto 0.5 g./m. This range of concentration has been velopment processes, and can easily be solved by making found to be suitable although amounts outside this range use of the experience gained in these known fields. may, of course, be employed.
  • the concentration depends
  • the image receiving layer contains compounds which mainly 011 the requirements of a Particular l'fipfodllcthm should be insensitive, or as restricted as possible in their process. sensitivity, to visible light under the conditions of the proc- Particularly suitable combinations Of sensitizers with egg of the invention, and which react with the transferred the image producing reducing agents can be determined image producing compounds to form colored products. by simple tests. Suitable tests for this purpose will be Numerous compounds have been found suitable for this described hereinafter. The choice of solvent and of the purpose. Chemically, these compounds belong to a Wide binding agent used for producing the light sensitive layer variety of classes so that their systematic chemical clasis also important for obtaining optimum results. Comsification is not possible.
  • suitable compounds or binations of components particularly suitable for any suitable combinations of an image producing compound given purpose can be determined by the usual tests known arranged in the light sensitive layer and of the reactant to the ordinary skillled person.
  • the image forming reaction in the image receiving T P p the light Sensitivfi y the Sensifilers and layer can be sufficiently clearly defined by simple laboraimase producing compound y be suspended or dissolved tory tests customarily employed in the art.
  • the two reactants must react when briefly heated in this form to the layer support. for a few seconds to a temperature of between about 80
  • the usual natural or synthetic film-forming polymers are and 200 C. to form a stable dye.
  • a second test must then suitable as binding agents for the light sensitive layer, e.g. be carried out to choose suitable image producing comproteins, especially gelatin, cellulose derivatives, especialpounds.
  • the purpose of this test is to show Whether the ly cellulose ethers, cellulose esters or carboxymethyl celluimage producing compound will react sufi'lciently rapidly lose, alginic acid and its derivatives, starch ether or galin the presence of the merocyanine dye on exposure to lactomannane, polyvinyl alcohol, polyvinyl pyrrolidone, light, so that, when the mixture is heated after it has been exposed, it will not produce a colored compound with the reactant in the image receiving layer.
  • the following classes of compounds are examples of suitable compounds in the image receiving layer for reaction with the image producing compound transferred from the light sensitive layer.
  • Heavy metal compounds especially compounds of metals of Groups IIIa to Va and Groups lb, IIb and VIb and VIII of the Periodic Table, e.g. compounds of the following heavy metals: cadmium, mercury, iron, cobalt, nickel, copper, silver, gold, bismuth or thallium. Salts of these metals with long chained aliphatic, carboxylic acids are especially suitable e.g. nickel stearate, cobalt palmitate, iron stearate, and the addition compound of bismuth nitrate with amines such as triethanolamine. It is found to be especially suitable to use silver compounds which are substantially insensitive to light under the conditions of the copying process according to the invention, e.g. the silver salts described in US.
  • the image receiving layer may also contain oxidizing agents and dye components which react imagewise with the transferred image producing compound by oxidative coupling to form dyes, e.g. the known color couplers of color photography which couple with oxidized phenylene diamine derivatives to produce dyes, or compounds which when in their oxidized form react under oxidizing conditions e.g. with pyrazolin-S-one compounds to yield colored coupling products.
  • oxidizing agents and dye components which react imagewise with the transferred image producing compound by oxidative coupling to form dyes, e.g. the known color couplers of color photography which couple with oxidized phenylene diamine derivatives to produce dyes, or compounds which when in their oxidized form react under oxidizing conditions e.g. with pyrazolin-S-one compounds to yield colored coupling products.
  • Suitable reactants for these reactions are e.g. oxidation products of p-phenylene diamines or their derivatives which react with pyrazolin-S- one
  • Diazonium salts which react with the transferred reducing agent, e.g. with aminophenols, aminonaphthols, phenylenediamine derivatives or pyrazolin-S-one compounds, to form a colored product. This reaction is similar in principle to the one employed in the known photographic diazo type process.
  • Leucophthalocyanines are also suitable for use as reactants for the reaction which produces the image dye.
  • Leucophthalocyanines which have not or could not be prepared from finished phthalocyanines are known as phthalocyanine precursors. This term is used, for example, in the article by B. R. A. Brooks, J. G. Burt, B. F. Skiles and M. S. Whelen, J. Org. Chem. 24, page 383 (1959).
  • the term phthalocyano-metal complexes is used for the same type of materials for which in the present context the term leucophthalocyanines is used.
  • Leucophthalocyanines according to this definition are colorless or only slightly colored products in which the phthalocyanine structure is already completely formed, and which can be converted into phthalocyanines by a reduction process. In this reduction process, constituents which the leucophthalocyanine molecule contains in addition to phthalocyanine may also be split off.
  • leucophthalocyanines may be prepared e.g. by first preparing a phthalocyanine, e.g.
  • Leucophthalocyanine which contain metal are more suitable for this reaction because those which are free from metal are relatively unstable.
  • the highly stable and only slightly colored leuco cobalt phthalocyanines are especially suitable.
  • leuco cobalt phthalocyanines which are described in Angewandte Chemie, 68, page 145 (1956), e.g. the phthalocyanine cobalt ethylene diamine complex.
  • ethylene diamine other diamines or polyamine may also be used as ligands, for example propylene diamine-(1,2), and -(1,3), monoethylpropylene diamine (1,3), hydroxyethylethylene diamine, N-methyl-N-fl-hydroxyethylpropylene diamine, N,N'-diethylethylene diamine, N,N-di-(B-aminoethyD-ethylene diamine, N,N'-di- (B-aminoethyD-ethylene diamine or N,N-di-[/3-(/3-aminoethyl)-aminoethyl]-amine or also monoamines such as 3- (2-ethylhexyloxy)-propylamine-(1) or stearylamine.
  • the solubility properties of the leuco-CoPc depend on the type of amine used in the molecule.
  • reactants can be completely omitted from the image-receiving layer.
  • image producing compounds for example phenols or naphthols which yield sufliciently colored compounds when heated alone or in the presence of atmospheric oxygen.
  • plain, uncoated paper may be used as image receiving material.
  • the image receiving layers may contain other additives which advantageously influence the color tone, contrast, stability, etc., of the copy.
  • Image receiving layers of this type are already known and have been described, for example, in German auslegeschrift Nos. 895,101; 1,003,577; 1,159,758; 1,004,043 and 1,165,410, in Dutch patent specification No. 277,086, in US. Pat. 3,335,006 and in Belgian patent specification Nos. 614,064 and 609,- 057.
  • the image receiving layers may also contain white pigments, e.g. zinc oxide, silicon oxide or titanium dioxide as fillers, for improving the whites and for controlling the tendency of the layers to stick, and they may contain terpene resins and organic acids for improving the stability in storage.
  • white pigments e.g. zinc oxide, silicon oxide or titanium dioxide as fillers
  • they may contain terpene resins and organic acids for improving the stability in storage.
  • Image receiving layers of this type have been described in US. Pat. Nos. 3,074,809 and 3,107,- 174.
  • the color tone of the images produced can be altered e.g. with compounds of the 1-(2H)-phthalazinone series. Toners of this type have been described in US. Pat. Nos. 3,080,254 and 3,446,648. Additives which accelerate the reduction reaction in the image receiving layer have also been found to be advantageous. Suitable compounds for this purpose are e.g. sterically hindered phenols such as 2,6-di-tertiary butyl-p-cresol. Compounds of this type have been described in US. Pat. 3,218,166. Furthermore, the image tone and image density can be improved with certain metal salts, e.g. copper-II stearate. Metal ion image intensifiers and their application have been described in German auslegeschrift No. 1,572,209.
  • the usual sources of light used in reproduction work such as mercury lamps, iodine quartz lamps or incandescent lamps, may be used for exposing the light sensitive layers according to the invention.
  • the spectral sensitivity of the light sensitive material depends on the nature of the dye used or the combination of dye and reducing image producing compound.
  • Exposure may be carried out either in contact or optically or by reflection.
  • Transfer of the image producing compounds from the unexposed areas of the light sensitive layers to the image receiving layer is carried out by heating at temperatures of between and 200 C. Heating may be effected e.g.
  • the image receiving layer and the light sensitive layer may be combined on one support.
  • a transparent support on which the image receiving layer e.g. a layer containing silver behenate dispersed in a copolymer of styrene and isobutylene, is applied first, and the light sensitive layer, e.g. an ethylcellulose layer containing the sensitizer and reducing compound, is applied on the image receiving layer.
  • the image receiving layer e.g. a layer containing silver behenate dispersed in a copolymer of styrene and isobutylene
  • the light sensitive layer e.g. an ethylcellulose layer containing the sensitizer and reducing compound
  • the sensitivity of these light sensitive layers may advantageously be increased or extended to other spectral regions to an extent depending on the absorption of the compounds according to the invention by combining the dyes used according to the invention with photoreducible dyes, e.g. those mentioned in US. Pat. 3,094,417, such as erythrosine.
  • the layer is dried in the usual manner.
  • the image receiving layer is prepared by grinding the following components for 6 hours in a ball mill:
  • the layer contains about 0.2 of silver per rn. in the form of silver behenate.
  • the light sensitive material is exposed behind a 2 step Wedge to a 1000 watt iodine quartz lamp from a distance of 30 cm. for 5 minutes.
  • the exposed layer is then brought into contact with the image receiving layer and heated to a temperature of 125 C. for 10 seconds or treated in an ordinary commercial heat development apparatus.
  • the layer is dried in the usual manner.
  • the light sensitive matrial is exposed through a positive transparent original to a 1000 watt normal incandescent lamp (tungsten filament) at a distance of 5 to 10 cm. for 30 seconds.
  • tungsten filament normal incandescent lamp
  • a text printed on ordinary paper may be used instead of a transparent original.
  • the exposure to reflected light required in this case takes 15 to 25 seconds under other- Wise the same conditions.
  • the exposed layer is then brought into contact with the image receiving layer described in Example 1 and the layers are heated to a temperature of to C. for 5 to 20 seconds or treated in an ordinary commercial heat development apparatus.
  • EXAMPLE 3 Light sensitive material A light sensitive layer is prepared from a solution of 30 mg. of dye No. l,
  • Image receiving material A layer is prepared from a solution 1.5 g. of 1-phenyl-3-methylpyrazolone-(5), 1 g. of sodium bromate,
  • a red posi- Image receiving material A layer cast on a paper support is prepared from 150 mg. of N,N-diethyl-p-aminophenyl-diazonium chloride zinc chloride complex,
  • Light sensitive material A light sensitive layer is prepared from a solution of 30 mg. of dye No. 29, 100 mg. of 1-phenyl-3-methyl-pyrazolin-5-one, 2.5 g. of ethylcellulose and 150 ml. of ethyl acetate.
  • the solution is applied to a layer support of glassine paper and dried in the usual manner.
  • Image receiving layer The following casting solution is applied to a layer support of baryta paper:
  • Image receiving material 50 mg. of a leuco cobalt phthalocyanine stearylamine complex prepared by the method described below are dissolved in 40 g. of a 1.5% polyvinylacetate solution in acetone and 26 g. of a 4% cellulose acetate solution in acetone, and the solution is cast on paper and dried.
  • the leuco CoPc used was prepared as follows:
  • Image receiving material An image receiving material is prepared from 5 g. of iron(II-I) chloride, 2 g. of nitrilotriacetic acid and 30 ml. of a 5% aqueous solution of polyvinyl alcohol. The solution is neutralized with ammonia and cast on paper.
  • Image receiving material 1 g. of bismuth nitrate is shaken for 6 hours in a ball mill with 40 g. of a 1.5% solution of polyvinyl acetate in acetone and 26 g. of a 4% solution of acetylcellulose in acetone.
  • the mixture is cast on paper and dried.
  • 0.6 g. of thallium(I) chloride or 0.8 g. of mercury(II) bromide may be used with equal success in the image receiving layer.
  • EXAMPLE 9 Light sensitive material as in Example 1. Processing is carried out as described in Example 2, but the image receiving material used is ordinary writing paper. A positive cyan image of the original is obtained.
  • Image receiving material Ammonia is added to a solution of 5 g. of copperfll) chloride in 75 ml. of H until the precipitate which forms redissolves, and 30 ml. of aqueous polyvinyl alcohol are then added and the solution is cast on paper and dried.
  • EXAMPLE 11 When used in combination with other dyes, e.g. erythrosine which has its sensitivity at 540 mm., the dyes listed in the following table extend the sensitivity of the light sensitive material to the blue or red region of the spectrum.
  • other dyes e.g. erythrosine which has its sensitivity at 540 mm.
  • the filters are permeable to the following wavelengths: 350 nm., 390 nm., 405 nm., 435 nm., 480 nm., 505 nm., 515 nm., 540 nm., 550 nm., 570 nm., 590 nm., 605 nm.
  • the light sensitive material is exposed behind the interference filters to a 1000 watt iodine quartz lamp from a distance of 30 cm. for a time varying between 5 and 30 minutes according to the dye used.
  • the exposed material is then brought into contact with the image receiving layer described in Example 1 and processed in an ordinary commercial heat development apparatus.
  • sensitizer is an [N-alkylbenzothiazole1- dimethine-[1,3-dialkylthiobarbituric acid] merocyanine.
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) a heterocyclic group or (5) cycloalkyl;
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) a heterocyclic group, (5) cycloalkyl, (6) hydroxyl, (7) amino or (8) an alkoxycarbonyl group;
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) amino or (5) alkoxy; or R and R together represent the members required to complete a carbocyclic or heterocyclic ring; and
  • R hydrogen or a 4-aminophenylamino group.
  • the heavy metal compound is a silver compound which has little or no sensitivity to light under the conditions of the process.
  • the image receiving layer contains a sterically hindered phenol that accelerates the reaction in the image-receiving layer.
  • a light-sensitive photographic layer containing a sensitizer sensitizing the layer to light and an imageproducing compound which can be transferred to an image-receiving layer at temperatures of between 80 and 200 C., but which is converted by exposure into nontransferrable reaction product in the presence of the sensitizer, the improvement wherein the sensitizer has the formula:
  • R cyclo alkyl or (3) aryl;
  • R CN, COR CON(R 2 or COOR 22
  • R hydrogen, alkyl having up to 4 carbon atoms, by-
  • droxyl alkoxy having up to 4 carbon atoms or aryl
  • R a saturated or unsaturated aliphatic group or aryl
  • X oxygen or sulphur
  • n 0, 1 or 2
  • Q the members required to complete a S-membered or 6-membered heterocyclic ring.
  • sensitizer is a [N-alkylbenzothiazole1- dimethine-[1,3-dialkyl-thiobarbituric acid] merocyanine.
  • sensitizer is the following sensitizer.
  • R (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) a heterocyclic group or (5) cycloalkyl;
  • R (1) hydrogen, (2) a saturated or olefinically un- References Cited saturated aliphatic group, (3) aryl, (4) a heterocyclic UNITED STATES PATENTS group, (5) cycloalkyl, (6) hydroxyl, (7) amino or 3,094,417 7/1963 Workman 96 76 R Y y P; 3,484,23 12 1969 O 9 29

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00174929A 1970-08-27 1971-08-25 Photography dry copying process with a merocyanine dye Expired - Lifetime US3764322A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702042531 DE2042531A1 (de) 1970-08-27 1970-08-27 Photographisches Trockenkopierverfahren

Publications (1)

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US3764322A true US3764322A (en) 1973-10-09

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Family Applications (1)

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US00174929A Expired - Lifetime US3764322A (en) 1970-08-27 1971-08-25 Photography dry copying process with a merocyanine dye

Country Status (8)

Country Link
US (1) US3764322A (enrdf_load_stackoverflow)
BE (1) BE771274A (enrdf_load_stackoverflow)
CA (1) CA972610A (enrdf_load_stackoverflow)
CH (1) CH581335A5 (enrdf_load_stackoverflow)
DE (1) DE2042531A1 (enrdf_load_stackoverflow)
FR (1) FR2107075A5 (enrdf_load_stackoverflow)
GB (1) GB1339487A (enrdf_load_stackoverflow)
IT (1) IT939359B (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232115A (en) * 1979-02-22 1980-11-04 E. I. Du Pont De Nemours And Company Bleachable photographic sensitizing dyes
WO1998051312A1 (en) * 1997-05-16 1998-11-19 Eli Lilly And Company Thiadiazinyl corticotropin-releasing factor binding protein ligand inhibitors
US20040067537A1 (en) * 2000-07-13 2004-04-08 Hahn Klaus M. Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US20050287518A1 (en) * 2000-07-13 2005-12-29 The Scripps Research Institute Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US20060235061A1 (en) * 2002-06-21 2006-10-19 Qlt,Inc. Methods of using benzothiophenone derivatives to treat cancer or inflammation
JP2008248211A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp アゾ色素およびアゾ化合物
CN113929656A (zh) * 2021-09-28 2022-01-14 西安交通大学 一种基于茚酮烯的发光材料及其制备方法和应用

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232115A (en) * 1979-02-22 1980-11-04 E. I. Du Pont De Nemours And Company Bleachable photographic sensitizing dyes
WO1998051312A1 (en) * 1997-05-16 1998-11-19 Eli Lilly And Company Thiadiazinyl corticotropin-releasing factor binding protein ligand inhibitors
US20040067537A1 (en) * 2000-07-13 2004-04-08 Hahn Klaus M. Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US20050287518A1 (en) * 2000-07-13 2005-12-29 The Scripps Research Institute Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US7176037B2 (en) 2000-07-13 2007-02-13 The Scripps Research Institute Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US7662644B2 (en) 2000-07-13 2010-02-16 The Scripps Research Institute Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US7745377B2 (en) 2000-07-13 2010-06-29 The Scripps Research Institute Labeled peptides, proteins and antibodies and processes and intermediates useful for their preparation
US20060235061A1 (en) * 2002-06-21 2006-10-19 Qlt,Inc. Methods of using benzothiophenone derivatives to treat cancer or inflammation
JP2008248211A (ja) * 2007-03-30 2008-10-16 Fujifilm Corp アゾ色素およびアゾ化合物
CN113929656A (zh) * 2021-09-28 2022-01-14 西安交通大学 一种基于茚酮烯的发光材料及其制备方法和应用

Also Published As

Publication number Publication date
BE771274A (nl) 1972-02-14
GB1339487A (en) 1973-12-05
DE2042531A1 (de) 1972-03-09
FR2107075A5 (enrdf_load_stackoverflow) 1972-05-05
CH581335A5 (enrdf_load_stackoverflow) 1976-10-29
CA972610A (en) 1975-08-12
IT939359B (it) 1973-02-10

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